CN102083526A - Process for upgrading a carbonaceous material using microchannel process technology - Google Patents

Process for upgrading a carbonaceous material using microchannel process technology Download PDF

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Publication number
CN102083526A
CN102083526A CN2009801213267A CN200980121326A CN102083526A CN 102083526 A CN102083526 A CN 102083526A CN 2009801213267 A CN2009801213267 A CN 2009801213267A CN 200980121326 A CN200980121326 A CN 200980121326A CN 102083526 A CN102083526 A CN 102083526A
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China
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catalyst
process microchannel
micro passage
aforementioned
passage reaction
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韦恩·W.·西蒙斯
罗伯特·德韦恩·利特
安娜·利·通科维奇
劳拉·J.·席尔瓦
丹尼尔·弗朗西斯·瑞安
布鲁斯·施坦格兰
约翰·布罗菲
杰弗里·S.·麦克丹尼尔
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Velocys Inc
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Velocys Inc
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
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    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Abstract

This invention relates to a process for converting a carbonaceous material to a desired product comprising one or more hydrocarbons or one or more alcohols, the process comprising: (A) gasifying the carbonaceous material at a temperature in excess of about 700 DEG C to form synthesis gas; and (B) flowing the synthesis gas in a microchannel reactor in contact with a catalyst to convert the synthesis gas to the desired product.

Description

Use the method for microchannel process technology upgrading carbonaceous material
According to 35 U.S.C. § 119 (e), the application number of the application's request submission on April 9th, 2008 is 61/043, the application number that 465 U.S. Provisional Patent Application, on October 10th, 2008 submit to is 61/104, the application number of submitting in 432 U.S. Provisional Patent Application and on February 13rd, 2009 is the priority of 61/152,645 U.S. Provisional Patent Application.These contents in first to file are incorporated present patent application in the quoted passage mode.
Technical field
The present invention relates to a kind of method of using microchannel process technology upgrading carbonaceous material.Described method can be used for carbonaceous material (for example living beings, solid waste etc.) is converted into one or more hydrocarbon or alcohol.Described hydrocarbon or alcohol can be used as synthetic fuel.
Background technology
Tens gallons of petroleum based fuels of the annual use of US military.It is expensive and consuming time that these fuel are delivered to remote military base, and such fuel preferred object of attacker normally.Therefore, problem provides a kind of more cheap and safer fuels sources.
Summary of the invention
The invention provides solution of the above problems.The present invention relates to that a kind of for example living beings, solid waste etc. are converted into the method for the hydrocarbon that can be used as synthetic fuel (for example motor vehicle fuel, diesel oil and aviation fuel etc.) and alcohol with carbonaceous material.The micro passage reaction that the inventive method has been used compact conformation and has been easy to transport.Therefore, the inventive method is applicable to can easily being transported to for example device in military base etc. of remote place.By the inventive method, can will be converted into fuel, for example motor vehicle fuel, diesel oil, aviation fuel etc. at such discarded object that the military base produced.For example, adopt the inventive method can produce the about 500 barrels of synthetic fuels of about 50-every day in such military base.The inventive method also is suitable for more massive application, and the solid waste of wherein carbonaceous material for example being lived is converted into for example synthetic fuel of useful product.
The present invention relates to a kind of carbonaceous material is converted into the method that contains one or more hydrocarbon or one or more pure target products, described method comprises: (A) under at least about 700 ℃ temperature the described carbonaceous material of gasification to form synthesis gas; And (B) make described synthetic air go into micro passage reaction to contact with catalyst so that described synthesis gas is converted into target product.Described product has various uses, comprises as synthetic fuel.
Description of drawings
In the accompanying drawings, identical parts have identical Reference numeral with feature.Most figure wherein are schematic diagrames, can draw in proportion.
Fig. 1 is the flow chart of the inventive method of representing with concrete form.Described method comprises that the micro passage reaction that uses gasification furnace and Fischer-Tropsch (FT) or generate alcohol is converted into one or more hydrocarbon or one or more alcohol with carbonaceous material.In described gasification furnace, described carbonaceous material is converted into synthesis gas.In described micro passage reaction, described synthesis gas is converted into one or more hydrocarbon or alcohol.
Except the steam that in described micro passage reaction, is used as heat-exchange fluid also as the gasifying agent in the described gasification furnace, Fig. 2 is the flow chart of the method identical with the method for example shown in Fig. 1.
Use the nitrogen separation device upstream that is included in described gasification furnace except the method for example shown in Fig. 3, and Fig. 3 is the flow chart of the method identical with the method for example shown in Fig. 1.In described nitrogen separation device, make nitrogen and air separation.With the oxygen that keeps as the gasifying agent in the described gasification furnace.
Except the method for example shown in Fig. 4 has been used the pyrolysis reactor, Fig. 4 is the flow chart with the identical method of method of example shown in Fig. 1.In described pyrolysis reactor, described carbonaceous material is converted into pyrolysis oil.With described pyrolysis oil as the carbon raw material in the described gasification furnace.
Except make liquid hydrocarbon for example tar separate with the synthesis gas that flows out described gasification furnace and be recycled to the described pyrolysis reactor, Fig. 5 is the flow chart of the method identical with the method for example shown in Fig. 4.
Fig. 6 has been to use the flow chart of the method for gasification furnace routine shown in Fig. 1 and micro passage reaction and steam methane reforming (SMR) micro passage reaction.The tail gas that described SMR micro passage reaction is used for flowing out from this micro passage reaction is converted into the synthesis gas that is recovered to this micro passage reaction.
Except the synthesis gas that makes carbon dioxide and flow out gasification furnace separated, Fig. 7 was the flow chart of the method identical with the method for example shown in Fig. 6.Poor (lean) carbon dioxide synthesis gas that obtains is flowed in the described micro passage reaction.
Except the carbon dioxide that separates with the synthesis gas that flows out described gasification furnace flows into the SMR micro passage reaction and mixes with tail gas from described micro passage reaction in this reactor and be converted into the synthesis gas, Fig. 8 is the flow chart of the method identical with method routine shown in Fig. 7.
Except the product that flows out the Fischer-Tropsch micro passage reaction is taken place in the hydrocracking micro passage reaction the hydrocracking reaction, Fig. 8 A is to be the flow chart of the identical method of the method for Fischer-Tropsch micro passage reaction with wherein said micro passage reaction routine shown in Fig. 1.
Fig. 9 and Figure 10 are the organigrams that is used to hold a plurality of Fischer-Tropsch or generates the container of pure micro passage reaction or a plurality of SMR micro passage reaction or a plurality of hydrocracking micro passage reactions.In Fig. 9 and Figure 10, show five Fischer-Tropsch or generate pure micro passage reaction, five SMR micro passage reactions or five hydrocracking micro passage reactions.
Figure 11-the 14th can be used on described Fischer-Tropsch or generates the organigram of the repetitive in the micro passage reaction of alcohol.Each repetitive shown in Figure 11-14 in the repetitive of example comprises Fischer-Tropsch with the conversion zone that contains catalyst and adjacent hot switching path or the process microchannel that generates alcohol.Make the heat-exchange fluid that in the hot switching path of example shown in Figure 11, flows according to flowing with described Fischer-Tropsch or the direction that generates the mobile cross-flow of the process fluid in the process microchannel of alcohol.Can make the heat-exchange fluid that in the hot switching path of example shown in Figure 12, flows according to described Fischer-Tropsch or generate alcohol process microchannel process fluid flow and the direction of stream or adverse current flows.The hot switching path of example shown in Figure 13 and Figure 14 provide heat-exchange fluid according to described Fischer-Tropsch or generate the flowing of direction of the mobile cross-flow of the process fluid in the process microchannel of alcohol.The hot switching path of example shown in Figure 13 and Figure 14 provides the heat exchange zone of the part of the length that only covers described Fischer-Tropsch or generate the conversion zone in the pure process microchannel.By the quantity of the hot switching path that contacts with the different piece thermodynamics of described process microchannel of control, adopt each scheme in the described embodiment that the heat exchange characteristics of adjustment can be provided.By the heat exchange characteristics of these adjustment, the more cooling duct of other parts than described process microchannel can be set in some part of described process microchannel.For example, can or be provided with than more cooling duct, the downstream part of described conversion zone near the porch of described conversion zone.By controlling the flow velocity of the heat-exchange fluid in the described hot switching path, can regulate heat exchange characteristics.For example, with the hot switching path of the inlet thermodynamics of described conversion zone contact in heat-exchange fluid can use relative high flow rate, be combined in the relative low flow velocity of the heat-exchange fluid in the hot switching path with the downstream part thermodynamics contact of described conversion zone.
Figure 15-the 20th can be used for described SMR process microchannel, burning gallery or Fischer-Tropsch or generate the catalyst of pure process microchannel or the organigram of catalyst carrier.The catalyst of example is the form of granular solids bed shown in Figure 15.The catalyst of example shown in Figure 16 has (flow-by) design of flowing through.The catalyst of example has and flows through (flow-through) structure shown in Figure 17.Figure 18-the 20th can be used to support the organigram of the fin component of described catalyst.
Figure 21-the 25th can be used for the organigram of the microchannel repetitive of described SMR micro passage reaction.In the described repetitive each comprises burning gallery and one or more SMR process microchannel.The burning gallery of example comprises and is used to make oxygen or oxygen source to flow into the interpolation passage stage by stage of described burning gallery shown in Figure 21-25.Figure 21 shows the inversion U-type SMR process microchannel adjacent with M-type burning gallery.Figure 22 shows the single SMR process microchannel adjacent with M-type burning gallery.Figure 23 shows two SMR process microchannel and M-type burning gallery, one of them SMR process microchannel is adjacent with described M-type burning gallery, and another SMR process microchannel is adjacent with first SMR process microchannel, and two SMR process microchannel all contact with described burning gallery thermodynamics.Figure 24 shows single burning gallery, be arranged on the interpolation passage stage by stage of a side of described burning gallery and the SMR process channel that is arranged on the opposite side of described burning gallery.Except the SMR process microchannel of repetitive of example shown in Figure 25 is the shape of inverted U-type microchannel, Figure 25 shows and the similar repetitive of repetitive of example shown in Figure 24.For purpose clearly, the passage that is separated from each other has been shown, but in fact described passage is to be layering or closely to arrange side by side, does not have the space therebetween in Figure 21-25.Described passage is enjoyed common wall in the punishment of passage contact-making surface.
Figure 26 and 27 is the organigrams that can be used in the employed Fischer-Tropsch of the inventive method or generate the surface characteristics in the passage that uses in pure micro passage reaction and/or the SMR micro passage reaction.
Figure 28 is the flow chart of the method described in the embodiment 1.
Figure 29 is the schematic diagram of the micro passage reaction described in the embodiment 2.
Figure 30 is the schematic diagram that is used to make the waveform (waveform) of the micro passage reaction described in the embodiment 2.
The specific embodiment
All scopes that disclose in the application's specification and claims and ratio threshold can make up in mode arbitrarily.Be understandable that unless otherwise prescribed, the semanteme of " (a) ", " (an) " and/or " described " can comprise one or more than one, and the semanteme of the title of representing with singulative can also comprise the plural form of this title.All combinations that define in claims can be made up in mode arbitrarily.
Term " microchannel " can refer to a kind of passage with at least one inside dimension, on the height of this inside dimension or the width to about 10 millimeters (mm), go up in one embodiment to about 5mm, go up in one embodiment, and go up in one embodiment to about 1mm to about 2mm.Described microchannel can comprise at least one inlet and at least one outlet, and wherein said at least one inlet is what to separate with described at least one outlet.A kind of hole may be not only in described microchannel.The passage that passes zeolite or mesoporous material can be not only in described microchannel.The length of described microchannel can be the height or width at least about twice, be in one embodiment the height or width at least about five times, and be in one embodiment the height or width at least about ten times.The internal height of described microchannel or width can be in the scopes of the about 10mm of about 0.05-, in one embodiment in the scope of the about 5mm of about 0.05-, in one embodiment in the scope of the about 2mm of about 0.05-, in one embodiment in the scope of the about 1.5mm of about 0.05-, in one embodiment in the scope of the about 1mm of about 0.05-, in one embodiment in the scope of the about 0.75mm of about 0.05-, and in one embodiment in the scope of the about 0.5mm of about 0.05-.Height or other inside dimensions of width can be arbitrary dimensions, for example, go up to about 3 meters about 3 meters of about in one embodiment 0.01-, and about 3 meters of about in one embodiment 0.1-.The length of described microchannel can be arbitrary dimension, for example, goes up to about 10 meters, about 10 meters of about in one embodiment 0.1-, about 10 meters of about in one embodiment 0.2-, about 6 meters of about in one embodiment 0.2-, and about 3 meters of about in one embodiment 0.2-.Described microchannel can have the cross section of arbitrary shape, for example, and square, rectangle, circle, semicircle, irregular quadrilateral etc.The shape of the cross section of described microchannel and/or size can vary along its length.For example, height or width can be gradient to relatively little size along the length of described microchannel from big relatively size, and vice versa.
Term " micro passage reaction " can refer to a kind of one or more devices that can carry out the process microchannel of reaction method therein that comprise.Described method can be Fischer-Tropsch or reaction method or the SMR reaction method that generates alcohol.When using two or more process microchannel, described process microchannel can be operated in parallel.Described micro passage reaction can comprise and is used to the top cover or the manifold group that make fluid flow into one or more process microchannel, and make fluid flow out the base or the manifold group of one or more process microchannel.Described micro passage reaction can comprise the hot switching path that one or more and one or more process microchannel are adjacent and/or thermodynamics contacts.Described hot switching path is used to heat and/or cools off fluid in the described process microchannel.When described hot switching path is used in the SMR micro passage reaction, can be burning gallery.Described hot switching path and/or burning gallery can be the microchannels.Described micro passage reaction can comprise and is used to the top cover or the manifold group that make heat-exchange fluid flow into described hot switching path, and make heat-exchange fluid flow out the base or the manifold group of described hot switching path.
Term " process microchannel " can refer to a kind of microchannel of manner of execution therein.Described method can fingering row Fischer-Tropsch (FT) or pure reaction or the SMR reaction of generation.
The term " volume " of the volume in the relevant process microchannel can comprise whole volumes that process fluid may flow through or flow through in process microchannel.This volume can comprise the volume in the surface characteristics, and this surface characteristics can be arranged in the described process microchannel and be applicable to that fluid is to flow through mode or the flowing of the mode of flowing through.
When passage of expression during with respect to the position of another passage, term " adjacent " can mean direct neighbor, so that one faces the wall and meditates or the multiaspect wall is separated described two passages.In one embodiment, described two passages can have a common wall.The thickness of described common wall can be different.But " adjacent " passage can not be by intervenient passage separately, and described intervenient passage may hinder the heat exchange between the described passage.A passage can be adjacent with another passage, and is only overlapping with the part of the size of described another passage.For example, one or more adjacent hot switching paths can are longer than or extend beyond to a process microchannel.
Term " thermodynamics contact " can refer to two main bodys, two passages for example, physics contact or adjacent one another are each other, perhaps not physics contact or not adjacent to each other each other, but still heat-shift each other.A main body that contacts with another main body thermodynamics can heat or cool off other main body.
Term " fluid " can refer to gas, liquid, gas and mixtures of liquids or contain gas or liquid, drop and/or the bubble of dispersing solid.Described drop and/or bubble can have unconventional or conventional shape and can have similar or different sizes.
Term " gas (gas) " or " steam (vapor) " can have same implication and exchange sometimes and use.
Term " time of staying " or " mean residence time " can refer to that fluid flows the internal volume in this occupied space divided by the average external volume flow velocity that flows at fluid under the employed temperature and pressure in the space of microchannel in described space.
Term " upstream " and " downstream " can refer in passage (for example process microchannel) or in process chart, with respect to the position of the fluid flow direction in described passage or the process chart.For example, the position in passage or in the process chart, when the part of a fluid streams that flows to this position did not also arrive at this position, this position was that part of downstream of described fluid.Position in described passage or process chart, when the part of a fluid streams by and when leaving this position, this position is that part of upstream of described fluid.Term " upstream " and " downstream " the definiteness upright position of differing is because passage used in the present invention can be level, vertically or at a certain angle tilt to place.
Term " clamping plate " can refer to smooth or smooth substantially thin slice or flat board.The thickness of described clamping plate can be the minimum dimension of described clamping plate and could be up to about 4mm, in one embodiment in the scope of the about 2mm of about 0.05-, in one embodiment in the scope of the about 1mm of about 0.05-, and in one embodiment in the scope of the about 0.5mm of about 0.05-.Described clamping plate can have length and width arbitrarily.
Term " surface characteristics " can refer in passage to upset depression on the conduit wall that flows and/or the projection on the conduit wall.The example of operable surface characteristics design has been shown in Figure 26 and 27.Described surface characteristics can be the rectangle (angled rectangles) of circle, sphere, truncated cone-shaped, oblong (oblongs), square, rectangle, band angle, to hook-shaped (checks), pointed shape (chevrons), blade shaped (vanes), airfoil (air foils), waveform or the like, and the combination of above-mentioned two or more shapes.Described surface characteristics can comprise time feature, the main wall of wherein said surface characteristics further comprises littler surface characteristics, and described littler surface characteristics can be groove shape, corrugated, zigzag, hole shape, burr shape (burrs), to hook-shaped, scalloped shaped (scallops) or the like.Described surface characteristics can have the degree of depth, width, and for the non-circular surfaces feature, can have length.The disclosed method according to the present invention, described surface characteristics are formed at the top or the inside of one or more surfaces inwall in the inwall of employed process microchannel, hot switching path and/or burning gallery.Described surface characteristics can refer to passive-type (passive) surface characteristics or passive-type composite character.Described surface characteristics can be used for Interference Flow (for example disrupt laminar streamline), and generation and the angled advection (advective flow) of overall flow direction.
Term " hot switching path " can refer to wherein contain the passage that heat is provided and/or absorbs the heat-exchange fluid of heat.Described hot switching path can absorb heat from the passage that adjacency channel (for example process microchannel) and/or one or more and described hot switching path thermodynamics contact, or heat is provided to such passage.Described hot switching path can absorb heat or provide heat to such passage from adjacent one another are but not adjacent with described hot switching path passage.In one embodiment, one, two, three or more passages can be adjacent one another are and be arranged between two hot switching paths.
Term " hot conductive walls " can refer to the common wall between process microchannel and adjacent hot switching path, and wherein heat passes described common wall from a passage and is passed to another passage.
Term " heat-exchange fluid " can refer to a kind of fluid that discharges and/or absorb heat.
Term " waveform " can refer to change into from the object on plane the Heat Conduction Material that links up of three-dimensional object.Described waveform can be used for forming one or more microchannels.Described waveform can comprise can be clipped in two relative plane laminas or the right angle corrugated insertion (insert) between the flat board.Described right angle corrugated is inserted the limit that can have rounding.In such method, three sides that can be by described waveform and limit one or more microchannels by described plane lamina or one of dull and stereotyped four edges.Described waveform can be made by any one of Heat Conduction Material that described micro passage reaction is made in disclosed being used for of the present invention.Such material can comprise copper, aluminium, stainless steel or the like.The thermal conductivity of described waveform can be about 1W/m-K or higher.
Term " overall flow direction " can refer to that fluid can be along the mobile vector of open approach in passage.
Term " overall flow zone " can refer to the open area in the microchannel.A coherent overall flow zone can be so that fluid flows through the microchannel fast and does not have obvious pressure drop.In one embodiment, flowing in described overall flow zone can be laminar flow.The overall flow zone can comprise the internal volume of microchannel and/or cross-sectional area at least about 5%, be about 5%-about 100% in one embodiment, be about 5%-about 99% in one embodiment, be about 5%-about 95% in one embodiment, about 90% for about 5%-in one embodiment, and be the internal volume of microchannel and/or about 30%-about 80% of cross-sectional area in one embodiment.
Term " open channel " or " passage of flowing through " or " open approach " can refer to passage (for example microchannel), it has the space at least about 0.01mm (gap) of passing whole passage extension, flows without any the obstacle influence so that fluid can flow through described passage.Described space can extend to about 10mm.
" cross-sectional area " of term passage (for example process microchannel) can refer to the area that the direction perpendicular to described inner fluid passage overall flow records, and can comprise that described passage contains the surface characteristics that may exist arbitrarily but do not comprise all areas of described conduit wall.For for the passage of curved in length, described cross-sectional area can be the area that records perpendicular to the direction of overall flow along straight line in reconnaissance place, and described straight line parallel is in described passage length and be positioned at the center (pressing area) of described passage.The size of height and width can be recorded by the distance of conduit wall to the conduit wall on its opposite.The use of the coating of described wall surface can not change these sizes.Described size can be a mean value of considering the variation that is caused by surface characteristics, surface roughness etc.
" open cross sectional " of term passage (for example process microchannel) can refer to that perpendicular to record described bulk fluid is flowed of the direction that bulk fluid in the described passage flows be the area of opening.Described open cross sectional can not comprise surface characteristics that the inner compartment thing for example may exist or the like.
The term " superficial velocity " that is used for the speed that fluid flows in passage can refer to the speed that produced divided by the cross-sectional area of described passage by the volume flow rate of described fluid under the inlet temperature of described passage and pressure.
Term " free flow velocity " can refer to that in passage the fluid that the flows speed along the sidewall of described passage to sufficiently long distance is so that described speed is in maximum.If there is not applicable boundary layer separation condition (slip boundary condition), the flow velocity of the side-walls of fluid in passage is zero, and increase reaches stationary value until this flow velocity but this flow velocity is along with the distance increase of sidewall.This stationary value is described " free flow velocity ".
In the present invention, term " process fluid " can be used for referring to reactant, product and any diluent or other fluids that can flow in process microchannel.
Term " conversion zone " can refer to the space in the microchannel, and the chemical conversion of chemical reaction or at least a material wherein takes place.Described conversion zone can comprise one or more catalyst.
Term " productive rate " can refer to leave the molal quantity of product of micro passage reaction divided by the molal quantity of the reactant that enters micro passage reaction.
Term " circulation " can refer to an one way by the reactant of micro passage reaction.
Term " grading catalyst " can refer to have the catalyst of the catalytic activity of one or more gradients.Described grading catalyst can have the concentration of variation or the catalytically-active metals of surface area.Described grading catalyst can have the catalytic activity site conversion rates of variation.Described grading catalyst can have physical property and/or as the function of distance and the form that changes.For example, it is low relatively reactive metal concentration that described grading catalyst can have in the porch of process microchannel, and rises to higher concentration in the exit near described process microchannel, and perhaps vice versa; Perhaps the closer to the center (being mid point) of process microchannel, the concentration of catalytically-active metals is low more, and the closer to the process microchannel wall, the concentration of catalytically-active metals is high more, and vice versa or the like.The thermal conductivity from position to another position can be different in process microchannel for grading catalyst.Can perhaps pass through to change the surface area of described carrier by the size of change catalytically-active metals site on the carrier that the surface of stability amasss, for example by change bearer type or particle size, and the surface area of change grading catalyst.Grading catalyst can have porous carrier, and the surface area of wherein said carrier may be higher or lower in the different piece of described process microchannel with the ratio of volume, the everywhere of using the identical described carrier of catalyst-coated then.Can use the combination of two or more previous embodiments.Described grading catalyst can have single catalyst component or multiple catalyst component (for example bimetallic or trimetallic catalyst).As the function of distance, described grading catalyst can change its character and/or composition from a position to another position gradually in process microchannel.Described grading catalyst can include the limit particle, and described particle all has catalytically-active metals in each particle " eggshell " formula distributes.Described grading catalyst can be along the length of process microchannel axially or transversely classification.Described grading catalyst can have the number in different catalyst components, different useful load and/or active catalytic site that can be from a position to another change in location in process microchannel.Can change the number in catalytic activity site by the porosity that changes described catalyst structure.This can realize by the catalysis material that uses the different amounts of cover technology (washcoating process) deposition.An example is the thickness that uses different porous catalysts along the length of described process microchannel, on the ground that needs greater activity thicker loose structure can be set thus.For the thickness of fixing or variable porous catalyst, can also the adjustment apertures rate.First hole dimension can be used with open area that is used to flow or space adjacent, and at least one second hole dimension can be used with described process microchannel wall adjacent.
Biomaterial that lives and just dead biomaterial that term " living beings " can refer to act as a fuel and use.The term living beings can refer to the plant as the bio-fuel plantation.The term living beings can comprise plant or the animal body that is used to obtain fiber, chemical substance or heat.Living beings can comprise the biodegradable discarded object of the burning that can act as a fuel.Living beings can comprise plant for example switchgrass (swtichgrass), hemp, corn, poplar, willow, sugarcane, oil palm or the like.
Term " coke " can refer to from carbonaceous material to extract out or to discharge the solid material of the remnants behind the gas.Coke can be formed in the combustion process of carbonaceous material.
Term " tar " can refer to the thickness black liquor that extracts from the destructive distillation of carbonaceous material.
Term " ash content " can refer to the remaining solid residue in carbonaceous material burning back.
Term " chain growth " can refer to because the growth of the molecule that reaction produces, at molecule described in this reaction along with increasing with the addition (for example addition of methylene group and hydrocarbon chain in Fischer-Tropsch synthesizes) of recruit's structure.
Term " hydrocarbon " can refer to pure hydrocarbon compound; Be aliphatic compound (for example alkane, alkene or alkynes), alicyclic compound (for example cycloalkane, cycloolefin), aromatic compound, fat-and alicyclic ring-substituted aromatic compound, fragrance replace aliphatic compound, fragrance replaces alicyclic compound or the like.Example can comprise methane, ethane, propane, cyclohexane, ethyl cyclohexane, toluene, ethylbenzene or the like.Term " hydrocarbon " can refer to the hydrocarbon compound that replaces; Promptly contain the substituent hydrocarbon compound of nonhydrocarbon.The substituent example of described nonhydrocarbon can comprise hydroxyl, amide groups, nitro or the like.Term " hydrocarbon " can refer to the hydrocarbon compound that hetero atom replaces; The hydrocarbon compound that promptly in chain or ring, except that containing carbon atom, also contains non-carbon atom.Described hetero atom can comprise for example nitrogen, oxygen, sulphur or the like.For each non-hydrocarbon substituent or hetero atom, described hydrocarbon compound can comprise about 10 or more a plurality of carbon atom.
Term " hydrocarbon of higher molecular weight " can refer to a kind of hydrocarbon that contains 2 or more a plurality of carbon atoms, contain 3 or more a plurality of carbon atom in one embodiment, contain 4 or more a plurality of carbon atom in one embodiment, contain 5 or more a plurality of carbon atom in one embodiment, and contain 6 or more a plurality of carbon atom in one embodiment.The hydrocarbon of described higher molecular weight can contain to about 100 carbon atoms, contain in one embodiment to about 90 carbon atoms, contain in one embodiment to about 80 carbon atoms, contain in one embodiment to about 70 carbon atoms, contain in one embodiment to about 60 carbon atoms, contain in one embodiment to about 50 carbon atoms, contain in one embodiment to about 40 carbon atoms, and contain in one embodiment to about 30 carbon atoms.The hydrocarbon of described higher molecular weight can be an aliphatic hydrocarbon.Example can comprise ethane, propane, butane, pentane, hexane, octane, decane, dodecane or the like.
Term " Fischer-Tropsch " or " FT " can refer to the chemical reaction that is expressed from the next:
nCO+2nH 2→(CH 2) n+nH 2O
This reaction is the exothermic reaction that can carry out in the presence of Fischer-Tropsch catalyst.N can be an Any Digit, for example from 1 to about 10, be 2 to about 10 in one embodiment, and be 2 to about 8 in one embodiment.
Term " Fischer-Tropsch product " or " FT product " can refer to the hydrocarbon products that made by fischer-tropsch process.The boiling point of described FT product under normal pressure can be equal to or greater than about 30 ℃.
Term " FT tail gas " can refer to the gaseous products that made by fischer-tropsch process, and the boiling point of described tail gas under normal pressure can be lower than about 30 ℃.
Term " generate alcohol reaction " can refer to the synthetic reaction that is expressed from the next:
nCO+H 2→C nH 2n+1OH+(n-1)H 2O
This reaction is the exothermic reaction that can carry out in the presence of the catalyst that generates alcohol.N can be an Any Digit, for example from 1 to about 10, be 2 to about 10 in one embodiment, and be 2 to about 8 in one embodiment.
Term " Co useful load " can refer to the gross weight of the weight of Co in the catalyst divided by described catalyst, and the gross weight of described catalyst is the gross weight that described Co adds any synergistic catalyst or promoter and any carrier.If described catalyst loading is on the engineered vector structure, for example foams, felt rug body, agglomerate body or fin can not comprise the weight of this project carrier structure body in the then described calculating.Similarly, if described catalyst attached on the conduit wall, can not comprise the weight of described conduit wall in the then described calculating.
Term " steam methane reforming " or " SMR " can refer to reaction:
H 2O+CH 4→CO+3H 2
This reaction is absorbed heat, and can carry out in the presence of the SMR catalyst.Described CO and H 2Product mixtures can refer to synthesis gas (synthesis gas) or synthesis gas (syn gas).Can pass through fuel (H for example 2) provide with the combustion reaction of the mixture of oxygen or oxygen source (for example air or oxygen-enriched air) and to implement this and react needed heat.Described combustion reaction is heat release, and can carry out in the presence of combustion catalyst.
Term " hydrocracking technology " refers to that the wherein one or more C-C bond fissions in hydrocarbon reactants generate the method for the product that contains two or more hydrocarbon products lower than the molecular weight of described hydrocarbon reactants.For example, C 12Alkane can be converted into C 7Alkane and C 5Alkane.
Term " mm " can refer to millimeter.Term " nm " can refer to nanometer.Term " ms " can refer to millisecond.Term " μ s " can refer to microsecond.Term " μ m " can refer to micron (micron) or micron (micrometer).Term " micron (micron) " has identical implication and can exchange use with " micron (micrometer) ".
Unless otherwise prescribed, all pressure are represented with absolute pressure.
The carbonaceous material that can be used for the inventive method can comprise arbitrarily and can be gasified to produce the organic material or the carbonaceous material of synthesis gas.Described carbonaceous material can comprise food source for example corn, soybean or the like.Described carbonaceous material can comprise non-food source.Described non-food source can refer to second generation bio-fuel.Described non-food source can comprise any carbonaceous material that is not used as food usually.The example of operable non-food source can comprise coal (for example low-grade coal, fat coal or the like), oil (for example crude oil, heavy oil, tar sand oil or the like), living beings, solid waste or the mixture of two or more wherein.Described non-food carbonaceous material can comprise life solid waste (MSW), bazardous waste, garbage derivatived fuel (RDF), tire, petroleum coke, rubbish (trash), refuse (garbage), living beings from decomposing system (digester), sewage sludge, animal excrements (chicken manure for example, the turkey excrement, cow dung, horsehit and other animal excrements), agricultural wastes, maize straw, switchgrass, timber, wood chip (wood cuttings), grass bits (grass cllipings), the building waste material, plastic material (for example plastic refuse), the ginning discarded object, landfill gas, natural gas or the like.Described non-food carbonaceous material can comprise polyethylene or polyvinyl chloride.Can use the mixture of above-mentioned two or more materials.
Described carbonaceous material can have the shape of big relatively solids and in step (A) before, can be ground into less object by for example auger (auger) solids that these are big relatively.
Described carbonaceous material can comprise water, and at least one embodiment of the present invention, it may be favourable removing part or all of water before in the gasification step (A) of the inventive method.This can realize by conventional dry technology.
Term " synthesis gas " refers to contain CO and H 2Admixture of gas.Synthesis gas (synthesis gas) refers to synthesis gas (syngas) sometimes.The synthesis gas that forms in the gasification step (A) of the inventive method can comprise CO and the H that contains different amounts 2Admixture of gas.In at least one embodiment of the inventive method, in step (B), use H 2With the mol ratio of CO may scope for about 0.5-about 4 in, in one embodiment in the scope of about 1-about 3, in one embodiment in the scope of about 1.5-about 2.5 and be that synthesis gas in the scope of about 1.8-about 2.2 is favourable in one embodiment.If the H that in step (A), produces 2Quantity not sufficient to satisfy H defined above 2With the mol ratio of CO, then can in described synthesis gas, add the H of additional quantity before in the step (B) of the inventive method 2Described synthesis gas can also comprise the CO of different amounts 2With water and granular solids and other impurity.In the step (B) of carrying out the inventive method before, can be with described CO 2, water, granular solids separates with described synthesis gas with other impurity or separate to small part.
In exemplary embodiment of the subject disclosure, will at first the inventive method be described in conjunction with Fig. 1-8.With reference to figure 1, method 100 has been used gasification furnace 110 and micro passage reaction 200.When being used for that synthesis gas is converted into one or more hydrocarbon, micro passage reaction 200 can refer to the Fischer-Tropsch micro passage reaction.When micro passage reaction 200 is used for synthesis gas is converted into the micro passage reaction that one or more alcohol the time can refer to generate alcohol.In operating process, described carbonaceous material is entered in the gasification furnace 110 via circuit 112.Gasifying agent (for example steam, oxygen and/or air) is entered in the gasification furnace 110 via circuit 114.In gasification furnace 110, heat described carbonaceous material and described gasifying agent and make its generating gasification reaction to generate synthesis gas.Described synthesis gas is flowed into the micro passage reaction 200 from gasification furnace 110 via circuit 116.The synthesis gas that flows out gasification furnace 110 may be in the temperature of rising, and for example more than 700 ℃, therefore, the temperature that reduced synthesis gas before described synthesis gas enters micro passage reaction 200 may be favourable.Use one or more heat exchangers in the circuit between gasification furnace 110 and micro passage reaction 200 as discussed below, described temperature classes is similar to the operating temperature of wishing in the micro passage reaction 200.Such heat exchanger can be a micro channel heat exchanger.The synthesis gas that flows out gasification furnace 110 may contain the water of undesirable amount, granular solids, impurity (for example sulphur, halogen, selenium, phosphorus, arsenic, nitrogen, carbon dioxide or the like) or the like.Can in the circuit between gasification furnace 110 and the micro passage reaction 200, use one or more solution-air adsorbent equipments (these devices can adopt one or more ionic liquid adsorbents), alternating temperature absorption (TSA) device, transformation absorption (PSA) to install, contain the concentration that the micro-channel device of layers of nanofibers or nano composite membrane, cyclone separator, condenser or the like reduce these materials.In micro passage reaction 200, make described synthesis gas flow through one or more process microchannel and contact with catalyst to generate target product.Described catalyst can be Fischer-Tropsch catalyst and can comprise one or more hydrocarbon by contact the product that generates with described Fischer-Tropsch catalyst.Replacedly, described catalyst can be to generate the catalyst of alcohol and can comprise one or more alcohol by contact the product that generates with described catalyst.These reactions all are exothermic reaction.Can use the heat-exchange fluid that flows through micro passage reaction 200 shown in arrow 204 and 206 to control these reactions.In one embodiment, described heat-exchange fluid comprises steam.Make the product of acquisition flow out micro passage reaction 200 via circuit 202.
Also can be except the steam that in micro passage reaction 200, is used as heat-exchange fluid as the gasifying agent in the gasification furnace 100, the method 100A of example shown in Fig. 2 is identical with the method 100 of example shown in Fig. 1.Make described steam flow into gasification furnace 110 via circuit 206 from micro passage reaction 200.In gasification furnace 110, in the gasification of described carbonaceous material, steam is used as gasifying agent.
Except method 100B comprises nitrogen separation device 300, identical with the method 100 of example shown in Fig. 1 at the method 100B of example shown in Fig. 3.Described nitrogen separation device 300 can comprise the device of any suitable separation of nitrogen and air.For example, nitrogen separation device 300 can comprise ionic liquid separator, alternating temperature absorption (TSA) device or transformation absorption (PSA) device.In operating process, make air enter nitrogen separation device 300 via circuit 302, in this separator, make the separation process of described air experience nitrogen and air separation.Thereby form the oxygen of oxygen-enriched air or purifying.Make described nitrogen flow out nitrogen separation device 300 via circuit 304.Make the oxygen of described oxygen-enriched air or purifying flow into gasification furnace 110 from nitrogen separation device 300 via circuit 114.In gasification furnace 110, the oxygen of described oxygen-enriched air or purifying is used as gasifying agent.Make the reaction of described carbonaceous material and described gasifying agent generating gasification to generate synthesis gas.Make described synthesis gas flow into micro passage reaction 200 from gasification furnace 110, described synthesis gas is reacted to generate aforesaid one or more hydrocarbon or one or more alcohol via circuit 116.
Except method 100C adopts pyrolysis reactor 400, identical with the method 100 of example shown in Fig. 1 at the method 100C of example shown in Fig. 4.In operating process, make described carbonaceous material enter pyrolysis reactor 400 via circuit 112.In pyrolysis reactor 400, make described carbonaceous material generation pyrolytic reaction, generate pyrolysis oil.Make described pyrolysis oil flow into gasification furnace 110 from pyrolysis reactor 400 via circuit 402.Make gasifying agent enter gasification furnace 110 via circuit 114.In gasification furnace 110, heat described pyrolysis oil and described gasifying agent and make its generating gasification reaction to generate synthesis gas.Make described synthesis gas flow into micro passage reaction 200 from gasification furnace 110, described synthesis gas is reacted to generate aforesaid one or more hydrocarbon or one or more alcohol via circuit 116.
For example tar is with the synthesis gas that flows out gasification furnace 110 separates except making liquid hydrocarbon, and the method 100D of example shown in Fig. 5 is identical with method 100C routine shown in Fig. 4.These liquid hydrocarbons are got back to the pyrolysis reactor 400 via circuit 118 from circuit 116.The living pyrolytic reaction of carbonaceous material hybrid concurrency in pyrolysis reactor 400 that makes the liquid hydrocarbon of recovery and enter pyrolysis reactor 400 via circuit 112 generates pyrolysis oil.Make described pyrolysis oil flow into gasification furnace 110 from pyrolysis reactor 400, in this gasification furnace, described pyrolysis oil is mixed with the gasifying agent that enters gasification furnace 110 via circuit 114 via circuit 402.In gasification furnace 110, heat described pyrolysis oil and described gasifying agent and make its generating gasification reaction to generate synthesis gas.Make described synthesis gas flow into micro passage reaction 200 from gasification furnace 110 via circuit 116.In micro passage reaction 200, described synthesis gas is converted into aforesaid one or more hydrocarbon or one or more alcohol.
The method 100E of example shown in Fig. 6 adopts aforesaid gasification furnace 110 and micro passage reaction 200 and in conjunction with steam methane reforming (SMR) micro passage reaction 500.The SMR reaction takes place in SMR micro passage reaction 500, wherein makes the tail gas that contains methane and the steam generation endothermic reaction with the generation synthesis gas.SMR micro passage reaction 500 can comprise the SMR process microchannel that a plurality of and a plurality of burning gallery thermodynamics contact.Can in described burning gallery, carry out combustion reaction and react needed heat so that described heat absorption SMR to be provided.In the operating process of method 100E, make carbonaceous material enter gasification furnace 110 via circuit 112, in this gasification furnace, described carbonaceous material is mixed with the gasifying agent that enters gasification furnace 110 via circuit 114.Heat described carbonaceous material and described gasifying agent and make its generating gasification reaction to generate synthesis gas.Make described synthesis gas flow into micro passage reaction 200, described synthesis gas is contacted with catalyst and react to generate aforesaid one or more hydrocarbon or one or more alcohol via circuit 116.Make product flow out micro passage reaction 200 via circuit 202.The tail gas that contains methane is separated with described product and flow into the SMR micro passage reactions 500 via circuit 208 from circuit 202.Make remaining product (product that does not promptly contain tail gas) via circuit 210 outflow systems.Make described tail gas flow through SMR micro passage reaction 500 with steam.Make described tail gas and described steam generation SMR reaction and be converted into synthesis gas.Described synthesis gas flows into micro passage reactions 200 via circuit 502 from SMR micro passage reaction 500, and described synthesis gas is mixed with synthesis gas from gasification furnace 110.Mixed syngas mixture flows in the micro passage reaction 200 and aforesaid reaction takes place.
Except making carbon dioxide and separating by the synthesis gas via circuit 116 outflow gasification furnaces 110 shown in the arrow 120, the method 100F of example shown in Fig. 7 is identical with the method 100E of example shown in Fig. 6.Make poor carbon dioxide synthesis gas (that is, not carbonated synthesis gas) flow into micro passage reactions 200, mix with synthesis gas from circuit 502 at poor carbon dioxide synthesis gas described in this reactor via circuit 122.Mixed syngas mixture reacts in micro passage reaction 200 to generate aforesaid one or more hydrocarbon or one or more alcohol.
Generate the synthesis gas except making the carbon dioxide that separates with the synthesis gas that flows out gasification furnace 110 via circuit 116 flow into SMR micro passage reaction 500 via circuit 120 and described carbon dioxide be mixed with tail gas and react, the method 100G of example shown in Fig. 8 is identical with the method 100F of example shown in Fig. 7.Make described synthesis gas flow out SMR micro passage reactions 500 and flow in the micro passage reaction 200 via circuit 502.In micro passage reaction 200, make from the synthesis gas of circuit 502 and from the synthesis gas hybrid concurrency of circuit 122 and give birth to reaction to generate aforesaid one or more hydrocarbon or one or more alcohol.
Comprise the Fischer-Tropsch product in the product that flows out micro passage reaction 200 via circuit 202, the method 100H of Fig. 8 A institute example is identical with the method 100 of example shown in Figure 1.Described Fischer-Tropsch product comprises the mixture of liquids and gases.Shown in arrow 203, the Fischer-Tropsch product of gaseous state is separated with the Fischer-Tropsch product of liquid state.Can make the Fischer-Tropsch product of described liquid state that the hydrocracking reaction takes place in hydrocracking micro passage reaction 700 then.Randomly, can in separative element or distillation unit, described Fischer-Tropsch liquid product be separated into light fraction and heavy distillat.Described heavy distillat can be sent in the described hydrocracking micro passage reaction 700.Can be with described light fraction as end product or process individually.Alternatively, described light fraction introducing can processed in the hydrocracking micro passage reaction 700 of heavy distillat.Can independently carry out hydrocracking to described light fraction in the hydrocracking micro passage reaction.Can make the light Fischer-Tropsch product that flows via circuit 202 enter hydrocracking micro passage reaction 700 and the light Fischer-Tropsch product of described lightweight is flowed with hydrogen feed and mix.Shown in arrow 702, described hydrogen feed is flow in the hydrocracking micro passage reaction 700.In hydrocracking micro passage reaction 700, described Fischer-Tropsch product is contacted with hydrocracking catalyst with hydrogen and reacts to generate target hydrocracking product.Shown in arrow 704, described hydrocracking product flows out hydrocracking reactor 700.In an optional embodiment, the Fischer-Tropsch product of liquid state can be separated into light fraction and heavy distillat, in hydrocracking micro passage reaction 700, hydrocracking is carried out in described heavy distillat then.Described hydrocracking reaction is heat release.Shown in arrow 706 and 708, can use the heat-exchange fluid that flows through micro passage reaction 700 to control described reaction.But described hydrocracking reaction may be a slight exotherm, and based on such fact, the use of described heat-exchange fluid is chosen wantonly.
In an optional embodiment, can be used for carrying out the identical micro passage reaction of Fischer-Tropsch reaction and carry out the hydrocracking reaction.In this embodiment, the micro passage reaction 200 that is used to carry out Fischer-Tropsch reaction can be transformed in the downstream in described Fischer-Tropsch reaction zone and comprise the hydrocracking conversion zone.Described hydrogen feed is flowed in the described hydrocracking conversion zone.Micro passage reaction 200 can also be transformed into and remove the Fischer-Tropsch product of gaseous state in the downstream in described Fischer-Tropsch reaction zone but in the upstream of described hydrocracking conversion zone and randomly remove the liquid Fischer-Tropsch product of light fraction.
The gasification step of the inventive method (A) comprises by making described carbonaceous material in temperature and gasifying agent reaction under at least about 700 ℃ described carbonaceous material is converted into synthesis gas.Described gasifying agent can comprise oxygen, air and/or steam.Can under at least about 800 ℃ temperature, carry out described gasification step (A), in one embodiment at least about 900 ℃ temperature, in one embodiment at least about 1000 ℃ temperature, in one embodiment at least about 1100 ℃ temperature, and in one embodiment at least about 1200 ℃ temperature.Can under the temperature of about 700 ℃ of scope-Yue 2500 ℃, carry out described gasification step (A), scope is about 800 ℃-Yue 2200 ℃ in one embodiment, scope is about 900 ℃-Yue 2000 ℃ in one embodiment, scope is about 1000 ℃-Yue 1800 ℃ in one embodiment, scope is about 1100 ℃-Yue 1800 ℃ in one embodiment, scope is about 1200 ℃-Yue 1800 ℃ in one embodiment, and about 1300 ℃-Yue 1500 ℃ of scopes in one embodiment.The temperature of employed rising makes described step be different from biological method in the process of step (A), for example produces the anaerobic digestion of biogas.
Do not wish to be limited by theory, think that following reaction may take place described carbonaceous material in the process of the step (A) of the inventive method:
1. pyrolysis (or liquefaction) reaction can take place when the heating carbonaceous material.Can discharge volatile matter and produce coke, cause for example going up by weight loss to about 70%.Described process depends on the characteristic of described carbonaceous material.These characteristics may determine the structure and the composition of described coke.
2. can combustion reaction take place when generating carbon dioxide and carbon monoxide at described volatile products and part of coke and oxygen reaction.This can be that follow-up gasification reaction provides heat.
3. described coke and carbon dioxide and steam generate the reaction of carbon monoxide and hydrogen.
4. reversible gas phase water gas shift reaction can reach balance under the temperature in described gasification furnace.This may make the concentration of carbon monoxide, steam, carbon dioxide and hydrogen reach balance.
Figure BPA00001272662800191
By such reaction, limited amount oxygen can be introduced in the described gasification furnace so that the burning of part carbonaceous material is to produce carbon monoxide and energy in first reaction.The mol ratio of oxygen and carbon can be about 0.01: in about 5: 1 scope of 1-, in one embodiment about 0.2: in about 2: 1 scope of 1-, in one embodiment about 0.5: in about 1.5: 1 scope of 1-, in one embodiment about 0.5: in about 1.2: 1 scope of 1-, and be about 1: 1 in one embodiment.Described combustion reaction can be used to drive second reaction that further carbonaceous material is converted into hydrogen and extra carbon monoxide.
Can in adverse current fixed-bed gasification furnace, co-current flow fixed bed gasification furnace, fluidized-bed gasification furnace or airflow bed gasification furnace (entrained flow gasifier), carry out described gasification step (A).Described adverse current fixed-bed gasification furnace can comprise the carbonaceous material fixed bed, and described gasifying agent (for example steam, oxygen and/or air) flows in the reverse flow configuration by this fixed bed.Perhaps remove and deash or ash content is discharged as slag by dry method.Described deslagging gasification furnace (slagging gasifier) may require the higher ratio of steam and oxygen and carbon to reach than the higher temperature of described ash content fusion temperature.May require carbonaceous material to have high mechanical properties and the component of not luming so that described carbonaceous material can form permeable bed.The production capacity of such gasification furnace may be low relatively.Because gas outlet temperature may be low relatively, so the thermal efficiency may be high.Can produce coke and methane by such method.
Except described gasifying agent flowed into described carbonaceous material and flows in the structure, fixed-bed gasification furnace and described adverse current type gasification furnace described and stream were similar.May need will be by the top of burning a spot of carbonaceous material or introducing described bed from the heat of external heat source.Described synthesis gas can leave the gasification furnace under the high temperature.Most of heat in the described heat can be passed to be added to described bed top gasifying agent to obtain energy efficiency.In such structure, tar can pass the coke hotbed.But the level of described tar may be lower than the adverse current type gasification furnace.
In described fluidized-bed gasification furnace, can be in described gasifying agent the described carbonaceous material of fluidisation.Perhaps remove and deash or make ash content as the not heavy agglomerate discharge of energy fluidizing by dry method.Temperature in the dry ashing gasification furnace may be low relatively, and thereby described carbonaceous material can be highly active relatively; Low-grade coal may be particularly suitable.Described reunion (agglomerating) gasification furnace can be operated under higher slightly temperature, and may be suitable for higher grade coal.The productive rate of carbonaceous material may be higher than fixed bed, but less than the airflow bed gasification furnace height.Because the cohesion of carbonaceous material, conversion ratio may be low relatively.The recovery of solid or follow-up burning can be used to improve conversion ratio.Fluidized-bed gasification furnace may be suitable for producing carbonaceous material highly corrosive and that may damage the ash content of deslagging gasification furnace furnace wall.
In described airflow bed gasification furnace, can adopt the solid carbonaceous material of oxygen or air gasification dry powder powder in also flowing, the liquid carbonaceous material of spray form or the powder slurry of described carbonaceous material.Described gasification reaction can occur in the agglomerate of fine and close fines shape.Because it is fine that operating temperature height and coal particle can separated from one anotherly get, so most of coal is suitable for such gasification furnace.Although owing to described gas is cooled off cause the thermal efficiency may be somewhat on the low side before cleaning, high temperature and high pressure also may mean can obtain higher productive rate.Although oxygen need be higher than the gasification furnace of other types, high like this temperature may mean that also tar and methane may not be present in the product synthesis gas.Because operating temperature may be greater than the ash content fusion temperature, so airflow bed gasification furnace can be removed most ash content as slag.May generate than ash content small part or that have superfine dry powder flying dust form or that have black flying dust powder slurry form.Some carbonaceous materials, particularly certain type living beings may form the slag of corrosion as the ceramic inner walls of protection gasification furnace outer wall.But the gasification furnace of part air flow bed type may not comprise ceramic inner walls but may contain internal water or the steam cooling wall that is covered by partly solidified slag.Such gasification furnace may not be subjected to the influence of corrosivity slag.The part carbonaceous material may have the ash content of high ash content fusion temperature.In this case, can be with lime stone and described fuel mix before gasification.Amount with the described fusion temperature of enough reductions is added lime stone.Described particles of carbonaceous material may be less than the gasification furnace of other types.This may mean that described carbonaceous material can be pulverous, and this may need the gasification furnace more energy than other types.
Can in the molten reactant metal device, carry out described gasification step (A).In described molten reactant metal device, described carbonaceous material is contacted with motlten metal with steam and reacts to generate synthesis gas.Described motlten metal can comprise that first with the steam that enters described reactor is according to following formula reactive activity metal (Me):
xMe+yH 2O→yH 2+Me xO y
Described carbonaceous material can react with the second portion of described steam to generate carbon monoxide and hydrogen.Described reactive metal can have the oxygen affinity similar to the oxygen affinity of hydrogen.Described reactive metal can comprise metal that one or more are following or their alloy: germanium, iron, zinc, tungsten, molybdenum, indium, tin, cobalt or antimony.Described reactive metal can be partially dissolved in the mixture of second metal or metal at least.The metal that dissolves described reactive metal can refer to dilute metal.Described dilution metal also can with steam reaction, in this case, described dilution metal can be selected from as above disclosed reactive metal, prerequisite is that the described reactive metal of the specific activity of described dilution metal is low.Described dilution metal can comprise one or more in nickel, copper, ruthenium, rhodium, palladium, silver, cadmium, rhenium, osmium, iridium, platinum, gold, mercury, lead, bismuth, selenium, the tellurium.In described motlten metal mixture, can use more than a kind of dilution metal.In one embodiment, described reactive metal can comprise that iron and described dilution metal can comprise tin.The molten reactant metal device that can be used to make described carbonaceous material be converted into synthesis gas can comprise United States Patent (USP) 7,232,472B2,6,685,754B2,6,682,714B2 and 6,663, the molten reactant metal device that discloses among the 681B2, described patent documentation is incorporated present patent application in the quoted passage mode.
Can in gasifying stove, carry out plasma described gasification step (A).Adopt such system, described carbonaceous material can be sent in the plasma converter, described plasma converter can comprise the rustless steel container that is full of nitrogen or normal air of sealing.Can in two electrodes, feed electric current (for example 650 volts of electric currents); This has removed nitrogen or airborne electronics and has produced plasma.Pass described isoionic stabling current and form powerful strong energy field, enough make described carbonaceous material resolve into its component element.Accessory substance can comprise material and the synthesis gas that is similar to glass, and the described material that is similar to glass can be used as the raw material of preparation high-strength asphalt or family expenses ceramic tile.Can make the described synthesis gas that is under for example about 2200 ℉ of high temperature (1204 ℃) leave described plasma converter.Then described synthesis gas is sent in the cooling system that produces steam.Described system can be used to drive the turbine that produces electric power, and part electric power can be used to described plasma converter that energy is provided, and remaining part can need as the heat or the electric power of factory simultaneously, perhaps exports back to utility network.Then described synthesis gas is continued to be fed into micro passage reaction 200.
Can or generate pure micro passage reaction 200 or one or more SMR micro passage reaction 500 or one or more hydrocracking micro passage reaction 700 with one or more Fischer-Tropsch (FT) reactor and place container 220.Container 220 has the structure of example as shown in Fig. 9 and Figure 10.With reference to figure 9 and Figure 10, container 220 comprises five Fischer-Tropsch reaction devices or generates micro passage reaction 200 or five SMR micro passage reactions 500 or five hydrocracking micro passage reactions 700 of alcohol.Such reactor is labeled as 200/500/700 in described figure.Such reactor is labeled as Fischer-Tropsch or generates micro passage reaction, SMR micro passage reaction or hydrocracking micro passage reaction 200/500/700-1,200/500/700-2,200/500/700-3,200/500/700-4, the 200/500/700-5 of alcohol in Figure 10.Although in described figure, disclose five micro passage reactions, be understandable that, the Fischer-Tropsch of the number of wishing arbitrarily or the micro passage reaction, SMR micro passage reaction or the hydrocracking micro passage reaction that generate alcohol can be arranged in the container 220.For example, container 220 can comprise about 1000 micro passage reactions 200,500 or 700 of about 1-, comprise in one embodiment about 750 of about 1-, in one embodiment comprise about 500 of about 1-, in one embodiment comprise about 250 of about 1-, in one embodiment comprise about 100 of about 1-, comprise about 50 and comprise about 20 micro passage reactions 200,500 or 700 of about 1-in one embodiment of about 1-in one embodiment.Container 220 can be a pressure resistant vessel.Container 220 comprises inlet 224 and 228 and export 222 and 226.
When container 220 used with Fischer-Tropsch or the micro passage reaction 200 that generates alcohol, inlet 224 linked to each other with manifold, and this manifold is used for making synthetic air to go into the Fischer-Tropsch of micro passage reaction 200 or generates pure process microchannel.Inlet 228 links to each other with manifold, and this manifold is used for making the hot switching path of heat-exchange fluid (for example steam) inflow micro passage reaction 200.Outlet 222 links to each other with manifold, and this manifold is used for making product to flow out the Fischer-Tropsch of micro passage reaction 200 or generates pure process microchannel.Outlet 226 links to each other with manifold, and this manifold is used for making the hot switching path of heat-exchange fluid outflow micro passage reaction 200.
When container 220 used with SMR micro passage reaction 500, container 220 comprised outlet 222 and inlet 224,228 and 226.Inlet 224 links to each other with manifold, and this manifold is used for making the SMR process microchannel of SMR charging (for example FT tail gas and steam) inflow SMR micro passage reaction 500.Inlet 228 links to each other with manifold, and this manifold is used for making the burning gallery of fuel (for example natural gas) inflow SMR micro passage reaction 500.Outlet 222 links to each other with manifold, and this manifold is used to make synthesis gas from SMR micro passage reaction 500 flow containers 220.Inlet 226 links to each other with manifold, and this manifold is used for making the interpolation passage stage by stage of oxygen or oxygen source (for example air) inflow SMR micro passage reaction 500.Container 220 also comprises and is used to make waste gas to flow out the outlet (not shown) of described SMR micro passage reaction 500.
When container 220 used with hydrocracking micro passage reaction 700, inlet 224 linked to each other with manifold, and this manifold is used for making the hydrocracking process microchannel of Fischer-Tropsch product from circuit 202 inflow hydrocracking micro passage reactions 700.Container 220 also comprises and is used for making hydrogen to flow into the inlet (not shown) of the process microchannel of hydrocracking micro passage reaction 700 via manifold.Inlet 228 links to each other with manifold, and this manifold is used for making the hot switching path of heat-exchange fluid inflow micro passage reaction 700.Outlet 222 links to each other with manifold, and this manifold is used for making the process microchannel of the Fischer-Tropsch product outflow micro passage reaction 700 of hydrocracking.Outlet 226 links to each other with manifold, and this manifold is used for making the hot switching path of heat-exchange fluid outflow micro passage reaction 700.Hydrocracking that described Fischer-Tropsch product is taken place reaction can be a slight exotherm only, thereby and in micro passage reaction 700, can not need to use hot switching path, can think that therefore hot switching path chooses wantonly.When using micro passage reaction 700, hydrogen feed gas that can be improved and the quality transmission between the Fischer-Tropsch product, based on such fact, it is favourable using the 700 pairs of Fischer-Tropsch products of micro passage reaction that have or do not have hot switching path to carry out hydrocracking.
Container 220 can use the material of any appropriate to make, and this material is enough at running cost-tropsch reactors or generates under pure micro passage reaction 200, SMR micro passage reaction 500, the hydrocracking micro passage reaction 700 needed temperature and pressures operate.For example, the shell 221 of container 220 and top cover 223 can be made by cast steel.Flange, connector and pipe fitting can be made by 316 stainless steels.Container 220 can have the diameter of any hope, for example, is the about 1000cm of about 10-, and is the about 300cm of about 50-in one embodiment.The axial length of container 220 can be the value of wishing arbitrarily, for example, and about 50 meters of about 0.5-, and about 20 meters of about in one embodiment 1-.
The micro passage reaction 200 of Fischer-Tropsch or generation alcohol can comprise a plurality of overlapping layer by layer or Fischer-Tropsch that is arranged side by side or process microchannel and the hot switching paths that generate alcohol.The micro passage reaction 200 of Fischer-Tropsch or generation alcohol can be the shape of cube fragment of brick.Each cube fragment of brick in cube fragment of brick like this can have length, width and height, and described length is in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.Described width can be in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.Described height is in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.
Micro passage reaction 200 and container 220 can be fully little and compact, thereby are easy to transportation.Therefore, can in the inventive method, use other equipment to transport for example military base, remote place such reactor and container, and such reactor and container can be used for, and for example solid waste, living beings etc. are converted into synthetic fuel, for example motor vehicle fuel, diesel oil, aviation fuel etc. with carbonaceous material.
The micro passage reaction 200 of each Fischer-Tropsch or generation alcohol can comprise a plurality of repetitives, and each repetitive wherein comprises one or more Fischer-Tropsch or generates process microchannel and one or more hot switching path of alcohol.Operable repetitive is included in repetitive 230,230A, 230B and the 230C of difference example among Figure 11-14.The micro passage reaction 200 of Fischer-Tropsch or generation alcohol can comprise about 1-about 1000 repetitives 230,230A, 230B and 230C, and comprises about 500 the such repetitives of about 10-in one embodiment.The catalyst that uses in repetitive 230-230C can have form arbitrarily, comprises different catalyst structure form as described below.
Figure 11 illustrates repetitive 230.With reference to Figure 11, be arranged to the process microchannel 232 of Fischer-Tropsch or generation alcohol adjacent with the heat exchange layers 234 that contains hot switching path 236.Hot switching path 236 can be the microchannel.Common wall 237 separates process microchannel 232 and heat exchange layers 234.Catalyst is arranged in the conversion zone 240 of process microchannel 232.In one embodiment, on the length of heat exchange layers 234 to 200% of the length of conversion zone 240, the length of heat exchange layers 234 is that about 50-of length of conversion zone 240 is about 175% in one embodiment, and the length of heat exchange layers 234 is about 75-about 150% of the length of conversion zone 240 in one embodiment.According to the direction shown in the arrow 250, reactant composition (for example synthesis gas) is flowed in the conversion zone 240 of process microchannel 232, contact with the catalyst of this conversion zone, and reaction generates target product.Shown in arrow 252, make product (for example one or more hydrocarbon or one or more alcohol) flow out process microchannel 232.According to process microchannel 232 in reactant composition and the direction of the mobile cross-flow of product, make heat-exchange fluid flow through hot switching path 236.The reaction of Fischer-Tropsch that is carried out in process microchannel 232 or generation alcohol is that heat-exchange fluid heat release and described provides cold for described reaction.
Alternatively, described process microchannel and the hot switching path setting of can in repetitive 230A, aliging.Except making hot switching path 236 half-twists and making the heat-exchange fluid that flows through hot switching path 236 flows with a direction, the repetitive 230A of example shown in Figure 12 is identical with the repetitive 230 of example shown in Figure 11, described direction can be with process microchannel 232 in the reactant and the direction of the mobile adverse current of product or with respect to the direction of reactant in the process microchannel 232 and product and the direction that flows.
Alternatively, described process microchannel and the hot switching path setting of can in repetitive 230B, aliging.Figure 13 illustrates repetitive 230B.With reference to Figure 13, be arranged to Fischer-Tropsch or the pure process microchannel 232a of generation adjacent with heat exchange layers 235.Heat exchange layers 235 contains the hot switching path 236 that a plurality of alignment parallel to each other are provided with, and each hot switching path 236 wherein is vertical angle longitudinal extension with the longitudinally with respect to process microchannel 232a.Heat exchange layers 235 is shorter than process microchannel 232a on length.Heat exchange layers 235 from or extend longitudinally to a little 247 near the inlet 246 of the conversion zone 240 of process microchannel 232a along process microchannel 232a, this development length is shorter than the length of the outlet 248 that extends to conversion zone 240.In one embodiment, on the length of heat exchange layers 235 to about 90% of conversion zone 240 length, the length of heat exchange layers 235 is about 5-about 90% of conversion zone 240 length in one embodiment, the length of heat exchange layers 235 is that about 5-of conversion zone 240 length is about 50% in one embodiment, and the length of heat exchange layers 235 is about 50-about 90% of conversion zone 240 length in one embodiment.The width of process microchannel 232a is expanded in the downstream area of the end 247 of heat exchange layers 235 or is extended.
Alternatively, described process microchannel and the hot switching path setting of can in repetitive 230C, aliging.Except repetitive 230C comprises the heat exchange layers 235a adjacent with process microchannel 232a, described heat exchange layers 235a is outside on the opposite face process microchannel 232a of heat exchange layers 235, and the repetitive 230C of example shown in Figure 14 is identical with repetitive 230B routine shown in Figure 13.Heat exchange layers 235a contains a plurality of parallel heat exchange passage 236a, and described parallel heat exchange passage is identical or similar with the hot switching path 236 that designs with above-mentioned in size.Heat exchange layers 235a from or extend to a little 249 near the inlet 246 of the conversion zone 240 of process microchannel 232a along the direction of process microchannel 232a length, this development length is shorter than the length of the end 247 that extends to heat exchange layers 235.On the length of heat exchange layers 235a to about 90% of heat exchange layers 235 length, the length of heat exchange layers 235a is about 5-about 90% of heat exchange layers 235 length in one embodiment, the length of heat exchange layers 235a is that about 5-of heat exchange layers 235 length is about 50% in one embodiment, and the length of heat exchange layers 235a is about 50-about 90% of the length of heat exchange layers 235 in one embodiment.The width of process microchannel 232a is expanded in the downstream area of the end 247 of heat exchange layers 235 and 235a and 249 respectively.
Process microchannel 232 and 232a can have the cross section of arbitrary shape, for example square, rectangle, circle, semicircle or the like.Can think that the inner height of each passage among process microchannel 232 and the 232a is the reduced size of the inside dimension of the direction that flows through process microchannel perpendicular to reactant and product.Each passage among process microchannel 232 and the 232a can have the inner height of going up to about 10mm, goes up in one embodiment to about 6mm, goes up in one embodiment to about 4mm, and goes up in one embodiment to about 2mm.In one embodiment, described height can be in the scope of the about 10mm of about 0.05-, in one embodiment in the scope of the about 6mm of about 0.05-, in one embodiment in the scope of the about 4mm of about 0.05-, and in one embodiment in the scope of the about 2mm of about 0.05-.Can think that the width of each process microchannel 232 and 232a is for flowing through another inside dimension of the direction of process microchannel perpendicular to reactant and product.The width of each process microchannel 232 and 232a can be an arbitrary dimension, for example goes up to about 3 meters, is about 3 meters of about 0.01-in one embodiment, and is about 3 meters of about 0.1-in one embodiment.The length of each process microchannel 232 and 232a can be arbitrary dimension, for example goes up to about 10 meters, is about 10 meters of about 0.2-in one embodiment, is about 6 meters of about 0.2-in one embodiment, and is about 3 meters of about 0.2-in one embodiment.
Hot switching path 236 can be that microchannel or described passage can have and make it be classified as the bigger size of non-microchannel.Each passage in the hot switching path 236 can have the cross section of arbitrary shape, for example square, rectangle, circle, semicircle or the like.Can think that the inner height of each passage in the hot switching path 236 is the reduced size of the inside dimension of the flow direction in described hot switching path perpendicular to reactant and product.Each passage in the hot switching path 236 can have the inner height of going up to about 2mm, in one embodiment in the scope of the about 2mm of about 0.05-, and in one embodiment in the scope of the about 1.5mm of about 0.05-.Pass another vertical inside dimension of flow direction of process microchannel with reactant and product, it is each width of channel in the described passage, it can be arbitrary dimension, for example go up to about 3 meters, be about 3 meters of about 0.01-in one embodiment, and be about 3 meters of about 0.1-in one embodiment.The length of each passage in the hot switching path 236 can be arbitrary dimension, for example goes up to about 10 meters, is about 10 meters of about 0.2-in one embodiment, is about 6 meters of about 0.2-in one embodiment, and is about 3 meters of about 0.2-in one embodiment.
The number of repetitive 230-230C in the micro passage reaction 200 can be the number of wishing arbitrarily, for example, and one, two, three, four, five, six, eight, ten, hundreds of, several thousand, several ten thousand, hundreds of thousands, millions of or the like.
At Fischer-Tropsch or generate in the design and operating process of pure micro passage reaction, provide that to optimize described reaction along the heat exchange performance of the length adjustment of described process microchannel be favourable.This can discharge in the hot switching path that is matched with at described micro passage reaction by the part that makes Fischer-Tropsch that carries out or the heat that reaction generated that generates alcohol in described process microchannel is realized by heat that heat-exchange fluid removed or the cold that provides.Compare with the postposition or the downstream part of described conversion zone, the Fischer-Tropsch in the preposition or upstream portion of the conversion zone of described process microchannel or to generate the extent of reaction of alcohol higher, and the heat that discharges thus is more.Therefore, compare the cold that needs more heats that discharged with reaction to be complementary in the upstream portion of described conversion zone with the downstream part of described conversion zone.More carry out heat exchange or the cooling duct that thermodynamics contacts by providing with the upstream portion of the conversion zone of described process microchannel than the downstream part of described conversion zone, obtain having the mobile of more heat exchange or cooling fluid, the heat exchange that can obtain to adjust thus.Such technical scheme is shown in Figure 13 and 14, wherein heat exchange layers 235 and the 235a longitudinally from the inlet 246 of conversion zone 240 along process microchannel 230B and 230C extends to a little 247 and 249, and described development length is shorter than the length of the outlet 248 that extends to described conversion zone 240.Alternatively or in addition, by changing the heat exchange performance that the heat exchange flow rate of flow of fluid can obtain to adjust in the hot switching path.Compare with the less heat exchange of needs or the zone of cold, can be in the zone of other heat exchange of needs or cold the flow velocity of heat-exchange fluid be improved.For example, than carrying out the hot switching path that thermodynamics contacts with the downstream part of the conversion zone of described process microchannel, heat-exchange fluid is favourable at the higher flow velocity that carries out in the hot switching path that thermodynamics contacts with the upstream portion of the conversion zone of process microchannel.Therefore, with reference to Figure 11, for example, with flow velocity may be lower close process microchannel 232 or the hot switching path 236 of the outlet of conversion zone 240 compare, higher near the flow velocity in the hot switching path 236 of the inlet of process microchannel 232 or conversion zone 240.The flow velocity of the heat-exchange fluid by selecting optimum hot switching path size and/or each hot switching path independent or in groups can carry out the optimal effectiveness design to the heat transmission from described process microchannel to described hot switching path.The additional alternative design that is used to regulate heat exchange can relate to the described Fischer-Tropsch of the specific location in described process microchannel or generate the selection of catalysts and the design (as use or other chemistry or the physical characteristic of particle size, catalyst formulation, bulk density, grading catalyst) of alcohol.Such alternative design may influence simultaneously from the heat of described process microchannel and discharge and to the heat transmission of described heat-exchange fluid.Can for the heat transmission provide the process microchannel of driving force and the temperature difference between the hot switching path can be stable also can be along the length variations of described process microchannel.
SMR micro passage reaction 500 can comprise a plurality of overlapping layer by layer or the SMR process microchannel, burning gallery or the interpolation passages stage by stage that are arranged side by side.SMR micro passage reaction 500 can be the shape of cube fragment of brick of example as shown in Fig. 9 and 10.Each cube fragment of brick in cube fragment of brick like this can have length, width and height, and described length is in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 50-.Described width can be in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 50-.Described height is in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 50-.
SMR micro passage reaction 500 can comprise a plurality of repetitives, and each repetitive wherein comprises one or more SMR process microchannel, burning gallery or interpolation passage stage by stage.Operable repetitive is included in repetitive 510,510A, 510B, 510C and the 510D of difference example among Figure 21-25.SMR micro passage reaction 500 can comprise about 1-about 1000 repetitives 510,510A, 510B, 510C or 510D, comprise in one embodiment about 750 of about 3-, in one embodiment comprise about 500 of about 5-, comprise about 250 and comprise about 100 the such repetitives of about 10-in one embodiment of about 5-in one embodiment.
The repetitive 510 of example comprises SMR process microchannel 512 and heating part 520 shown in Figure 21.Heating part 520 comprises burning gallery 530 and stage by stage interpolation passage 540 and 540A.Process microchannel 510 is inverted U-shaped and comprises the conversion zone 516 that is provided with SMR catalyst (not shown).Shown in arrow 514, described SMR charging (for example combination of FT tail gas and steam) is entered in the SMR process microchannel 512, flow through described SMR process microchannel, in conversion zone 516, contact with described SMR catalyst, the reaction of generation steam methane reforming contains CO and H thereby generate 2Synthesis gas.Shown in arrow 518, make described synthesis gas flow out described SMR process microchannel.Burning gallery 530 is M shape burning microchannels, and it comprises the conversion zone 534 that is provided with the combustion catalyst (not shown).Burning gallery 530 also comprises the perforate part 538 in its sidewall, so that described oxygen or oxygen source are from stage by stage interpolation passage 540 and 540A inflow burning gallery 530.Shown in arrow 532, make fuel enter burning gallery 530 and flow in the conversion zone 534.Shown in arrow 542 and 542A, make described oxygen or oxygen source enter interpolation passage 540 and 540A stage by stage and flow through perforate part 538 to flow in the conversion zone 534 in the burning galleries 530.Described fuel is mixed with described oxygen or oxygen source, contact, and the combustion reaction of heat and burnt gas takes place to produce with described combustion catalyst.Shown in arrow 536, make described burnt gas flow out burning gallery 530.
SMR process microchannel 512 in repetitive 510A is straight tubes, flow through the microchannel but not be inverted the U-shaped microchannel, and the repetitive 510A of example is identical with repetitive 510 shown in Figure 22.
Except repetitive 510B comprised two adjacent SMR process microchannel that are called as SMR process microchannel 512 and 512A, the repetitive 510B shown in Figure 23 was identical with repetitive 510A.SMR process microchannel 512 is adjacent with burning gallery 530.SMR process microchannel 512A and SMR process microchannel 512 are adjacent and contact with burning gallery 530 thermodynamics.
Except the burning gallery 330 of example shown in Figure 24 is straight tube passage but not M shape passage, and only use outside the interpolation passage 540 stage by stage, the repetitive 510C of example shown in Figure 24 is identical with repetitive 510A routine shown in Figure 22.
Except the SMR process microchannel 512 of repetitive 510D is to be inverted the U-shaped microchannel but not the straight tube microchannel, the repetitive 510D of example shown in Figure 25 is identical with unit 510C routine shown in Figure 24.
Micro passage reaction 700 can comprise a plurality of overlapping layer by layer hydrocracking process microchannel and hot switching paths.But as mentioned above, described hot switching path is for hydrocracking micro passage reaction 700 and nonessential, can think that therefore the use of described hot switching path chooses wantonly.Hydrocracking micro passage reaction 700 can be the shape of cube fragment of brick of example as shown in Fig. 9 and 10.The length of described cube of fragment of brick can be in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.The width of described cube of fragment of brick can be in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.The height of described cube of fragment of brick is in the scope of the about 1000cm of about 10-, and in one embodiment in the scope of the about 200cm of about 20-.Can make described Fischer-Tropsch product, perhaps the liquid state of described at least Fischer-Tropsch product or heavy liquid part and hydrogen enter in the described hydrocracking process microchannel, and can make the product of hydrocracking flow out described hydrocracking process microchannel.Can make heat-exchange fluid (if you are using) flow through described hot switching path.Micro passage reaction 700 can have incoming flow top cover or manifold and product base or manifold, shown in incoming flow top cover or manifold reactant is flowed in the process microchannel, described product base or manifold can make product flow out process microchannel.When hot switching path uses with micro passage reaction 700, can adopt heat exchange inlet manifold and heat exchange outlet manifold, described inlet manifold can make heat-exchange fluid flow in the hot switching path, and described outlet manifold can make heat-exchange fluid flow out hot switching path.
Hydrocracking reactor 700 can comprise one or more repetitives, and each repetitive can comprise one or more process microchannel and randomly comprise one or more hot switching paths.Each microchannel in the described process microchannel can comprise one or more conversion zones, and reactant reaction generates target product in this zone.Catalyst is present in described one or more conversion zones with solid form.Described catalyst can comprise the homogeneous catalyst that is fixed in solid.In one embodiment, can make the combination of each process microchannel and one or more adjacent reactant flow channels so that the hydrogen of Tian Jiaing enters in the described process microchannel stage by stage.Described process microchannel and described adjacent reactant flow channels may have common wall, are provided with a plurality of openings in described common wall.Such opening can be used for making the hydrogen from described adjacent reactant flow channels to flow into described process microchannel.Described incoming flow top cover can comprise one or more manifolds that are used for the mixture of reactant is distributed to described process microchannel.Alternatively, described incoming flow top cover can comprise the independent manifold that is used for described reactant is distributed to individually described process microchannel and described adjacent reactant flow channels.
Fischer-Tropsch or generate described adjacent reactant flow channels in described hot switching path, the described burning gallery in the SMR micro passage reaction and interpolation passage stage by stage and the hydrocracking micro passage reaction 700 in the micro passage reaction 200 of alcohol and hot switching path (if you are using) can be that microchannel or described passage can have and make it be classified as the size of non-microchannel.For example, such passage can have inner height or the width of going up to about 50mm, goes up in one embodiment to about 25mm, and goes up in one embodiment to about 15mm.Process microchannel, described SMR process microchannel and the described hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol are the microchannels.Each microchannel in the described microchannel can have the cross section of arbitrary shape, for example, and square, rectangle, circle, semicircle or the like.Each microchannel can have the inner height of going up to about 10mm, goes up in one embodiment to about 5mm, and goes up in one embodiment to about 2mm.The height of each microchannel in the described microchannel can be in the scope of the about 10mm of about 0.05-, be the about 5mm of about 0.05-in one embodiment, be the about 2mm of about 0.05-in one embodiment, and be the about 1.5mm of about 0.05-in one embodiment.The width of each microchannel in the described microchannel can be an arbitrary dimension, for example goes up to about 3 meters, is about 3 meters of about 0.01-in one embodiment, and is about 3 meters of about 0.1-in one embodiment.The length of each microchannel can be arbitrary dimension, for example goes up to about 10 meters, is about 10 meters of about 0.2-in one embodiment, is about 6 meters of about 0.2-in one embodiment, and is about 3 meters of about 0.2-in one embodiment.
The process microchannel and the hot switching path of Fischer-Tropsch in the micro passage reaction 200 of Fischer-Tropsch or generation alcohol or generation alcohol, SMR process microchannel in the SMR micro passage reaction 500, burning gallery and interpolation passage stage by stage and the hydrocracking process microchannel in the hydrocracking micro passage reaction 700, adjacent reactant flow channels and hot switching path (if you are using) can have rectangular cross section and side by side vertical alignment in plane of orientation or side by side horizontal alignment in the location overlay plane.Such plane can be from the horizontal plane angle of inclination of steeving.Such layout can refer to the parallel-plate layout.Such passage can be arranged on the modular type compact unit that is used for amplification.
Fischer-Tropsch or the micro passage reaction 200, SMR micro passage reaction 500 and the hydrocracking micro passage reaction 700 that generate alcohol can be made by any materials, and such material can provide enough intensity, dimensional stability and thermal conduction characteristic to realize the operation of goal approach.Such material can comprise the combination of alloy, brass, steel (for example stainless steel), quartz, silicon or above-mentioned two or more materials of aluminium, titanium, nickel, platinum, rhodium, copper, chromium, aforementioned any one metal.Each micro passage reaction can be made by the stainless steel with one or more copper that are used to form described passage or aluminium waveform.
Can utilize prior art to make micro passage reaction 200, SMR micro passage reaction 500 and the hydrocracking micro passage reaction 700 of Fischer-Tropsch or generation alcohol, described technology comprises the combination of Wire-cut Electrical Discharge Machining (wire electrodischarge machining), traditional processing, laser cutting, photochemistry processing, electrochemistry processing, moulding, water jet, punching press, etching (for example chemical etching, photochemical etching or plasma etching) and said method.
Have the part that is removed and form the clamping plate (shims) of flow channel by formation, can make up Fischer-Tropsch or generate micro passage reaction 200, SMR micro passage reaction 500 and the hydrocracking micro passage reaction 700 of alcohol.One repeated clamping plate can be assembled Fischer-Tropsch or generate micro passage reaction, described SMR micro passage reaction and the described hydrocracking micro passage reaction of the alcohol device with the formation integration via diffusion bonding (diffusion bonding), Laser Welding (laser welding), diffusion welding (DW) (diffusion brazing) and similar approach.Described micro passage reaction can be assembled by the combination of clamping plate or push pedal (laminae) and part (partial) thin slice or belt body (strips).In such method,, form described passage or area of space to reduce the amount of required material by the thin slice of belt body or part is assembled.
The waveform that use has the form of right angle corrugated insertion can make up Fischer-Tropsch or generate pure micro passage reaction 200, SMR micro passage reaction 500 and hydrocracking micro passage reaction 700.The undulatory thin slice in described right angle can have the limit of rounding rather than sharp keen limit.Such insertion can be clipped between two relative plane laminas or clamping plate.In such method, can on four edges, limit described microchannel at three sides and by described plane lamina by described corrugated thin slice.Can form described process microchannel and described hot switching path by such mode.The micro passage reaction that adopts waveform to make is disclosed among the WO 2008/030467, and the document is incorporated in the present patent application in the quoted passage mode.
Process microchannel, SMR process microchannel and/or burning gallery and the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol can comprise one or more surface characteristics, and described surface characteristics is the form of depression and/or projection on one or more inwalls of described process microchannel.Example is shown in Figure 26 and 27.Hot switching path in the micro passage reaction 200 of Fischer-Tropsch or generation alcohol and the hot switching path (if you are using) in the hydrocracking micro passage reaction 700 and the adjacent reactant flow channels in the hydrocracking micro passage reaction 700 also can comprise such surface characteristics.Described surface characteristics can be used to disturb flowing of fluid mobile in the described passage.Can strengthen mixing and/or heat conduction to described mobile interference.Described surface characteristics can be the form on patterned surface.Described Fischer-Tropsch or generate micro passage reaction, SMR micro passage reaction and/or the hydrocracking micro passage reaction of alcohol can be by making a plurality of clamping plate are compressed together.On one or two main surface of described clamping plate, can comprise surface characteristics.Alternatively, can use some thin slices or clamping plate and some belt bodies or partial sheet that micro passage reaction, SMR micro passage reaction and/or the hydrocracking micro passage reaction of described Fischer-Tropsch or generation alcohol are assembled, to reduce the total amount of making the required metal of described device.The clamping plate that contain surface characteristics can contain the clamping plate pairings (two opposites a microchannel) of surface characteristics with another.With only on a main surface, have the passage of surface characteristics to compare, pairing can produce better mixing or heat conduction strengthens.Described pattern can comprise the pit of being with twill, described pit is set makes on its whole width that cover microchannel surface substantially.The one patterned surface characteristics zone of facing the wall and meditating can occupy part or all length of microchannel surface.Can be provided with surface characteristics make its length that covers channel surface at least about 10%, in one embodiment at least about 20%, in one embodiment at least about 50% and in one embodiment at least about 80%.The pit of each band twill can comprise one or more angles with respect to flow direction.With respect to other pit surface feature, continuous pit surface feature can comprise similarly or the angle that replaces.
Surface characteristics can be arranged on therein more than the one side microchannel wall on or within embodiment in, one face the wall and meditate on or within described surface characteristics can have and be based upon second the pattern of pattern identical (or similar) on facing the wall and meditating, but described surface characteristics is round the center line rotation of described main channel average overall flow direction.Therein surface characteristics may be on relative wall or within embodiment in, one face the wall and meditate on or within described surface characteristics can be the mirror image of the described feature on wall relatively substantially.Surface characteristics can be arranged on therein more than the one side microchannel wall on or within embodiment in, one face the wall and meditate on or within described surface characteristics can have with at second the pattern of pattern identical (or similar) on facing the wall and meditating, but described surface characteristics is round the vertical axis rotation of described main channel average overall flow direction.In other words, described surface characteristics can be turned over turnback with respect to described main channel average overall flow direction, and rotates with respect to the center line of described main channel average overall flow direction.On relative or the adjacent wall or within surface characteristics can be directly aligned with each other or directly alignment mutually, but can at least a portion of described wall length, constantly reappear along described wall.Surface characteristics can be placed on three or more inner surfaces of passage.For three faces or the channel shape of face are still less arranged, as triangle, avette, oval, circular or the like, described surface characteristics can cover about 20%-about 100% of described microchannel girth.
Patterned surface can comprise a plurality of patterns that overlap each other.The model in hole or array can be arranged to adjacently with heat exchange walls, and for example the array of the band twill of surface characteristics is overlapping and adjacent with the open channel that is used to flow at the top can to make second pattern.The thin slice adjacent with open space can have the pattern that passes described sheet thickness, can pass described thin slice and enters following pattern so that flow.Flow and to take place as the result of advection (advection) or diffusion.As example, first thin slice with array of through hole (through holes) can be arranged on the hot conductive walls, and will have second thin slice that twill passes the array of groove (through slots) and be arranged on described first thin slice.This provides more surface area for adhering to catalyst.Described pattern can reappearing on another is faced the wall and meditated at least in described process microchannel.Described pattern can be offset on two relative walls.Described inner most patterned surface (those define the surface of flow channel) can have pattern, for example the twill array.The two sides of described twill array can be arranged to simultaneously be arranged to opposite face is arranged to against the direction that flows along the direction that flows along direction that flows or one side.By changing the surface characteristics of two relative walls, in the described fluid that flows downward along center or open space, can form different flow fields and vorticity degree.
Described surface characteristics can be arranged to flow direction angled through described passage.Described surface characteristics can be arranged to respect to flow direction into about 1 °-Yue 89 ° angle, be about 30 °-Yue 75 ° angle in one embodiment.Orientation angle can be the oblique angle.Can described surface characteristics with angle be set along flow direction or against flow direction.Can force the part of described fluid to enter in the depression of described surface characteristics with flowing of described surface characteristics fluid in contact, and other fluids flow above described surface characteristics.Flowing in described surface characteristics can be consistent with described surface characteristics, and angled with the overall flow direction in the described passage.When fluid flows out described surface characteristics, be x, y, the z coordinate system of z direction for described overall flow, wherein said fluid can apply momentum at x and y direction.This may cause generation disturbance or whirlpool in the flowing of described fluid.Such pattern may help mixing.
Two or more surface characteristics zone series connection in the described process microchannel can be provided with, so that by the first surface characteristic area, by using at least one second surface characteristic area of different flow pattern, realize the mixing of described fluid then.
Described surface characteristics can have two layers or more a plurality of overlap each other or with three dimensional pattern be intertwined the layer.Pattern in each independent layer can be identical or different.Each layer or only flowing in a layer can turn round and round or advection (advect).Can be used for forming other surface area with the non-conterminous subgrade in overall flow path of described passage.Described flowing can be turned round and round at the ground floor of surface characteristics, and enters in the second layer or the more a plurality of subgrade to promote reaction by molecular diffusion.Can make three-dimensional surface characteristics by metal casting, photochemistry processing, laser cutting, etching, RF ablation or additive method, wherein different patterns can be resolved into as the independent plane that overlaps each other.The surface characteristics of three-dimensional can be arranged to described microchannel in the overall flow path adjacent, wherein said surface characteristics has the different degree of depth, shape and/or position, follow have different depth, the Ya Tezheng of the pattern of shape and/or position.
The example of three-dimensional surface features can be included in the angle of inclination or the zigzag that at the interface embed adjacent with overall flow path, described microchannel.Described zigzag below, may have the structure of a series of three-dimensionals, the structure of described three-dimensional links to each other with surface characteristics adjacent to the overall flow path, but is made up of the structure of difformity, the degree of depth and/or position.Be provided with the subgrade passage make its directly do not drop on described microchannel in the adjacent open surface feature in overall flow path the below and make above-mentioned upper strata passage by one or more bendings two dimension or three-dimensional passage to link to each other be further favourable.Such method helps forming the time of staying distribution that is fit in described microchannel, wish that wherein time of staying distribution has broad and narrower contrast.
Can be with the length and the width of the mode defining surface feature identical with width with the length of passage.The described degree of depth can be the distance that described surface characteristics sinks to or rises from the surface of described microchannel.The degree of depth of described surface characteristics can be consistent with the direction of the micro-channel device of stacking overlapping and binding, described micro-channel device have be formed on the described sheet surface or within surface characteristics.The size of described surface characteristics can refer to the full-size of surface characteristics, and for example, the degree of depth of circular groove can refer to depth capacity, promptly arrives the degree of depth of the bottom of described circular groove.
Described surface characteristics can have the degree of depth that goes up to about 5mm, be last in one embodiment to about 2mm, in one embodiment in the scope of the about 5mm of about 0.01-, in one embodiment in the scope of the about 2mm of about 0.01-, and in one embodiment in the scope of the about 1mm of about 0.01-.The width of described surface characteristics can be enough to make it almost across described microchannel width (for example herringbone (herringbone) design), but in one embodiment (as inserting feature) across as described in the microchannel width about 60% or still less, be about 50% or still less in one embodiment, be about 40% or still less in one embodiment, be in the scope of about 0.1%-about 60% of described microchannel width in one embodiment, be in the scope of about 0.1%-about 50% of described microchannel width in one embodiment, and be in the scope of about 0.1%-about 40% of described microchannel width in one embodiment.The width of described surface characteristics can be in the scope of the about 100cm of about 0.05mm-, in one embodiment in the scope of the about 5cm of about 0.5mm-, and in one embodiment in the scope of the about 2cm of about 1-.
A plurality of surface characteristics or surface characteristics zone can be contained in the passage, and comprise the surface characteristics with the recessed one or more microchannel wall of different depth.Distance between the described pit can be in the scope of the about 10mm of about 0.01mm-, and in one embodiment in the scope of the about 1mm of about 0.1-.Described surface characteristics can exist along the total length of microchannel or be present in the part or zone of described passage.Described part or zone with surface characteristics can be discontinuous, with the mixing that promotes the hope in the zone of adjusting or unit operations (for example separate, cooling etc.).For example, may have the surface characteristics that closely distributes alternately on one centimetre of part of passage, be four centimetres the smooth passage that does not contain surface characteristics then, is two centimetres of parts with loose surface characteristics at interval then.Term " at interval loose surface characteristics " refers to have pitch or the feature surface characteristics to the distance of feature, and described pitch or feature are to the distance of the feature width greater than about 5 times described surface characteristics.
Described surface characteristics can be arranged in one or more surface characteristics zone, extend on the whole axial length of passage substantially in this zone.In one embodiment, passage can have the surface characteristics of extending on about 50% or still less axial length of its axial length, and be in one embodiment its axial length about 20% or still less.In one embodiment, described surface characteristics can be extended on the axial length of about 10%-about 100% of the axial length of described passage, about in one embodiment 20%-about 90%, about in one embodiment 30%-is about 80%, and is about 40%-about 60% of the axial length of passage in one embodiment.
Each surface characteristics is striden journey (leg) can become the angle of inclination with respect to described overall flow direction.Can with described feature across length or span be defined as with described feature towards vertical direction.For example, surface characteristics can be the twill depression that becomes miter angle with respect to the plane perpendicular to the mean direction of the overall flow in the main channel, described main channel has the opening of 0.38mm or span or feature across length, and has the elongated degree of feature stream of 5.6mm.Described circulation length can be the distance of end to end on the longest direction from described surface characteristics, and described span or can be distance (not being the degree of depth) on the shortest direction across characteristic length.The described surface characteristics degree of depth can be the distance apart from described main channel.For the surface characteristics with non-homogeneous width (span), described span can be average in the average span of described circulation length.
Surface characteristics can comprise based in described surface characteristics bottom or the pit or the projection in the described outstanding zone at place, described surface characteristics top.If the described zone of locating at described surface characteristics top equals or exceeds in the zone at place, described surface characteristics bottom, can think that then described surface characteristics caves in.If the zone at place, described surface characteristics bottom exceeds in the zone at place, described surface characteristics top, can think that then described surface characteristics is a projection.For such description, described surface characteristics may be described as depression, but be understandable that, can alternatively described surface characteristics be defined as projection by the aspect ratio that changes described surface characteristics.For the process microchannel that limits by wall, described wall only traverses the top of described surface characteristics, especially for smooth passage, the all surface characterizing definition can be in depression, and be understandable that, by making surface characteristics can form similar passage from the base projections of passage, this passage has the cross section of the bottom that comprises described surface characteristics.
The process microchannel of described Fischer-Tropsch or generation alcohol, SMR process microchannel and/or burning gallery and/or hydrocracking process microchannel can have at least about 20%, in one embodiment at least about 35%, in one embodiment at least about 50%, in one embodiment at least about 70% and in one embodiment at least about the inner surface (promptly measuring in the cross section perpendicular to the net flow direction of passing described passage) of 90% the passage that comprises described surface characteristics perpendicular to length.Described surface characteristics can cover the continuous distance (stretch) at least about 1cm, and in one embodiment at least about 5cm.In the situation of closed channel, with from the bottom of described surface characteristics or top or between between the closed channel that evenly extends of steady state value compare the ratio of the cross section that the percentage of the covering of surface characteristics can be covered by surface characteristics.Described closed channel can be smooth passage.For example, if passage has patterned top or lower surface and the side wall surface of patterned high 0.1cm not, (wide) 0.9cm is striden on each surface in described top or the lower surface, and surface characteristics will be contained in the surface of so described passage 90%.
Process microchannel, SMR process microchannel and/or the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol can be sealed on all sides, and described in one embodiment passage can have common square or rectangular cross section (in the situation of oblong channel, can with the surface characteristics pattern setting on two main faces).For common square or oblong channel, described passage can be in only sealing on two or three sides, and only described two or three side wall surfaces can be used for the calculating of above-mentioned surface characteristics percentage.Can on the cylindrical channel of axial cross section, described surface characteristics be set with stable or variation.
Each pattern in the described surface characteristics pattern can reappear along the one side of described passage, and described pattern has spacing variation or rule between the surface characteristics on the described passage overall flow direction.The part embodiment can only comprise the single journey (leg) of striding of each surface characteristics, and other embodiments can comprise a plurality of journeys (two, three or more) of striding.For (wide-width) passage of wide, the file that composite surface feature or repetition surface characteristics can be set makes it adjacent one another are on described width of channel.For each pattern of described surface characteristics pattern, when described pattern repeated along the overall flow direction of described main channel, described depths of features, width, span and spacing can be to change or constant.In addition, have with different two characteristic surface dimensions of striding the summit of journey of angle connection alternate embodiment can be arranged, stride journey in surface characteristics described in the described embodiment and can not link to each other on described summit.
Described Fischer-Tropsch catalyst can comprise Fischer-Tropsch catalyst arbitrarily.Described Fischer-Tropsch catalyst can comprise metal or its oxide of at least a catalytic activity.In one embodiment, described Fischer-Tropsch catalyst may further include catalyst carrier.In one embodiment, described Fischer-Tropsch catalyst may further include at least a promoter.The metal of described catalytic activity can comprise the combination of Co, Fe, Ni, Ru, Re, Os or above-mentioned two or more materials.Described carrier material can comprise the combination of aluminium oxide, zirconia, silica, aluminum fluoride, fluorided alumina, bentonite, cerium oxide, zinc oxide, silica-alumina, carborundum, molecular sieve or above-mentioned two or more materials.Described carrier material can comprise resistant to elevated temperatures oxide.Described promoter can comprise I A, II A, III B or IV B family's metal or its oxide, lanthanide series metal or metal oxide or actinide metals or metal oxide.In one embodiment, described promoter is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th or its oxide, or the mixture of above-mentioned two or more materials.The example of spendable catalyst comprises that those are in United States Patent (USP) 4,585,798; 5,036,032; 5,733,839; 6,075,062; 6,136,868; 6,262,131B1; 6,353,035B2; 6,368,997B2; 6,476,085B2; 6,451,864B1; 6,490,880B1; 6,537,945B2; 6,558,634B1; U.S. Patent Application Publication 2002/0028853A1; 2002/0188031A1; With the catalyst disclosed in the 2003/0105171A1; Because these patents or patent application have disclosed the content about Fischer-Tropsch catalyst and preparation method thereof, so described patent or patent application are incorporated present patent application in the quoted passage mode.
In one embodiment, described Fischer-Tropsch catalyst can comprise the Co that is loaded on the carrier and randomly comprise synergistic catalyst and/or promoter, wherein said Co useful load is by weight at least about 5%, in one embodiment by weight at least about 10%, in one embodiment by weight at least about 15%, in one embodiment by weight at least about 20%, in one embodiment by weight at least about 25%, in one embodiment by weight at least about 28%, in one embodiment by weight at least about 30%, in one embodiment by weight at least about 32%, in one embodiment by weight at least about 35%, and in one embodiment by weight at least about 40%.In one embodiment, described Co useful load can be about 5-about 50% by weight, be about 10-about 50% in one embodiment by weight, be about 15-about 50% in one embodiment by weight, be about 20%-about 50% in one embodiment by weight, be about 25-about 50% in one embodiment by weight, be about 28-about 50% in one embodiment by weight, about 50% for about 30-by weight in one embodiment, and be about 32-about 50% in one embodiment by weight.The metal dispersity of the metal of the catalytic activity of described catalyst (being Co and randomly a kind of synergistic catalyst and/or promoter) can be that about 1-is about 30%, and is about 20% for about 2-in one embodiment, and is about 3-about 20% in one embodiment.Described synergistic catalyst can be Fe, Ni, Ru, Re, Os or its oxide, or the mixture of above-mentioned two or more materials.But described promoter I A, II A, III B or IV B family's metal or its oxide, lanthanide series metal or metal oxide or actinide metals or metal oxide.In one embodiment, described promoter is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th or its oxide, or the mixture of above-mentioned two or more materials.Can use by weight based on the concentration of the gross weight (being the weight of catalyst, synergistic catalyst, promoter and carrier) of described catalyst to about 10% synergistic catalyst, and be about 0.1-about 5% in one embodiment by weight.Can so that with on by weight based on the concentration of the gross weight of described catalyst to about 10% promoter, and be about 0.1-about 5% in one embodiment by weight.
Described Fischer-Tropsch catalyst can comprise the Co that is supported by aluminium oxide; The useful load of described Co is by weight at least about 25%, in one embodiment by weight at least about 28%, and in one embodiment by weight at least about 30%, and in one embodiment by weight at least about 32%; Described Co decentralization is at least about 3%, in one embodiment at least about 5%, and in one embodiment at least about 7%.
Described Fischer-Tropsch catalyst can comprise the composition of representing with following formula
CoM 1 aM 2 bO x
Wherein: M 1Be Fe, Ni, Ru, Re, Os or its mixture, and M in one embodiment 1Be Ru or Re or its mixture; M 2Be Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th, or the mixture of above-mentioned two or more materials; A is the number in about 0.5 scope of 0-, and is 0-about 0.2 in one embodiment; B is the number in about 0.5 scope of 0-, and is 0-about 0.1 in one embodiment; And x is the number that satisfies the required oxygen of element valence balance in the formula.
Can adopt a plurality of impregnation steps to prepare described Fischer-Tropsch catalyst, calcining (intercalcination) step in wherein can between each impregnation steps, carrying out.At least in one embodiment, use the useful load of the metal that plays catalytic action of so formed catalyst of method and the promoter of choosing wantonly than wherein not using the method for so interior calcining step higher.In one embodiment, will play the metal (for example Co) of catalytic action and optional synergistic catalyst (for example Re or Ru) and/or promoter through the following steps and be loaded into carrier (as Al 2O 3) on: (A) flood described carrier, so that the intermediate product of catalytic action to be provided with the metal that has comprised catalytic action and the synergistic catalyst of choosing wantonly and/or the composition of promoter; (B) intermediate product that plays catalytic action of calcining formation in step (A); (C) be soaked in the intermediate product of the calcining that forms in the step (B) with the another kind of composition that comprises catalytic metal and optional synergistic catalyst and/or promoter, so that the another kind of intermediate product that plays catalytic action to be provided; And (D) another kind of calcining formation in step (C) plays the intermediate product of catalytic action, so that the target product of catalytic action to be provided.Use just wet impregnation method (incipient wetness impregnation process) metal and the optional synergistic catalyst and/or the promoter of described catalytic action can be impregnated on the described carrier.Can repeating step (C) and (D) one or many, until the useful load of the hope of the metal that has reached catalytic action and optional synergistic catalyst and/or promoter.The composition that contains the metal of described catalytic action can be the nitrate solution of described metal, for example, and cobalt nitrate solution.Can proceed described method and reach about by weight 20% or more useful load until the metal (for example Co) of described catalytic action, in one embodiment about by weight 25% or more, in one embodiment about by weight 28% or more, in one embodiment about by weight 30% or more, in one embodiment about by weight 32% or more, in one embodiment about by weight 35% or more, in one embodiment about by weight 37% or more, and in one embodiment about by weight 40% or more.Each step in the described calcining step can be included in about 100 ℃-Yue 500 ℃ described catalyst of the interior heating of temperature range, be about 100 ℃-Yue 400 ℃ in one embodiment, and be about 350 ℃ of about 250-in one embodiment, be about 100 hours of about 0.5-heat time heating time, be about 24 hours of about 0.5-in one embodiment, and be about 3 hours of about 2-in one embodiment.Described temperature rises to described calcining heat with the speed of about 1-20 ℃/min.Can before described calcining step, carry out drying steps, dry described catalyst under the about 200 ℃ temperature of about 75-wherein, and be about 75 ℃-Yue 150 ℃ in one embodiment, be about 100 hours of about 0.5-drying time, and about 24 hours of about in one embodiment 0.5-.In one embodiment, can with described catalyst about 90 ℃ dry about 12 hours down, at about 110-120 ℃ of about 1.5 hours of the about 1-of drying down, can make temperature rise to 110-120 ℃ from 90 ℃ then with the speed of about 0.5-1 ℃/min.
Described Fischer-Tropsch catalyst can comprise the metal oxide of metal, metal oxide or mixing.Described metal can be the mixture of cobalt, iron, ruthenium or above-mentioned two or more materials.Described catalyst can comprise Co or its carbide or oxide.Such catalyst can also comprise one or more alkali metal, alkaline-earth metal, transition metal, rare earth metal and/or lanthanide series metal.Such catalyst can be loaded on the carrier, and if so, available carrier can comprise metal oxide, for example the combination of aluminium oxide, titanium oxide, zirconia and silica, mesoporous material, zeolite, resistant to elevated temperatures metal or above-mentioned two or more materials.Can carry out modification to described carrier by the oxide that adds a spot of one or more transition metal.Described catalyst can be any one in the disclosed Fischer-Tropsch catalyst of WO 2008/104793 A2, and the document is incorporated in the present patent application in the quoted passage mode.
Described Fischer-Tropsch catalyst can comprise on the content by weight the cobalt to about 60%, about by weight in one embodiment 10%-about 60%, about by weight in one embodiment 20%-about 60%, about by weight in one embodiment 30%-about 60%, about by weight in one embodiment 35%-is about 60%, and about by weight in one embodiment 35%-about 50%.Such catalyst can comprise cobalt and carrier.
Described Fischer-Tropsch catalyst can comprise cobalt and carrier.Can adopt United States Patent (USP) 7,183, the such catalyst of method activation disclosed in the 329B2, the document is incorporated in the present patent application in the quoted passage mode.Such method comprises using and contains the catalyst precarsor that contains cobalt compound and carrier at least about the gas activation of the hydrocarbon of 5mol%.
Because catalyst may change in reaction environment, therefore catalyst in the activity form (active form) and the catalyst in the precursor forms can be contained simultaneously in employed in this application term " catalyst ".Term " catalyst precarsor " can be interpreted as not only containing widely the catalyst precarsor or those catalyst precarsors unreduced or that in reaction, do not use that have just prepared by its catalysis, also be encompassed in the catalyst precarsor arbitrarily that can be used as catalyst after the activation, for example the catalyst that in reaction, has used by its catalysis.In like manner, be appreciated that term " activation " not only comprises the untapped or unreduced catalyst precarsor of activation, also comprises the catalyst that activation is used or reduce.Therefore, described term is included in the interior any activation of scope of its regeneration that contains used catalyst.
Can be by using the described Fischer-Tropsch catalyst of hydrocarbon activating catalyst precursor preparation.Described catalyst precarsor can comprise cobalt compound and carrier.Described carrier can be the carrier arbitrarily that can support the catalyst in the goal response.Described carrier can be an inert carrier, or can be active carrier.The example of operable carrier comprises aluminium oxide, modified aluminas, spinel oxide, silica, improved silica, magnesia, titanium oxide, zirconia, zeolite, β-aluminate and various forms of carbon.Described aluminium oxide or modified aluminas can be for example Alpha-alumina, beta-alumina or gama-alumina.Because beta-alumina and spinel oxide (for example six barium aluminates) have stability, so these materials may be favourable.Described carbon can be the form or the CNT of activated carbon.Can use zeolite.Described carrier can comprise hole or passage.
Cobalt compound can use together with described catalyst precarsor arbitrarily.Described cobalt compound can be the form of salt, for example water soluble salt or oxide.The example of spendable cobalt salt can comprise cobalt nitrate, cobalt acetate, cobalt benzoate, cobalt oxalate or acetylacetone cobalt.Because halide can influence carrier, so may wish to avoid using the halogenation cobalt.The example of operable cobalt oxide is Co 3O 4Can use one or more cobalt salts and/or its oxide.
Can adopt any known method to prepare described catalyst precarsor.Described catalyst precarsor can be added into and use solvent for example water or organic solvent for example in the carrier of the solution form of alcohol.Described alcohol can comprise about 4 carbon atoms of 1-.Such alcohol can comprise methyl alcohol and ethanol.Can remove described solvent then.Can by at room temperature or the down dry about 1-of temperature (for example about 50 ℃-Yue 250 ℃) that is higher than room temperature removed described solvent in about 24 hours.Can use the combination of a plurality of drying steps.Can be at room temperature with about 10 hours of the dry about 2-of the catalyst precarsor that is supported, about 8 hours of the about 2-of drying at elevated temperatures then, the temperature of described rising is for example about 100 ℃-Yue 200 ℃, and is about 120 ℃ in one embodiment.
If necessary, the solution that contains described catalyst precarsor can further comprise other component.For example, the solution of described catalyst precarsor can also comprise promoter or modifier.Described promoter can comprise the salt of alkaline-earth metal, for example magnesium nitrate, calcium nitrate, barium nitrate and/or strontium nitrate.Described promoter can also comprise the oxide of alkali metal, alkaline-earth metal or transition metal, and described oxide derivatives is from the water soluble compound of described metal, as described the salt of metal, for example LiNO 3, KNO 3, RbNO 3, Ba (NO 3) 2, Mg (NO 3) 2, Ca (NO 3) 2, Sr (NO 3) 2, Zr (NO 3) 2XH 2O, Ce (NO 3) 3XH 2O and UO (NO 3) 2Can in any way described promoter be loaded on the described carrier,, particularly flood or flood altogether with connecting of described cobalt compound for example by dipping.
Described modifier can comprise rare-earth modifier, for example salt of transition metal or rare earth or oxide, for example nitrate of lanthanum and/or cerium or acetate, or the d-district transition metal oxide of Mn, W, Nb and Vn for example.Described modifier can be immersed in described modifier in the described catalyst carrier then derived from the water soluble compound of described metal salt for example, under the temperature in about 300 ℃-Yue 1000 ℃ scope in air about 24 hours of the about 1-of calcining.Described promoter and modifier can use separately also and in the above-mentioned substance two or more can be used in combination.
Can adopt sol-gel (sol gel) method to prepare the described catalyst precarsor that is supported.For example, at " modern catalysts (Catalyst Today) " 35 (1997), 293-317 (people such as Gonzalez) and " modern catalysts " 41 (1997) have been described such method among the 3-19 (people such as J.Livage).For example, in initial " pregel (pregelation) " step, can make hydroxide or alcohol and metal precursor for example hydrolysis and simmer down to gel in the presence of water.Can in follow-up " behind the gel (post gelation) " step, add cobalt compound then, then with described gel drying and calcining.
The described catalyst precarsor that is supported can comprise the cobalt of the about 30wt% of about 0.05-, and the cobalt of the about 15wt% of about in one embodiment 0.5-.Based on the gross weight of the described catalyst precarsor that is supported, the described catalyst precarsor that is supported can comprise the cobalt compound of the about 50wt% of about 0.5-, promoter and the modifier of the about 20wt% of 0-or the modifier of the about 5wt% of about 0.01-of the about 10wt% of 0-.The described catalyst precarsor that is supported can comprise the cobalt compound of the about 40wt% of about 5-, the promoter of the about 3wt% of 0-and the modifier of the about 3wt% of 0-.
Can use the described catalyst precarsor that is supported of the gas activation that contains hydrocarbon.Described hydrocarbon can be a hydrocarbon arbitrarily.Described hydrocarbon can be saturated or undersaturated, for example contains 1,2 or 3 or the more a plurality of pairs of keys and/or triple bond.Described hydrocarbon can be linear, ring-type or contain side chain.Described hydrocarbon can also be aliphatic hydrocarbon or aromatic hydrocarbon, perhaps contains fat-based and aromatic radical simultaneously.Described hydrocarbon can be saturated hydrocarbons or the unsaturated hydrocarbons that contains to about 5 carbon atoms, and contains in one embodiment to about 4 carbon atoms.Described hydrocarbon can comprise the mixture of methane, ethane, acetylene, propane, propylene, butylene or above-mentioned two or more materials.
Described activated gas can comprise the described hydrocarbon at least about 5mol%, in one embodiment at least about 10mol%, and in one embodiment at least about 20mol%, and in one embodiment at least about 40mol%.The gas that contains described hydrocarbon can only comprise described hydrocarbon or described gas and can further comprise to about 10mol%, go up extremely about 20mol% in one embodiment and go up the extremely inert gas of about 40mol%, for example nitrogen and/or argon gas in one embodiment.Described gas can also comprise active component, for example also can activate the another kind of component of described catalyst precarsor.For example, described gas can comprise hydrogen.Described gas can comprise the combination of methane and/or ethane and hydrogen.If use hydrogen can adopt the ratio of hydrocarbon and hydrogen arbitrarily, for example can be at about 0.04: 1 or 0.05 based on the described ratio of mole: in about 100: 1 scope of 1-, perhaps about 0.1: 1 or about 0.5: about 10: 1 of 1-.
By activating under the atmosphere that the described catalyst precarsor that is supported is placed described activated gas.Described activated gas can pass the described catalyst precarsor that is supported.Activation temperature can be about 300 ℃ or higher, for example is about 400 ℃-Yue 1000 ℃, or is about 400 ℃-Yue 800 ℃.The duration of activation can be at least about 30 minutes, was at least in one embodiment about 1 hour, and about 20 hours of for example about 1-, and be about 5 hours of about 2-in one embodiment.Described activation temperature can be according to the different in kind of described catalyst precarsor and/or described hydrocarbon difference.Can use at normal pressure for carrying out described activation step, but also can use decompression or supercharging.
Can in reaction vessel, activate described catalyst precarsor, in this container, use the catalyst that is activated to react usually, perhaps can in other container, activate described catalyst precarsor.A large amount of oxidations can take place when the described catalyst exposure that is activated is in air.In order to stablize described catalyst, described catalyst can be placed and contain a small amount of for example atmosphere of the inert gas of the oxygen of about 1mol% (for example nitrogen or argon gas) and handle.Described catalyst can be placed described activated reactor, extract a spot of oxygen simultaneously out.Therefore, for example, can be by the processing in the atmosphere that oxygen reduces at least about 30 minutes or at least about stablizing the described catalyst that is activated in 1 hour, the atmosphere that described oxygen reduces comprises the oxygen that is less than about 20mol%, or be less than the oxygen of about 10mol%, or be less than the oxygen of about 5mol%, or be less than the oxygen of about 2mol%.
Can adopt United States Patent (USP) 7,304, the method for describing among 012 B2 prepares described Fischer-Tropsch catalyst, and the document is incorporated in the present patent application with citation form.Such method comprises the catalyst that preparation is supported or contains the catalyst precarsor of carbon.Said method comprising the steps of: (a) preparation (i) at least a catalyst carrier or catalyst carrier precursor, the (ii) at least a compound that contains metal, wherein said metal is selected from the liquefied mixture of V, Cr, Mn, Fe, Co, Ni, Cu, Mo and W and (iii) at least a polarity of solvent organic compound as the described compound that contains metal, and described liquefied mixture comprises the water based on the about 20wt% of 0-of the gross weight of described mixture; (b) described mixture is transformed into lotion or solid residue; And (c) in containing the atmosphere of aerobic the burning described residue at least in part described organic compound be converted into carbon and form described catalyst that is supported or catalyst precarsor.
In step (a), can prepare liquefied mixture: (i) catalyst carrier or catalyst carrier precursor by following at least three kinds of components; (ii) one or more contain the compound of metal and (iii) one or more randomly use described solvent as the described polarity of solvent organic compound solvent that contains the compound of metal with water.
Can simultaneously three kinds of all components be mixed.Can at room temperature or mix described component under the temperature that raises, for example in the about 200 ℃ temperature of about 20-, the about 80 ℃ temperature of about in one embodiment 40-, and the about 60 ℃ temperature of about in one embodiment 40-.
In an optional embodiment, can in preliminary step, earlier two kinds of components in described three kinds of components be mixed, add the third component then to finish described liquefied mixture.Can in preliminary step, component (ii) and (iii) be mixed.These two kinds of components can form transparent solution.Afterwards, can add component (i) and finish described liquefied mixture, be solid carrier as fruit component (i), and then described mixture may comprise solid particle.Can make described liquefied mixture at elevated temperatures, for example, the temperature that about 20-is about 200 ℃, and the about 80 ℃ temperature of about in one embodiment 30-.
Component (i) can be catalyst carrier or catalyst carrier precursor.Catalyst carrier can be the form of one or more solid particles.Described catalyst carrier precursor is initial can be the form of liquid or solution.For example, in case described catalyst carrier precursor is added in the described liquefied mixture then described precursor carrier can form solid catalyst carrier in position.Described catalyst carrier precursor can form catalyst carrier in step of converting (b) or combustion step (c).
Described catalyst carrier can be inert carrier or active carrier.The example of operable carrier can comprise soild oxide, carbide, zeolite, carbon and boron nitride.Such carrier can comprise aluminium oxide, modified aluminas, spinel oxide, silica, improved silica, magnesia, titanium oxide, zirconia, molecular sieve, zeolite, β-aluminate and various forms of carbon.Described aluminium oxide or modified aluminas can be for example Alpha-alumina, beta-alumina or gama-alumina.Beta-alumina and spinel oxide (for example six barium aluminates) are useful especially.Described carbon can be the form or the CNT of activated carbon.Can use zeolite.Described carrier can comprise hole or passage.Described zeolite can comprise zeolite A, X zeolite, zeolite Y, ZSMs, MCMs or AlPO 4
Described catalyst carrier precursor can be derived from Al (NO 3) 39H 2O and Mg (NO 3) 2At " modern catalysts (Catalyst Today) " 35 (1997), 293-317 (people such as Gonzalez) and " modern catalysts " 41 (1997) have been described operable catalyst precarsor among the 3-19 (people such as J.Livage) in further detail.
Described catalyst carrier can be derived from the nitrate of for example IIA family or IIIA family metal.For example, can use aluminum nitrate or magnesium nitrate.Described nitrate can be the form of hydrate.Example can comprise Al (NO 3) 39H 2O and Mg (NO 3) 26H 2O.In step (a), can with described nitrate and organic compound for example urea and/or ammonium citrate mix, to form transparent solution.Can randomly add water.In order to finish described liquefied mixture, can with the compound that contains metal for example cobalt nitrate be added in the described mixture.In the step in follow-up step of converting and combustion step, can form catalyst that is supported or the catalyst precarsor that is supported.
Described catalyst can be a porous.Particle size can be the about 20mm of about 0.1 μ m-, perhaps is the about 5mm of about 0.2 μ m-.Surface area can be greater than about 5m 2/ g, or greater than about 10m 2/ g, or greater than about 50m 2/ g, or greater than about 200m 2/ g.Can use one or both or more kinds of combinations in the catalyst carrier.
The component of described liquefied mixture (ii) can comprise the compound that one or more contain metal.The catalytic active component of described catalyst can be derived from such compound that contains metal.Metal in the described compound that contains metal can comprise the mixture of V, Cr, Mn, Fe, Co, Ni, Cu, Mo, W or above-mentioned two or more materials.Can with other metal for example the mixtures of at least a or above-mentioned two or more materials in Zr, U, Ti, Th, Hf, Ce, La, Y, Mg, Ca, Sr, Cs, Rb, Mo, W, Cr, Mg, rare earth metal, the noble metal (noble metal) as for example promoter or modifier.For example, the described compound that contains metal can comprise at least a and at least a metal that is selected from lanthanide series metal, actinide metals and transition metal series in the periodic table of elements among V, Cr, Mn, Fe, Co, Ni, Cu, Mo or the W.Described additional metals can be f-district or d-district metal.
Described other metal can be one or more metals that are selected from noble metal (for example Pd, Pt, Rh, Ru, Ir, Au, Ag and Os), transition metal (for example Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg, Tl) and 4f-district lanthanide series metal (for example La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu).In such metal, Pd, Pt, Ru, Ni, Co, Fe, Cu, Mn, Mo and W may be useful especially.
The described compound that contains metal can comprise other element.The described compound that contains metal is the form of salt.The described example that contains the salt of metal can comprise nitrate, citrate, halide, hydroxide, phenates, acetate, benzoic acid eye, oxalates and acetylacetonate.
The component of described liquefied mixture (iii) can be a polar organic compound.Described organic compound can be used as the solvent of component (i) and can be used as component solvent (ii).Described organic compound can be can the atmosphere that contains aerobic for example air in the presence of any polar organic compound of burning.In the process of burning, described organic compound can be converted into the carbon that may exist, for example described carbide that contains the compound metal (ii) of metal with the form of elemental carbon or carbide.Part or all of organic compound can be converted into carbon, thereby and can make the part organic compound completing combustion described carbon is converted into carbon monoxide or carbon dioxide, then described carbon is removed from described catalyst or described catalyst precarsor with gas form.Described organic compound can be through not producing the particularly compound of oxide ash content of ash content after the described combustion step.Described organic compound can be that a kind of burning back of not containing forms for example compound of the element of oxide of residue easily.Such element can comprise for example metal, phosphorus and/or silicon.
The example of operable organic compound comprises ammonium salt, amino acid and the surfactant of organic amine, organic carboxyl acid and salt thereof (for example ammonium salt), alcohol, phenol and hydroxide.Described alcohol can be those alcohol that comprise about 30 carbon atoms of 1-or comprise about 15 carbon atoms of 1-.Spendable alcohol can comprise methyl alcohol, ethanol and ethylene glycol.The example of described carboxylic acid can be citric acid or oxalic acid.Other organic compound can be the compound that contains for example one or more hydroxyls of functional group, amino, amide groups, carboxyl, ester group, aldehyde radical, ketone group, imido grpup, imide.Such compound can comprise urea, azanol, trimethylamine, triethylamine, tetramethyl ammonium chloride and etamon chloride.Described organic compound can comprise EDTA, urea and/or ammonium citrate.
Described organic compound at room temperature or can be the form of liquid under the temperature of preparation during described mixture.Can heat described organic compound earlier is added into it in described mixture then.Described organic compound at room temperature or under the temperature of preparation during described mixture, also can be the form of solid, under these circumstances, with the mixture heating for preparing so that the fusion of described organic compound makes described metallic compound dissolving then.Can use the mixture of organic compound.Can also add water, for example to promote the dissolving of described metallic compound.
When water is used for described liquefied mixture, may need to control the water yield.For example, certain catalyst carrier precursor is as Fe (NO 3) 39H 2O and Al (NO 3) 39H 2O, the water that contacts effective dose when one just forms gel easily.Therefore, should make the amount of employed water in the step (a) remain minimum of a value to avoid the formation of hydrolysis gel.Such water yield may be enough for making described catalyst precarsor partial hydrolysis, but is not enough to described catalyst precarsor is converted into polymer.Especially, can use with respect on the gross weight of described mixture to the water of about 20wt%.
Can add water individually or can be for example exist as the crystallization water or the water of coordination of a component in the described component.
Described mixture can also comprise other component.Such component comprises promoter and/or modifier.Described promoter can comprise alkali salt for example magnesium nitrate, calcium nitrate, barium nitrate and/or strontium nitrate.Described modifier can comprise the rare-earth modifier for example nitrate of rare-earth salts, for example lanthanum and/or cerium or the oxide of acetate or described d-district transition metal.Can use the oxide of phosphorus, boron, gallium, germanium, arsenic and antimony.Can use described promoter and modifier or being used in combination individually with above-mentioned two or more materials.
The mixture that makes in step (a) can be a liquefied mixture.Although term " liquefied mixture " means such fact that described mixture is the homogeneous liquid form, described mixture can comprise solid particle.For example, after the homogeneous phase liquefied mixture that forms described organic compound, optional water and metallic compound, can add the particle of insoluble inert carrier.For example, if having catalyst carrier rather than catalyst carrier precursor, then described liquid can comprise solid carrier particle.The described compound that contains metal should contact with described carrier or precursor carrier, and this can realize by using liquid mixture.
The component of using in step (a) (i): (ii): weight ratio (iii) is 0.1-80: 1-90: 1-99 or about 0.5-60: 2-80: 10-90.Described weight ratio can be according to the difference of the purposes of the hope of final catalyst and difference.Atomic ratio that can be by the metal in the compound that contains metal of carbon in the described organic compound and described dissolving (C: M) define the amount of organic compounds.Described atomic ratio can be at least 0.4: 1 or about 20: 1 of about 1-.
After described liquefied mixture is made, can in step (b), described liquefied mixture be transformed into lotion or solid residue.This can realize by the described mixture of heating.Such heating steps can be the needed extra any heating of the described organic compound of fusion, although required the described heating of aforesaid heating only to maintain in the step (b).Described heating changes described liquefied mixture into solid, for example evaporation or the decomposition by described organic solvent.Can the evaporation of water arbitrarily of described liquefied mixture will be present in.Heating described mixture, to make its temperature that reaches can be the arbitrary temp that is higher than room temperature, for example about 50 ℃-Yue 250 ℃, and can form solid residue until it with the described mixture of time (about 24 hours of for example about 1-) heating arbitrarily.Can use the combination of a plurality of drying steps.At first at room temperature the about 2-of drying is about 10 hours, and is dry at elevated temperatures then, for example about 100 ℃-Yue 200 ℃ or about 120 ℃.
Described mixture can burn in step (c).Can in air, carry out described combustion step.Alternatively, can use purity oxygen or the oxygen in the inert atmosphere of nitrogen or other inert gases for example.Such combustion step can be independent of the heating in the step (b), perhaps described two steps can be used in combination, for example by only continuing to add hot mixt except that after desolvating.
Ignition temperature can be about 200 ℃-Yue 1000 ℃, perhaps about 400 ℃-Yue 600 ℃.Can make described combustion step continue any a period of time, for example, about 60 minutes or still less, perhaps about 30 minutes or still less, perhaps about 15 minutes or still less, about 15 minutes of perhaps about 5-.Described combustion step can make described polar organic compound be converted into carbon and volatilizable thing.Do not wish to be limited by theory, think that described combustion step can completely or partially make the described compound that contains metal change the form of metal and/or one or more oxides, oxycarbide or carbide or the mixture of above-mentioned two or more materials into.Described combustion step can also make described promoter and/or modifier (if they exist) be converted into the form of oxide.
Can carry out the preparation of described Fischer-Tropsch catalyst by at first the described compound that contains metal and polar organic compound being mixed.Such mixture may be thickness and adhere to solid catalyst carrier, can be coated in the outer surface of described carrier, described carrier only has limited " interior " for example infiltration in hole of surface.After described combustion step, can obtain so-called " eggshell " formula catalyst, all or nearly all catalyst may be present in the surface of described carrier in this catalyst.Such method makes described catalyst in the distribution of the lip-deep distribution of the described carrier catalyst when only making water as solvent better and more even.
Can also carry out the preparation of described Fischer-Tropsch catalyst by at first the described compound that contains metal being mixed the carrier that adds solubility then with described organic compound.After burning, can make described catalyst be distributed in " outward " surface and " interior " surface of described carrier simultaneously.Such method makes the distribution of described catalyst on whole carrier being more evenly distributed than aforesaid well-known catalysts.
Described Fischer-Tropsch catalyst or catalyst precarsor are distributed on " outward " surface of described carrier or in " interior " surface.Can make described catalyst or catalyst precarsor be distributed in whole carrier substantially or only on the outer surface of described carrier.Can control the distribution of active catalytic components or its precursor.
Described Fischer-Tropsch catalyst or catalyst precarsor can comprise might form carbon.For example, described carbon can be used as that elemental carbon exists or exists as the form of metal carbides or oxycarbide.Described carbon content could be up to about 8wt% based on the gross weight of described catalyst or catalyst precarsor, perhaps about 0.01-8wt%, or the about 2wt% of about 0.01-.
Based on the gross weight of described catalyst that is supported or catalyst precarsor, described Fischer-Tropsch catalyst that is supported or catalyst precarsor can comprise the catalyst of the about 50wt% of about 0.5-or the modifier of catalyst precarsor, the about 10wt% promoter of 0-and the about 5wt% of 0-.Described catalyst that is supported or catalyst precarsor can comprise catalyst or catalyst precarsor, the promoter of the about 3wt% of 0-and the modifier of the about 3wt% of 0-of the about 40wt% of about 5-.
Can be by hydrogen or appropriate hydrocarbon gas or hydrocarbon vapour described Fischer-Tropsch catalyst that is supported of activation or catalyst precarsor.Remove described solvent by heating, thereby make described organic compound be deposited in the hole of described catalyst carrier.Then can be with described catalyst carrier and the described compound that contains metal.Alternatively, described catalyst carrier and the described metallic compound that contains can be integrated.Such method can generate catalyst or the catalyst precarsor that is supported, and in the described catalyst or catalyst precarsor that is supported, can make described catalyst or catalyst precarsor be positioned at the outer surface of described porous particle substantially.
The described catalyst that generates alcohol can comprise the catalyst arbitrarily that is fit to synthesis gas is converted into one or more alcohol.The described catalyst that generates alcohol can comprise the mixture that catalyst metals among Nb, Ta, Mo, W, Tc, the Re or above-mentioned two or more materials form with freedom or combining form.Described catalyst metals and synergistic catalyst metallic yttrium, lanthanide series metal, actinide metals or above-mentioned two or more materials can be made up with the mixture that freedom or combining form form.The described catalyst that generates alcohol can comprise RhAg, CuCo, CuThO xAnd/or CoMoS.Term " with freedom or combining form " means that the metal target component can be used as the combination existence of metal, alloy, compound, addition product or above-mentioned substance.Representative compound comprise hydroxide, oxide, sulfide, sulfate, halide, carbide, cyanide, nitride, nitrate, phosphate, boride, silicide, silicate, oxyhalide, carboxylate (for example acetate and acetoacetate), oxalates, carbonate, carbonyl compound (carbonyls), halide, the cluster compound of metal bridging, metal be partial cation or anionic compound or the like.Described addition product is the product of chemical addition.Can with the molecule of polar solvent or electron donating solvent, former solvent (former solvent) or complexant for example ammonia (ammonia), aliphatic or aromatic amine, imines, amino alcohol, carboxylic acid, amino acid, dialkyl group-and trialkyl-and triaryl phosphine ,-arsine and
Figure BPA00001272662800521
(stibines) and oxide, mercaptan, amineothiot or the like replace or be not added in the described catalyst metals with not replacing.At United States Patent (USP) 4,762, such catalyst has been described in 858, the document is incorporated present patent application in the quoted passage mode.
The described catalyst that generates alcohol can comprise methanol synthesis catalyst, copper/cobalt-based or the copper/cobalt improved Fischer-Tropsch catalyst based on copper or copper modification, and (for example Rh) is catalyst based for rare metal, or Mo or MoS 2Catalyst based.At United States Patent (USP) 4,122,110,4,298,354,4,492,773 and 4,882,360 and " synthetic cyclostrophic being turned to the summary of current research document of the efficient catalytic technology of ethanol " (" energy and fuel (Energy and Fuel) ", XXXX of people such as Subramani, xxxx, 000-000,2007) described such catalyst in, described document is incorporated present patent application in the quoted passage mode.
Described catalyst and the dehydration catalyst that generates alcohol can be used in combination, think that the unsaturated hydrocarbons route provides synthesis gas.The example of operable dehydration catalyst comprises acidic oxide, for example aluminium oxide, silica-alumina, zeolite and silicon-aluminium-phosphate synthesis of molecular sieve.Disclosed such catalyst in US 2006/0020155A1 and US 2007/0244000A1, described document is incorporated present patent application in the quoted passage mode.The described catalyst that generates alcohol can be mixed in identical conversion zone with described dehydration catalyst or combines.Alternatively, described dehydration catalyst can be arranged on the described downstream that generates the catalyst of alcohol, perhaps in identical micro passage reaction or in different micro passage reactions.
Described SMR catalyst can comprise SMR catalyst arbitrarily.Described SMR catalyst can comprise La, Pt, Fe, Ni, Ru, In, W and/or its oxide, or the mixture of above-mentioned two or more materials.In one embodiment, described SMR catalyst can further comprise MgO, Al 2O 3, SiO 2, TiO 2Or the mixture of above-mentioned two or more materials.In one embodiment, described SMR catalyst can be included in the 13.8%-Rh/6%-MgO/Al on the metal felt of FeCrAlY alloy 2O 3, the felt watermark (wash coating) of the FeCrAlY metal by about 0.25mm of used thickness and porosity about 90% prepares described catalyst.In one embodiment, described SMR catalyst can be derived from La (NO 3) 36H 2The O aqueous solution.In one embodiment, described SMR catalyst can be derived from Pt (NH 3) 4(NO 3) 2Solution.In one embodiment, described SMR catalyst can be derived from being deposited on one or more layers Al 2O 3On La (NO 3) solution and Rh (NO 3) solution.
Described combustion catalyst can comprise Pd, Pr, Pt, Rh, Ni, Cu and/or its oxide, or the mixture of above-mentioned two or more materials.In one embodiment, described combustion catalyst may further include Al 2O 3, SiO 2, MgO or above-mentioned two or more materials mixture.In one embodiment, described combustion catalyst can be derived from being deposited on Al 2O 3Pd (NO on the layer 3) 2Solution.In one embodiment, described combustion catalyst can comprise the Pr and the Pd layer of the precursor that uses the nitrate form and use Pt (NH 3) 4(NO 3) 2The Pt layer of solution.
Described hydrocracking catalyst can comprise hydrocracking catalyst arbitrarily.Such catalyst can comprise zeolite catalyst, and described zeolite catalyst comprises β zeolite, omega zeolite, L-zeolite, ZSM-5 zeolite and Y-type zeolite.Described hydrocracking catalyst can comprise the combination of one or more cross-linked clays (pillared clays), MCM-41, MCM-48, HMS or above-mentioned two or more materials.Described hydrocracking catalyst can comprise the combination of Pt, Pd, Ni, Co, Mo, W or above-mentioned two or more materials.Described hydrocracking catalyst can comprise resistant to elevated temperatures inorganic oxide, for example aluminium oxide, magnesia, silica, titanium oxide, zirconia and silica-alumina.Described hydrocracking catalyst can comprise hydrogenation component.The example of the hydrogenation component that is fit to comprises the metal of IVB family in the periodic table of elements and VIII family and the compound of such metal.Molybdenum, tungsten, chromium, iron, cobalt, nickel, platinum, iridium, osmium, rhodium and ruthenium can be used as described hydrogenation component.At United States Patent (USP) 6,312, such catalyst has been described among 586 B1, described document is incorporated present patent application in the quoted passage mode.
Can with described Fischer-Tropsch, generate alcohol, SMR, burning and/or hydrocracking catalyst be arranged on independent conversion zone or they be arranged in a plurality of conversion zone in described process microchannel or the burning gallery.In each conversion zone, can use identical or different catalyst.Described catalyst can be the catalyst of classification.In each conversion zone, the length in the one or more zones in or the heat exchange area that thermodynamics contacts adjacent with described conversion zone can change aspect its size.For example, in one embodiment, the length in the one or more zones in the described heat exchange area may be less than about 50% of the length of each conversion zone.Perhaps, what the length in the one or more zones in the described heat exchange area can be greater than the length of each conversion zone is about 50%, goes up to about 100% of the length of each conversion zone.
Described Fischer-Tropsch, generate alcohol, SMR, burning and/or hydrocracking catalyst can have size arbitrarily and the geometric configuration that is suitable for described process microchannel.Described catalyst can be the form of granular solids (as particle, powder, fiber or the like) with medium grain diameter of the about 1000 μ m (micron) of about 1-, the about 500 μ m of about in one embodiment 10-, the about 300 μ m of about in one embodiment 25-, and the about 300 μ m of about in one embodiment 80-.In one embodiment, described catalyst is the form of the fixed bed of granular solids.
Catalyst, the SMR catalyst of described Fischer-Tropsch or generation alcohol, combustion catalyst and/or hydrocracking catalyst can be the forms (as shown in Figure 15) of the fixed bed of granular solids.The medium grain diameter of described granular solids can be little, and the length of each process microchannel can be short relatively.Described medium grain diameter can be in the scope of the about 1000 μ m of about 1-, the about 500 μ m of about in one embodiment 10-, and the length of each process microchannel can be last to the scope of about 500cm, the about 500cm of about in one embodiment 10-, and the about 300cm of about in one embodiment 50-.
With reference to Figure 15, the catalyst 261 with bed or granular solids form is contained in the process microchannel 260.Shown in arrow 262, reactant enters fixed bed, and through reaction, shown in arrow 263, product flows out described fixed bed.
Catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst of described Fischer-Tropsch catalyst, generation alcohol can be loaded on the porous carrier structure for example combination of foams, felt rug, agglomerate or above-mentioned substance.Employed term " foams " refers to a kind of structure among the application, and this structure has the continuous wall that limiting holes runs through this structure.Employed term " felt rug " refers to form therein the structure of the fiber in gap among the application.Employed term " agglomerate " refers to a kind of silk thread of entanglement such as the structure of steel wire among the application.Described catalyst can be loaded on a kind of honeycomb structure body.Described catalyst can be loaded on the carrier structure body of flowing through, the felt that for example has adjacent space, foams with adjacent space, fin with space, cover on the substrate that is inserted into arbitrarily (washcoat) perhaps is parallel to described flow direction, the gauze of respective voids is provided for flowing.
Figure 16 illustrates the example of the structure of flowing through.In Figure 16, catalyst 266 is contained in the process microchannel 265.Shown in arrow 268 and 269, open channel 267 makes fluid pass process microchannel 265 to flow.Described reactant contacts with described catalyst and reacts and generates product.
Catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst of described Fischer-Tropsch catalyst, generation alcohol can be loaded in and flow through on the carrier structure body, for example foams, felt rug, pill, powder or gauze.Figure 17 illustrates the example that flows through structure.In Figure 17, flow through catalyst 271 and be contained in the process microchannel 270, shown in arrow 272 and 273, described reaction-ure flowing catalyst 271 and reaction generate described product.
The carrier structure body that is used to flow through catalyst can be made of material, and this material comprises the combination of silica gel, foams copper, sintered stainless steel fiber, steel wool, aluminium oxide or above-mentioned two or more materials.In one embodiment, described carrier structure body can by Heat Conduction Material for example metal make, import into or spread out of described catalyst to strengthen heat.
Can be directly with described Fischer-Tropsch catalyst, generate catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst cover of alcohol on the inwall of described process microchannel or burning gallery, be grown directly upon on the described conduit wall from solution, perhaps be coated on the fin structure body.Described catalyst can be the form of the continuous material of monolithic porous, perhaps has a lot of sheets of physics contact.In one embodiment, described catalyst can comprise a kind of continuous material, and has continuous porosity so that molecule can pass described catalyst diffusion.In this embodiment, described fluid flows through described catalyst but not flows around it.It is about 99% that the cross-sectional area of described catalyst can occupy about 1-of cross-sectional area of described process microchannel and/or burning gallery, and about in one embodiment 10-about 95%.Can record described catalyst by BET has greater than about 0.5m 2The surface area of/g, and in one embodiment greater than about 2m 2/ g.
Described Fischer-Tropsch catalyst, the catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst that generate alcohol can comprise boundary layer on porous carrier, the described porous carrier and the catalyst material on the described boundary layer.Described boundary layer can be the solution that is deposited on the described carrier, perhaps can be by chemical vapour sedimentation method or physical vapor deposition deposition.In one embodiment, described catalyst has porous carrier, cushion, boundary layer and catalyst material.Layer arbitrarily in the aforementioned layers can be continuous or can be discontinuous, with the form of spot or point or contain the space or the form of the layer in hole.Recording described porous carrier by mercury porosimetry can have at least about the about 1000 microns average pore size of 5% porosity and about 1-(bore dia and divided by hole count).Described porous carrier can be porous ceramics or metal foam body.Other available porous carriers comprise carbide, nitride and composite.Described porous carrier can have the porosity of about 30%-about 99%, and about in one embodiment 60%-about 98%.Described porous carrier can be the form of the combination of foams, felt rug, agglomerate or above-mentioned substance.The open chamber of described metal foam body can be about 20 holes of per inch (ppi)-Yue 3000ppi, and the about 1000ppi of about in one embodiment 20-, and the about 120ppi of about in one embodiment 40-.Term " ppi " refers to the maximum number (direction of measuring is irrelevant therewith, but in anisotropic material, described measurement is finished) in the hole of per inch on the direction of maximum hole count in isotropic material.
Described cushion, when existing, can have the composition and/or the density that not only are different from described porous carrier but also are different from described boundary layer, and in one embodiment, described cushion has the thermal coefficient of expansion between the thermal coefficient of expansion of described porous carrier and described boundary layer.Described cushion can be metal oxide or metal carbides.Described cushion can comprise Al 2O 3, TiO 2, SiO 2, ZrO 2Or the combination of above-mentioned substance.Described Al 2O 3Can be α-Al 2O 3, γ-Al 2O 3Or the combination of above-mentioned substance.Described cushion can be formed different subgrades by two or more and form.For example, when described porous carrier was metal, for example the stainless steel foams can use by two kinds and form the cushion that different subgrades is formed.First subgrade (contacting with described porous carrier) can be TiO 2Second subgrade can be to place described TiO 2On α-Al 2O 3In one embodiment, described α-Al 2O 3Subgrade is a dense layer, for following metal surface provides protection.Then, the boundary layer that can deposit low density high surface area is aluminium oxide for example, as the carrier of catalytic active layer.
The thermal coefficient of expansion of described porous carrier can be different from the thermal coefficient of expansion of described boundary layer.In such embodiments, need cushion transition between two kinds of thermal coefficient of expansions.Can regulate the thermal coefficient of expansion of described cushion by the composition of controlling described cushion, to obtain the thermal coefficient of expansion with the thermal coefficient of expansion compatibility of described porous carrier and boundary layer.Described cushion should not have opening or aperture, thereby provides best protection for following carrier.Described cushion can be an atresia.The thickness of described cushion can be less than half of the average pore size of described porous carrier.The thickness of described cushion can be the about 10 μ m of about 0.05-, the about 5 μ m of about in one embodiment 0.05-.
In one embodiment, under the situation that does not have cushion, can obtain enough adhesions and chemical stability.In this embodiment, can save described cushion.
Described boundary layer can comprise the combination of nitride, carbide, sulfide, halide, metal oxide, carbon or above-mentioned substance.Described boundary layer has high surface and/or the catalyst-carrier interactions of hope is provided for the catalyst that is supported.Described boundary layer can be made up of the metal arbitrarily that uses as catalyst carrier traditionally.Described boundary layer can comprise metal oxide.The example of operable metal oxide comprises α-Al 2O 3, SiO 2, ZrO 2, TiO 2, tungsten oxide, magnesia, vanadium oxide, chromium oxide, manganese oxide, iron oxide, nickel oxide, cobalt oxide, cupric oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminium oxide, lanthanide oxide, zeolite and above-mentioned substance combination.The catalytically-active materials that described boundary layer can not have any other as catalytic active layer is deposited on described boundary layer.Described boundary layer can be used in combination with catalytic active layer.Described boundary layer can also be formed different subgrades by two or more and form.The thickness of described boundary layer can be less than half of the average pore size of described porous carrier.The thickness of described boundary layer can be the about 100 μ m of about 0.5-, and the about 50 μ m of about in one embodiment 1-.Described boundary layer can be crystallization or amorphous.Described boundary layer can have at least about 1m 2The BET surface area of/g.
Catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst of described Fischer-Tropsch catalyst, generation alcohol are deposited on the described boundary layer.Alternatively, described catalyst material is deposited on the described boundary layer.Described catalyst layer closely is dispersed on the described boundary layer.Described described catalyst layer " dispersion " or " deposition " of making comprises on described boundary layer that traditionally the small catalyst granules of understanding that makes is scattered in: on described carrier layer (the being boundary layer) surface, in the crack of described carrier layer and in the open bore of described carrier layer.
Catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst of described Fischer-Tropsch catalyst, generation alcohol can be loaded into the assembly that contains one or more fins that is arranged in the described process microchannel.Example is shown among Figure 18-20.With reference to Figure 18, fin component 280 comprises the fin 281 that is installed on the fin carrier 283, and fin carrier 283 is superimposed upon on the diapire 284 of process microchannel 285.Fin 281 stretches out the inside that enters process microchannel 285 from fin carrier 283.Fin 281 can extend to process microchannel 285 upper wall 286 inner surface and contact with described inner surface.Fin channels 287 between the fin 281 provides passage for the process microchannel 285 that reactant and product is flow through be parallel to described finned length.Each fin in the fin 281 all has outer surface at its each side.Described outer surface provides carrier substrates for described catalyst.Described reactant can flow through fin channels 287, contact with the catalyst that supports on the outer surface of fin 281, and reaction generates product.Except fin 281a and not exclusively extend to the inner surface of upper wall 286 of microchannel 285, the fin component 281a of example is similar with fin component 280 routine shown in Figure 18 shown in Figure 19.Fin 281b in fin component 280b has the trapezoidal cross section, and the fin component 280 of example shown in the fin component 280b of example and Figure 18 is similar shown in Figure 20.Each fin in the described fin has the supreme height to process microchannel 285 of height of about 0.02mm, the about 10mm of about 0.02-in one embodiment, the about 5mm of about in one embodiment 0.02-, and the about 2mm of about in one embodiment 0.02-.The width of each fin can be the about 5mm of about 0.02-, the about 2mm of about in one embodiment 0.02-, and the about 1mm of about in one embodiment 0.02-.The length of each fin can be the random length that goes up to the length of process microchannel 285, go up in one embodiment to about 10m, be the about 10m of about 0.5-in one embodiment, be the about 6m of about 0.5-in one embodiment, and be the about 3m of about 0.5-in one embodiment.Space between each fin in the described fin can be to be worth arbitrarily, and can be the about 5mm of about 0.02-, is the about 2mm of about 0.02-in one embodiment, and is the about 1mm of about 0.02-in one embodiment.In the process microchannel 285, the fin number of every centimetre of process microchannel 285 width can be about 1-about 50, be every centimetre of about 30 fins of about 1-in one embodiment, be every centimetre of about 10 fins of about 1-in one embodiment, be every centimetre of about 5 fins of about 1-in one embodiment, and be every centimetre of about 3 fins of about 1-in one embodiment.Each fin in the described fin can have rectangle or the square cross section as shown in Figure 18 or 19, perhaps trapezoidal cross-section as shown in Figure 20.When the length of fin is seen, each fin is linear, taper or serpentine-like configuration.Described fin component can be made by material arbitrarily, and this material provides enough intensity, dimensional stability and thermal conduction characteristic with by the described process microchannel of expection operation.Such material comprises: the combination of the alloy of any metal in steel (for example stainless steel, carbon steel or the like), aluminium, titanium, nickel, platinum, rhodium, copper, chromium, the aforementioned metal, monel metal, Inconel, brass, polymer (for example thermosetting resin), pottery, glass, quartz, silicon or aforementioned two or more materials.Described fin component can be by Al 2O 3Or Cr 2O 3Moulding material is made.Described fin component can be made by alloy that contains Fe, Cr, Al and Y or the alloy that contains Ni, Cr and Fe.
Catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst of described Fischer-Tropsch catalyst, generation alcohol can be the forms of grain bed, can be according to forming or carrying out classification with heat conduction inert material to particle.Described active catalyst is distributed on the described heat conduction inert material.The example of operable heat conduction inert material comprises bortz powder, carborundum, aluminium, aluminium oxide, copper, graphite or the like.Described catalyst bed component can be about by weight 100% a active catalyst-by weight less than about 50% active catalyst.Described catalyst bed component can be the active catalyst of about by weight 10%-about 90%, and about by weight in one embodiment 25%-about 75%.In an alternative embodiment, can make described heat conduction inert material be distributed in the center or the described catalyst particles intragranular of described catalyst.Described active catalyst is deposited on contains in outside, inside and the interval of the complex structure body of described hot conduction inert material.When placing process microchannel or burning gallery, the catalyst composite structure body of formation can have the effective heat conductivity at least about 0.3W/m/K, in one embodiment at least about 1W/m/K, and in one embodiment at least about 2W/m/K.
Can in described process microchannel or burning gallery, only carry out local classification by catalyst, SMR catalyst, combustion catalyst and/or the hydrocracking catalyst to described Fischer-Tropsch catalyst, generation alcohol.For example, process microchannel can comprise the catalyst bed with first conversion zone and second conversion zone.Can carry out classification to top or bottom (or front portion or rear portion) of described catalyst bed according to forming, thus, in all or part described first or second conversion zone, use more or less active catalyst.The composition that reduces in a conversion zone may produce less heat by per unit volume, thereby reduces thermal potential point and produce the possibility of undesirable accessory substance (for example methane in the Fischer-Tropsch reaction).In all or part first and/or second conversion zone, can carry out classification to described catalyst by inert material.Described first conversion zone can comprise first catalyst or the inert material of forming, and second conversion zone can comprise second and form catalyst or inert material simultaneously.
Can in the different axial region of described process microchannel or burning gallery, use different particle sizes, offer by the catalyst bed of classification.For example, very little particle can be in first conversion zone, used, bigger particle can be in second conversion zone, used simultaneously.Average particulate diameter can be less than the height of described process microchannel or half of space.Described very little particle can be less than 1/4th of the height of described process microchannel or space.Bigger particle may make the pressure drop on the per unit length of described process microchannel less, and also may reduce the validity of described catalyst.The available heat conduction of the catalyst bed of large-size particle may be lower.Smaller particles can be used for those and need improve the whole heat conducting zone of catalyst bed, perhaps alternatively, can use bigger particle to reduce the local speed of heat production.
By the required the evolving path of limiting catalyst can obtain relatively short time of contact, to the high selectivity of target product and the relative low deactivation rate of catalyst.When described catalyst is thin layer form on the engineered vector (for example metal foam body) or the thin layer form on the described process microchannel wall, can realize technique scheme.The air speed that this can obtain to increase.Can use chemical vapour sedimentation method to make described catalyst film.The thickness of described thin layer can be last to about 1 micron scope, in one embodiment in the about 1 micron scope of about 0.1-, and in one embodiment in the about 0.5 micron scope of about 0.1-, and about in one embodiment 0.25 micron.By dwindling described the evolving path, such thin layer can reduce the time of reactant in the active catalyst structure.This can reduce the time of reactant in described activity of such catalysts part.The possibility of result is to have improved the selection rate of product and reduced unwanted accessory substance.The advantage of this catalyst distribution pattern may be, the traditional catalyst of low-heat conduction binding thing that may be bound to inertia with the part of activity of such catalysts wherein is different, and the active catalyst film can closely contact with the wall of engineering structural system or described process microchannel.Adopt such technical scheme, in micro passage reaction, can obtain high thermal conduction rate and can closely control temperature.This can obtain at elevated temperatures the ability of (dynamics faster) operation, and does not cause the formation of undesirable accessory substance, therefore produces higher productivity and productive rate, and prolongs catalyst life.
The structure that can change the pure micro passage reaction 200 of SMR micro passage reaction 500, hydrocracking micro passage reaction 700 and/or described Fischer-Tropsch or generation is with the coupling kinetics.Near the microchannel height of the inlet of first conversion zone of process microchannel or top end or space can less than in second conversion zone near the outlet of described process microchannel or the microchannel height or the space at place, bottom.Alternatively, described conversion zone can be less than half of described process microchannel length.For example, the one 25%, 50%, 75% or 90% of described process microchannel length can be as first process microchannel height or the space of first conversion zone, and can use second higher height or the space in second conversion zone in the described first conversion zone downstream.Such structure may be fit to carry out Fischer-Tropsch or generate the alcohol reaction.In described process microchannel height or space, can adopt other hierarchy plans.For example, can use first height or space so that first conversion zone to be provided near the porch of described microchannel, can use second height or space so that second conversion zone to be provided at the downstream part of described first conversion zone, and can use the 3rd height or space near the exit of described microchannel so that the 3rd conversion zone to be provided.Described first with the 3rd the height or the space can be identical or different.The described first and the 3rd height or space can be greater than or less than described second height or the space.Described the 3rd the height or the space can less than greater than described second the height or the space.Described second height or space can be greater than or less than described the 3rd height or space.
By making regenerative fluid flow through passage contacts the described Fischer-Tropsch catalyst of can regenerating, generates alcohol with catalyst catalyst, SMR catalyst, combustion catalyst and/or hydrocracking catalyst.Described regenerative fluid can comprise hydrogen or diluted hydrogen stream.Diluent can comprise the mixture of nitrogen, argon gas, helium, methane, carbon dioxide, steam or above-mentioned two or more materials.The temperature of described regenerative fluid can be about 400 ℃ of about 50-, and is about 350 ℃ of about 200-in one embodiment.In the process of such regeneration step, the pressure in the described passage can be about 40 atmospheric pressure of about 1-, is about 20 atmospheric pressure of about 1-in one embodiment, and is about 5 atmospheric pressure of about 1-in one embodiment.The time of staying of described regenerative fluid in described passage is about 1000 seconds of about 0.01-, and is about 0.1 second-Yue 100 seconds in one embodiment.
When catalyst is Fischer-Tropsch catalyst, can be by the following mode described catalyst of regenerating: with the H in the reactant composition 2: the mol ratio of CO was increased at least about 2.5: 1, be increased at least about in one embodiment 3: 1, then under the temperature in about 150 ℃-Yue 300 ℃ of scopes, in one embodiment under the temperature in about 180 ℃-Yue 250 ℃ of scopes, make the adjusted feed composition of generation flow through described process microchannel and contact a period of time with described catalyst, described time of contact is in the about 100 hours scope of about 0.1-, in one embodiment in the about 20 hours scope of about 0.5-, so that the catalyst of regeneration to be provided.Flowing and making described hydrogen stream cross described process microchannel and contact with described catalyst and can adjust described feed composition by all feed gas of disturbance except hydrogen.Can increase H 2Flow to provide and to contain H 2The time of contact identical with the reactant composition of CO.Described adjusted feed composition can comprise H 2, and described composition is characterised in that and does not contain CO.In case described catalyst is reproduced, then the catalyst by making described regeneration with comprise H 2Contact with the initial reactant composition of CO and can continue described fischer-tropsch process.
Process microchannel, SMR process microchannel, burning gallery and/or the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol are characterised in that to have the overall flow path.Term " overall flow path " refers to the open approach (coherent overall flow zone) in described process microchannel or burning gallery.The overall flow zone that links up makes fluid flow through described passage fast and big pressure drop do not occur.In one embodiment, the fluid in described overall flow zone is mobile is laminar flow.It is about 10 that overall flow zone in each process microchannel or burning gallery can have about 0.05-, 000mm 2Cross-sectional area, the about 5000mm of about in one embodiment 0.05- 2, and the about 2500mm of about in one embodiment 0.1- 2It is about 95% that described overall flow zone can comprise about 5%-of described process microchannel or burning gallery cross section, about in one embodiment 30%-about 80%.
Could be up to the time of contact of catalyst, SMR catalyst and/or the combustion catalyst of described reactant and described Fischer-Tropsch or generation alcohol about 2000 milliseconds (ms), in about 10-arrives the scope of about 2000ms, the about 1000ms of about in one embodiment 10-, and the about 500ms of about in one embodiment 20ms-.In one embodiment, could be up to about 300ms described time of contact, the about 300ms of about in one embodiment 20-, the about 150ms of about in one embodiment 50-, the about 125ms of about in one embodiment 75-, and about in one embodiment 100ms.In one embodiment, could be up to about 100ms described time of contact, and the about 100ms of about in one embodiment 10-.
Described Fischer-Tropsch or the mobile air speed (or the gas space velocity (GHSV) in the unit interval) of fluid that generates in pure process microchannel, SMR process microchannel and/or the burning gallery can be at least about 1000hr -1(standard litres of charging/hour/volume in the described process microchannel rise number) or (hr) at least about 800ml charging/(g catalyst).Described air speed can be that about 1000-is about 1,000,000hr -1, the about 800000ml charging of perhaps about 800-/(g catalyst) (hr).In one embodiment, described air speed can be about 10, and 000-is about 100,000hr -1, perhaps about 8,000-is about 80, and 000ml charging/(g catalyst) is (hr).
In described hydrocracking reactor, the liquid air speed (LHSV) in the unit interval of liquid flow can be the about 100hr of about 0.1- -1(volume of the volume of charging/hr/ catalyst), the about 100hr of about in one embodiment 1- -1, the about 100hr of about in one embodiment 5- -1, the about 100hr of about in one embodiment 10- -1, the about 50hr of about in one embodiment 1- -1, and the about 50hr of about in one embodiment 5- -1
Described Fischer-Tropsch or the pressure that generates in pure process microchannel, SMR process microchannel and/or the hydrocracking process microchannel could be up to about 100 atmospheric pressure, in one embodiment in about 100 the atmospheric scopes of about 1-, about 75 atmospheric pressure of about in one embodiment 1-, about 40 atmospheric pressure of about in one embodiment 2-, about 50 atmospheric pressure of about in one embodiment 10-, and about 30 atmospheric pressure of about in one embodiment 20-.
When fluid flows in process microchannel, SMR process microchannel, burning gallery and/or the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol, the pressure drop of described fluid could be up to about 10 the every rice grain pattern of atmospheric pressure roads long (atm/m), and go up in one embodiment to about 5atm/m, and go up in one embodiment to about 3atm/m.
Described Fischer-Tropsch or generate Reynolds number that the fluid in process microchannel, SMR process microchannel, burning gallery and/or the hydrocracking process microchannel of alcohol flows can be in the scope of about 10-about 4000, and about in one embodiment 100-about 2000.
Mean temperature in the described fischer-tropsch process microchannel can be at about 150-about 300 ℃, and about 300 ℃ of about in one embodiment 200-.
Mean temperature in the described process microchannel that generates alcohol can be in the about 500 ℃ scope of about 200-, and about 350 ℃ of about in one embodiment 200-.
Mean temperature in the described SMR process microchannel can be in the about 400 ℃ scope of about 100-, and about 350 ℃ of about in one embodiment 150-.
Mean temperature in the described hydrocracking process microchannel can be in about 100 ℃-Yue 700 ℃ scope, about in one embodiment 250 ℃-Yue 500 ℃, about in one embodiment 350 ℃-Yue 450 ℃, and about in one embodiment 370 ℃-Yue 400 ℃.
The temperature that enters described Fischer-Tropsch or generate the micro passage reaction 200 of alcohol and randomly enter the heat-exchange fluid of hydrocracking micro passage reaction 700 can be about 100 ℃-Yue 400 ℃, and and about in one embodiment 200 ℃-Yue 300 ℃.The temperature that flows out the heat-exchange fluid of described hot switching path can be in about 150 ℃-Yue 450 ℃ scope down, and about in one embodiment 200 ℃-Yue 350 ℃.The time of staying of described heat-exchange fluid in described hot switching path is the about 2000ms of about 1-, and the about 500ms of about in one embodiment 10-.When described heat-exchange fluid flow through described hot switching path, the pressure drop of described heat-exchange fluid could be up to about 10atm/m, the about 10atm/m of about in one embodiment 1-, and the about 5atm/m of about in one embodiment 2-.Described heat-exchange fluid can be the form of steam, liquid or steam and mixtures of liquids.The Reynolds number that described heat-exchange fluid flows in hot switching path is about 4000 for about 10-, and about in one embodiment 100-about 2000.
Heat-exchange fluid that use and that randomly use in hydrocracking micro passage reaction 700 can be the heat-exchange fluid arbitrarily that is suitable for cooling off the Fischer-Tropsch exothermic reaction in the micro passage reaction 200 of described Fischer-Tropsch or generation alcohol.Such heat-exchange fluid can comprise air, steam, aqueous water, gaseous nitrogen, other gases (comprising inert gas), carbon monoxide, oil (for example mineral oil) and the Dow A (Dowtherm A) that sells such as Union Carbide Corporation (Union Carbide) and the heat-exchange fluid of first promise conduction oil (Therminol).
Micro passage reaction 200 hot switching paths that use and that randomly use in hydrocracking micro passage reaction 700 at described Fischer-Tropsch or generation alcohol can comprise process channel, carry out the endothermic reaction in described passage.Such heat exchange process passage can be the microchannel.The example of the heat absorption technology that can carry out at described hot switching path comprises steam reformation and dehydrogenation reaction.The steam reformation of the alcohol that takes place under about 200 ℃-Yue 300 ℃ scope is the example of operable heat absorption technology.The synchronous endothermic reaction that increases for the heat sink (heat sink) that improvement is provided can make the typical heat flux substantially on the order of magnitude of convection current heat of cooling flux.
When described heat-exchange fluid flowed into described Fischer-Tropsch or generate the micro passage reaction 200 of alcohol and randomly flow into hydrocracking micro passage reaction 700, partial phase change or full phase change may take place in described heat-exchange fluid.Except removing the heat by the convection current cooling, described phase change can remove extra heat from described process microchannel.For the liquid heat-exchange fluid that is vaporized, the needed evaporation latent heat of described heat-exchange fluid can produce from described Fischer-Tropsch or generate the extra heat process microchannel conduction and that randomly conduct from the little process channel of described hydrocracking of alcohol.In one embodiment, about by weight 50% heat-exchange fluid can be gasified, about by weight 35% can be gasified in one embodiment, about by weight 20% can be gasified in one embodiment, and about by weight 10% can be gasified in one embodiment.In one embodiment, about by weight 10%-can be gasified to about 50%.
At Fischer-Tropsch or generate in micro passage reaction 200, SMR micro passage reaction 500 and/or the hydrocracking micro passage reaction 700 of alcohol, the heat flux that is used for heat exchange can be at the about 500 watts of (W/cm of the about 0.01-of every square centimeter of surface area of the heat exchange walls of one or more process microchannel of described micro passage reaction 2) scope in, in one embodiment at the about 250W/cm of about 0.1- 2Scope in, and in one embodiment at the about 125W/cm of about 1- 2Scope in.The heat flux that is used for convective heat exchange in described micro passage reaction can be at the about 250W/cm of about 0.01- 2Scope in, the about 50W/cm of about in one embodiment 0.1- 2Scope in, the about 25W/cm of about in one embodiment 1- 2, and the about 10W/cm of about in one embodiment 1- 2The heat flux that is used for the described heat-exchange fluid of phase transformation and/or heat release or the endothermic reaction can be at the about 500W/cm of about 0.01- 2Scope in, the about 250W/cm of about in one embodiment 1- 2, the about 100W/cm of about in one embodiment 1- 2, the about 50W/cm of about in one embodiment 1- 2, the about 25W/cm of about in one embodiment 1- 2, and about in one embodiment 1 to about 10W/cm 2
Because this extra cooling and/or heating can reduce or eliminate undesirable accessory substance undesirable have overactivity more can parallel reaction in formation, based on such fact, so the control of the heat exchange in the reaction process of described Fischer-Tropsch or generation alcohol, SMR technology and/or the optional described hydrocracking process may be favourable for the selection rate of controlling the head for target product.
The pressure of each the independent hot switching path in Fischer-Tropsch or the micro passage reaction 200 that generates alcohol neutralize hydrocracking reactor 700 randomly can use passive structure body (as barrier), hole and/or the mechanical component control that is located at described hot switching path upstream or described channel interior.By controlling the pressure of each heat exchange inside microchannels, can control the temperature in each heat exchange microchannel.When described passive structure body, hole and/or mechanical component made described pressure reduce to the pressure of hope, each hot switching path can use higher inlet pressure.By controlling the temperature in each hot switching path, can control described Fischer-Tropsch or generate the process microchannel of alcohol or the temperature in the hydrocracking process microchannel.Therefore, for example,, can under the temperature of hope, operate each fischer-tropsch process microchannel by in or hot switching path that thermodynamics contacts adjacent, using specific pressure with described process microchannel.This has the advantage of accurately controlling each Fischer-Tropsch or generating the process microchannel temperature of alcohol.By accurately controlling each fischer-tropsch process microchannel temperature, advantage is that the temperature profile and the integral body of described method on energy requirement that can obtain to adjust reduce.
In amplifying (scale up) device,, may require to make the quality of described process fluid to be uniformly distributed in the described microchannel for concrete application.Such application may be when need adopting adjacent hot switching path heating or cool off described process fluid.By changing cross-sectional area, can obtain uniform mass flow distribution from a parallel microchannels to another microchannel.Can use the uniformity of the described mass flow distribution of the quality index factor as follows (the Q-factor) definition.0% the Q-factor means absolute even distribution.
Q = m · max - m · min m · max × 100
The variation of cross-sectional area may cause the difference of the shear stress on the wall.In one embodiment, the Q-factor that is used for the micro passage reaction 200 of hydrocracking micro passage reaction 700, SMR micro passage reaction 500 and/or Fischer-Tropsch or generation alcohol can be less than about 50%, in one embodiment less than about 20%, in one embodiment less than about 5%, and in one embodiment less than about 1%.
The superficial velocity that fluid in microchannel, SMR process microchannel and/or the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol flows is at least about 0.01 meter of per second (m/s), in one embodiment at least about 0.1m/s, in one embodiment in the scope of the about 100m/s of about 0.01-, in one embodiment in the scope of the about 1m/s of about 0.01-, in one embodiment in the scope of the about 10m/s of about 0.1-, and in one embodiment in the scope of the about 100m/s of about 1-.
The free flow velocity that fluid in microchannel, SMR process microchannel and/or the hydrocracking process microchannel of described Fischer-Tropsch or generation alcohol flows is at least about 0.001 metre per second (m/s) (m/s), in one embodiment at least about 0.01m/s, in one embodiment in the scope of the about 200m/s of about 0.001-, arrive in the scope of about 100m/s about 0.01 in one embodiment, and in one embodiment in the scope of the about 200m/s of about 0.01-.
In the micro passage reaction of described Fischer-Tropsch or generation alcohol, the CO conversion ratio can be every circulation about 40% or higher, be about 50% or higher in one embodiment, be about 55% or higher in one embodiment, be about 60% or higher in one embodiment, be about 65% or higher in one embodiment, and be about 70% or higher in one embodiment.The term of Shi Yonging " circulation " refers to the one way of reactant by described process microchannel in this application.
The selection rate of the methane in described Fischer-Tropsch (FT) product can be about 25% or lower, about in one embodiment 20% or lower, about in one embodiment 15% or lower, about in one embodiment 12% or lower, and about in one embodiment 10% or lower.
The productive rate of Fischer-Tropsch product can be every circulation about 25% or higher, about in one embodiment 30% or higher, about in one embodiment 40% or higher.
In an embodiment of described fischer-tropsch process, it is about 50% that the conversion ratio of CO is at least, and the selection rate of methane is about 15% or lower, and the productive rate of product is at least every circulation about 35%.
Nitrogen separation device 300 can comprise the microchannel separator of use ionic liquid as liquid absorbent.Described microchannel separator can comprise membrane separator, in described membrane separator, by using capillary force to make the mixing or the back-mixing minimum of the liquids and gases (for example air) in the microchannel, described liquid absorbent (being described ionic liquid) is kept or be strapped in passage or structure inside.Described microchannel separator can comprise device, and in described device, also flow in the common mode that flows in the inboard that the fluid mixture and the gas of liquid absorbent are sent into described micro-channel device jointly or the outside.Described fluid can flow into and flow out the surface characteristics of described device.Described microchannel separator can comprise device, in described device, described gas and liquid-absorbant flow in the common mode that flows and mix to form high interfacial area by a series of barriers with stacking bed form of porous of ring-type, spherical or other shapes of flowing through.Described microchannel separator can comprise device, and in described device, thin contactor flat board makes mutually separately to promote counter-current flow.Described contactor flat board can comprise enough little aperture so that the capillary pressure of described liquid can be retained in described liquid one side of described contactor flat board, and described air-flow is retained in the opposite side of described contactor flat board.Can as the described ionic liquid of described liquid absorbent can comprise one or more imidazoline quaternary ammonium salts and/or one or more in season fragrance-5 yuan or 6 yuan heterocyclic compound, for example imidazole salts, pyridiniujm or the like.Such ionic liquid can comprise 1-butyl-3-methylimidazole hexafluoro mesylate, 1-octyl group-3 methylimidazole hexafluoro mesylate, 1-butyl-3-methylimidazole nitrate, 1-octyl group-3 methylimidazole tetrafluoro first borate, 1-ethyl-3-methylimidazole sulfovinate and/or N-butyl-pyridinium tetrafluoro first borate.United States Patent (USP) 6,579,343 B2 and 6,623,659 B2, U.S. Patent application 2006/0251588 A1 and International Application No. WO 02/34863 A1 disclose operable ionic liquid, and these patents and application are incorporated in the present patent application in the quoted passage mode.
In nitrogen separation device 300, can adopt alternating temperature absorption (TSA) or transformation absorption (PSA) technology.United States Patent (USP) 6508862B1 discloses TSA and the PSA technology that can be used for the aforementioned use microchannel that separates with 6652627B1 and U.S. Patent Publication 2005/0045030A1, and described document is incorporated in the present patent application in the quoted passage mode.
Described ionic liquid separator, (the CO for example of removing foreign matter gas and material during TSA separator and/or PSA separator can use with formed synthesis gas from gasification furnace 110 in the circuit between gasification furnace 110 and the micro passage reaction 200 2, sulphur compound H for example 2S, granular solids or the like).
Can in the circuit between gasification furnace 110 and the micro passage reaction 200, use the micro-channel device that has adopted layers of nanofibers or nano composite membrane.United States Patent (USP) 6,326,326 B1,6,531,224 B1,6,733,835 B2,6,753,038 B2,6,846,554 B2 and 7,122,106 B2 disclose operable nanofiber and nano composite membrane, and described patent is incorporated in the present patent application in the quoted passage mode.
It is disadvantageous having the impurity such as sulphur, halogen, selenium, phosphorus, arsenic etc. in the synthesis gas that flows out gasification furnace 110.Remove aforementioned impurity or reduce the concentration of aforementioned impurity from synthesis gas before can in described micro passage reaction 200, reacting.The technology of removing or reducing the amount of these impurity is well-known technology in this area.For example, can use ZnO guard bed in the circuit between gasification furnace 110 and micro passage reaction 200 to remove sulphur impurity.The amount of the impurity in the described synthesis gas is reduced on the by volume to about 5%, in one embodiment on the by volume to about 1%, in one embodiment on the by volume to about 0.1%, and in one embodiment on the by volume to about 0.05%.
The method for pyrolysis that carries out in pyrolysis reactor 400 can be included in oxygen-free gas or the described carbonaceous material of heating under the situation of other reactants (except the possible steam) arbitrarily.Described method for pyrolysis can comprise anhydrous process.Described method for pyrolysis can comprise fast or the flash distillation method for pyrolysis, the a period of time of under the temperature in described method in 350 ℃-500 ℃ scope described carbonaceous material heating being lacked relatively, the described time goes up to about 2 seconds, in one embodiment in the about 2 seconds scope of about 0.5-.Can adopt described method for pyrolysis to produce liquid product, described liquid product can be meant pyrolysis oil.Described method for pyrolysis can carry out in auger reactor, melting reactor (ablative reactor), commentaries on classics bevel-type reactor, fluid bed or recirculating fluidized bed.
The pyrolytic reaction of carrying out in the auger reactor comprises that use is in the hot sand of the end of screw and the charging of particles of carbonaceous material.Described screw mixes described sand and carbonaceous material and with the mixture of the described two kinds of materials of carrying of described method for pyrolysis.
Described melting method is included at a high speed and sprays particles of carbonaceous material to hot metal surface down.This can realize by the metal surface of using the high speed rotation in the particles of carbonaceous material bed.As alternative, can make described particle be suspended in the carrier gas and introduce under high speed that described particle makes at a high speed that it passes that wall is heated revolve the branch tube.
Described commentaries on classics awl method comprises the mixture of heating sand and particles of carbonaceous material and described mixture is introduced in the cone of rotation.Because the rotation of cone, thus with the carrying out of described pyrolytic process by the mixture of centrifugal force through described sand of cone surface transport and carbonaceous material.
For described fluidized-bed reactor, particles of carbonaceous material is introduced by in the gas fluidized hot sand bed.Because the rate of heat transfer height of the sand that is fluidized, thereby realize the Fast Heating of described particles of carbonaceous material.Provide heat by heat-exchanger pipeline, the burning gases of heat can flow through described pipeline.
For described circulating fluid bed reactor, particles of carbonaceous material can be introduced the recirculating fluidized bed of hot sand.Gas, sand and particles of carbonaceous material can be moved together.Described carrier gas can be the product gas that is recycled, but it also can be burning gases.The high heat transfer rate of described sand can realize the Fast Heating of described particles of carbonaceous material.Separator can separate with coke granule with hot sand with steam by described product gas.Can in the combustor vessel that is fluidized, heat described sand grains again and described sand grains is recycled to described reactor.
The Fischer-Tropsch product that forms in micro passage reaction 200 can comprise gaseous products cut and liquid product cut.Described gaseous products cut can comprise that the boiling point under the normal pressure is lower than about 350 ℃ hydrocarbon (for example passing the tail gas of midbarrel).Described liquid product cut (enriched fraction) can comprise that boiling point is at about hydrocarbon (for example passing the vacuum gas oil of heavy paraffin hydrocarbon) more than 350 ℃.
Use the combination of high pressure for example and/or low temperature gas-liquid separator or low pressure separator or separator described boiling point can be lower than about 350 ℃ Fischer-Tropsch product cut and be separated into tail gas cut and enriched fraction, for example have the normal alkane and the more high boiling hydrocarbon of about 20 carbon atoms of about 5-.Remove one or more boiling points greater than after about 650 ℃ cut, boiling point can be separated into the paraffin distillate of boiling point in 350 ℃-650 ℃ scope greater than about 350 ℃ cut (enriched fraction).Described paraffin distillate can comprise the linear paraffin with about 50 carbon atoms of about 20-and the more high boiling branched paraffin of relatively small amount.Use fractionation can effectively carry out described separation.
The Fischer-Tropsch product that forms in micro passage reaction 200 can comprise methane, paraffin and other heavy high molecular weight product.Described product can comprise alkene, for example ethene, just with different-alkane and combination thereof.Such product can comprise the hydrocarbon in the fuel boiling range, and described fuel boiling range comprises jet oil or diesel oil boiling range.
Branching may be favourable in multiple terminal is used, especially when needs improve octane number and/or reduce pour point.Isomerized degree can be greater than every mole of n-alkane of about 1 mole of isoparaffin, every mole of n-alkane of about in one embodiment 3 moles of isoparaffins.When described product was used for Dresel fuel compositions, described product can comprise Cetane number at least about 60 hydrocarbon mixture.
Described Fischer-Tropsch product further can be handled to form lubricating base oil or diesel oil.For example, the product hydrocracking that makes in the micro passage reaction 200 can be advanced distillation and/or isoversion then so that lubricating base oil, diesel oil, jet fuel or the like to be provided.Can adopt United States Patent (USP) 6,103, the method that discloses in 099 or 6,180,575 is carried out hydroisomerization to described Fischer-Tropsch product; Adopt United States Patent (USP) 4,943,672 or 6,096,940 carry out hydrocracking and hydroisomerization; Adopt the method that discloses in the United States Patent (USP) 5,882,505 to dewax; Perhaps adopt United States Patent (USP) 6,013,171,6,080,301 or 6,165,949 carry out hydroisomerization and dewaxing.Because the method for the synthetic hydrocarbon of processing Fischer-Tropsch that these patents are disclosed and the end product that is made by such method, these patents are incorporated present patent application in the quoted passage mode.
The hydrocracking carried out in described hydrocracking micro passage reaction 700 reaction can comprise hydrogen and from the reaction between the Fischer-Tropsch product of micro passage reaction 200, perhaps one or more hydrocarbon of separating from described Fischer-Tropsch product (for example one or more liquid or paraffin Fischer-Tropsch product).Described Fischer-Tropsch product can comprise one or more long chain hydrocarbons.In the method for described hydrocracking, for example can pass through C 23Cut is cracked into C 12-C 22The medium range carbon number increase desirable diesel oil distillate.Can use excessive hydrogen will produce at one's own expense-paraffin distillate of Tuo micro passage reaction 200 sends into hydrocracking micro passage reaction 700 and carries out phase reaction.Under the reaction condition of the temperature and pressure that raises, a part of liquid charging can be converted into gas phase, and remaining liquid part can flow along catalyst of living in.In the hydrocracking system of routine, form liquid stream.The use of micro passage reaction that is used for hydrocracking reaction is in the unique advantage of many aspects.These aspects can comprise dynamics, pressure drop, heat transfer and mass transfer.
The Fischer-Tropsch hydrocarbon products of hydrocracking in hydrocracking micro passage reaction 700 can comprise arbitrarily can be by the hydrocarbon of hydrocracking.Such hydrocarbon can comprise the hydrocarbon that contains one or more C-C keys that can rupture in the process of hydrocracking.Describedly can be comprised the aromatic compound that saturated fat compounds of group (for example alkane), unsaturated fat compounds of group (for example olefine, alkine), alkyl (for example alkyl) replace, aromatic compound that alkylene (hydrocarbylene) (for example alkylidene (alkylene)) replaces or the like by the hydrocarbon of hydrocracking.
The feed composition of hydrocracking reactor 700 can comprise one or more diluent materials.The example of such diluent can comprise nonreactive hydrocarbon diluent or the like.By weight can be about 99% based on the concentration of the described diluent of weight of described Fischer-Tropsch product for 0-, be that 0-is about 75% in one embodiment by weight, and be 0-about 50% in one embodiment by weight.Described diluent can be used for reducing the viscosity of viscous fluid product.The viscosity of the described feed composition in the hydrocracking reactor 700 can be in the scope of about 1 centipoise of about 0.001-, about 1 centipoise of about in one embodiment 0.01-, and about 1 centipoise of about in one embodiment 0.1-.
The hydrogen that enters in the described feed composition of hydrocracking micro passage reaction 700 can be at every cubic centimetre of (ccm) Fischer-Tropsch of about 2000 standard cubic centimeters of about 10-(sccm) hydrogen product with the ratio of Fischer-Tropsch product, the about 1800sccm/ccm of about in one embodiment 100-, the about 1200sccm/ccm of about in one embodiment 350-.Described hydrogen feed may further include water, methane, carbon dioxide, carbon monoxide and/or nitrogen.
H in the described hydrogen feed 2Can be derived from other method, steam recombination method (H for example 2The mol ratio of/CO is about 3 product stream), method for partical oxidation (H 2The mol ratio of/CO is about 2 product stream), self-heating recombination method (H 2The mol ratio of/CO is about 2.5 product stream), CO 2Recombination method (H 2The mol ratio of/CO is about 1 product stream), coal gasification method (H 2The mol ratio of/CO is about 1 product stream) and the combination of said method.For each incoming flow in these incoming flows, use routine techniques (for example film separates or absorption) can make described H 2Separate with remaining component.
Can be comprised the midbarrel of boiling temperature in the scope of about 260-270 ℉ (127-371 ℃) by the Fischer-Tropsch product of hydrocracking.Term " midbarrel " generally includes the cut of diesel oil, jet fuel and kerosene boiling spread.The boiling spread of term " kerosene " and " jet fuel " typically refers to the temperature range of 260-550 ℉ (127-288 ℃), and " diesel oil " boiling spread is often referred to the boiling point of hydrocarbon between about 700 ℉ of about 260-(127-371 ℃).Describedly can be comprised gasoline or naphthalene cut by the Fischer-Tropsch product after the hydrocracking.Such cut is considered to C usually 5The end point of fraction of-400 ℉ (204 ℃).
The described target product that generates the method for alcohol can comprise that one or more have the alcohol of about 10 carbon atoms of 1-, is about 5 carbon atoms of 1-in one embodiment, is about 5 carbon atoms of 2-in one embodiment.Described product can comprise methyl alcohol.Described product can comprise the mixture of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol, 1-amylalcohol, 2-amylalcohol or above-mentioned two or more materials.The mixture of pure and mild alcohol like this can be used as fuel or postcombustion.For example, such alcohol can be added into gasoline to replenish described gasoline.
Embodiment 1
Use Chem CAD to carry out the method simulation.Described process is shown among Figure 28.With reference to Figure 28, method 600 comprises drier 601, blender 607, gasification furnace 610, modified chamber (tempering chamber) 615, superheater 620, cancellation chamber (quench chamber) 625, washer 630, cyclone separator 635, condenser 640,645 and 650, blender 655, Fischer-Tropsch (FT) micro passage reaction 660, heat exchange steam-return line 663, separator 670 and 675, blender 680 and fractionating column 685 and 690.Described method has also adopted heat exchanger 636,641,646,656,673 and 674.Such heat exchanger can be micro channel heat exchanger.Can also in the method for institute's example, use compressor 642,647 and 652.In following table 1-3, disclosed the composition of the temperature, pressure, flow velocity and the different fluid that in method 600, are adopted.
The operating process of the method 600 of example as shown in 28 is described now.In the following description, the temperature and pressure of different fluid is illustrated in the bracket.Temperature with ℃ and pressure represent with bars.In some cases, such numerical value is rounded by the value that described Chem CAD simulation is produced.The complete value that produces by Chem CAD is shown among the table 1-3.To make by weight water content be 70% domestic solid garbage (MSW) via circuit 602 (15 ℃, 1bar) flow in the drier 601, in described drier, described MSW is concentrated.Make separated water via circuit 604 (89 ℃ 1bar) flow out drier 601.Make steam via circuit 603 (250 ℃, 25bars) flow in the drier 601, heat described MSW, and via circuit 605 (225 ℃ 25bars) flow out drier 601.Making by weight water content is that 14.2% the MSW that is concentrated is via (89 ℃ in circuit 606,1bar) flow in the blender 607, in described blender, make the MSW that is concentrated with from (121 ℃ in circuit 687, fractionating column light fraction 18bars) and from circuit 692 (121 ℃, 18bars) fractionating column tower bottom product mixes.The mixed flow (described mixed flow can refer to mix carbonaceous feed) that makes the MSW, fractionating column light fraction and the fractionating column tower bottom product that are concentrated is via circuit 608 (94 ℃ 1bar) flow to gasification furnace 610 from blender 607.Make oxygen (15 ℃ 1bar) flow to gasification furnace 610 via circuit 609.In gasification furnace 610, heat the carbonaceous feed and the described oxygen of described mixing and make its generating gasification reaction generate synthesis gas.Shown in arrow 617, from gasification furnace 610, remove and deash.
Make described synthesis gas via circuit 611 (1480 ℃ 1bar) flow to modified chamber 615 from gasification furnace 610.Make water via circuit 612 and 614 (15 ℃ 1bar) flow to modified chamber 615.Make steam flow out described modified chamber 615 via circuit 619.Make described synthesis gas via circuit 616 (1013 ℃ 1ba) flow to superheater 620 from modified chamber 615.Make steam via circuit 618 (225 ℃ 1bar) flow to and flow through superheater 620, then via circuit 621 (450 ℃ 25bars) flow out superheater 620.Make described synthesis gas via circuit 622 (235 ℃ 1bar) flow to and flow through cancellation chamber 625 from superheater 620.Make water via circuit 612 and 613 (15 ℃ 1bar) flow to and flow through cancellation chamber 625, then via circuit 627 (67 ℃ 1bar) flow out cancellation chamber 625.Make described synthesis gas via circuit 626 (67 ℃ 1bar) flow into the washers 630 from cancellation chamber 625.Impurity is separated with described synthesis gas and make described impurity via circuit 632 (67 ℃ 1bar) flow out washer 630.Make described synthesis gas via circuit 631 (67 ℃ 1bar) flow into the cyclone separator 635 from washer 630.Solid particle is separated with described synthesis gas.Remove solid particle via circuit 638.Make described synthesis gas via circuit 637 (67 ℃ 1bar) flow to and flow through heat exchanger 636 from cyclone separator 635, then via circuit 637a (24 ℃ 1bar) flow in the condenser 640 the described synthesis gas of condensation in this described condenser.Make water via circuit 644 (24 ℃ 1bar) flow out condenser 640.Make described synthesis gas via circuit 643 (24 ℃ 1bar) flow to and flow through compressor 642 from condenser 640, then via circuit 643a (125 ℃ 2.6bars) flow to and flow through heat exchanger 641 from compressor 642.Make described synthesis gas via circuit 643b (24 ℃ 2.6bars) flow to condenser 645 from heat exchanger 641, the described synthesis gas of condensation in this condenser.In condenser 645, from described synthesis gas, remove and anhydrate and make described water via circuit 648 (24 ℃ 2.6bars) flow out described condenser.Make described synthesis gas via circuit 649 (24 ℃ 2.6bars) flow to and flow through compressor 647 from condenser 645, then via circuit 649a (101 ℃ 5.5bars) flow to and flow through heat exchanger 646.Make described synthesis gas via circuit 649b (24 ℃ 5.5bars) flow to condenser 650 from heat exchanger 646, the described synthesis gas of condensation in this condenser.Make water via circuit 651a (24 ℃ 1bar) flow out condenser 650.Make described synthesis gas via circuit 651 (24 ℃ 5.5bars) flow out condenser 650 and flow to then and flow through compressor 652.
Make described synthesis gas via circuit 653 (243 ℃ 25bars) flow to blender 655 from compressor 652.The described synthesis gas that flow via circuit 653 have 0.989 H 2: the CO ratio.Make hydrogen via circuit 654 (37 ℃, 15bars) flow to blender 655, hydrogen is mixed with described synthesis gas.The mixture of synthesis gas and hydrogen can refer to the synthesis gas of upgrading.The synthesis gas of described upgrading has 1.896 H 2: the CO ratio.The synthesis gas of described upgrading flows through heat exchanger 656 from blender 655, and via (220 ℃ in circuit 657,25bars) flow to and flow through Fischer-Tropsch (FT) micro passage reaction 660 from heat exchanger 656, in the heat release of synthesis gas generation described in this reactor FT reaction to form the FT product.
The steam cooling Fischer-Tropsch micro passage reaction 660 of coolant vapours loop 663 is flow through in employing.Make steam via circuit 664 (150 ℃ 26bars) enter described coolant vapours loop 663 and flowing among the blender 664a.Make steam via circuit 664b (222 ℃ 26bars) flow out blender 664a and flow to then and flow through heat exchanger 668.Heat exchanger 668 contacts with FT micro passage reaction 660 thermodynamics, then with described FT micro passage reaction heat-shift.Described synthesis gas is converted into described FT product in FT micro passage reaction 660 when, with described steam cooling FT micro passage reaction 660.Make steam via circuit 664c (225 ℃ 25bars) flow out heat exchange 668 and flow to container 666.Make steam via circuit 665 (225 ℃, 25bars) flow container 666 and flow out coolant vapours loop 663.Make steam via circuit 664d (225 ℃ 25bars) flow to and flow through pump 667 from container 666.Make described steam via circuit 669 (225 ℃ 27bars) flow to blender 664a from pump 667.
Make described FT product via circuit 661 (230 ℃, 18bars) flow to separator 670 from FT micro passage reaction 660, in this separator, described FT product is separated.Make gaseous state FT product via circuit 671 (230 ℃ 18bars) flow out separator 670.Make liquid FT product via circuit 672 (230 ℃ 18bars) flow out separator 670 and flow to blender 680.Make described gaseous state FT product flow through heat exchanger 673 and flow to circuit 671a (80 ℃, 18bars).Make coolant water from circuit 682 (30 ℃ 5bars) flow to and flow through heat exchanger 673 (34.2 ℃, 3.5bars) outflow heat exchanger 673 via circuit 683 then.Make described gaseous state FT product via circuit 671a (80 ℃, 18bars) flow to and flow through heat exchanger 674 then from heat exchanger 674 flow to and flow through circuit 671b (35 ℃, 18bars) and flow to three road separators 675.Make gaseous mixture via circuit 676 (35 ℃ 18bars) flow out three road separators 675.Such gaseous mixture can be meant FT tail gas.Make liquefied mixture via circuit 677 (35 ℃ 18bars) flow out three road separators 675.Described liquefied mixture can be meant process condensate.
Make liquid FT product via circuit 678 (35 ℃, 18bars) flow to blender 680 from three road separators 675, in this blender, described liquid FT product is mixed with liquid FT product from circuit 672.The liquid FT product of described mixing via circuit 681 (121 ℃, 18bars) flow to fractionating column 685 from blender 680, in this fractionating column, the liquid FT product of described mixing is carried out fractionation.Make the light fraction product via circuit 687 (121 ℃ 18bars) flow out fractionating column 685 and flow to blender 607.Make liquid FT product via circuit 686 (121 ℃, 18bars) flow out fractionating column 685 and flow to fractionating column 690, in fractionating column 690, the liquid product of described mixing is carried out fractionation.Make liquid FT product via circuit 691 (121 ℃ 18bars) flow out fractionating column.Liquid FT product like this can refer to synthetic fuel.Make tower bottom product via circuit 692 (121 ℃ 18bars) flow out fractionating column 690 and flow to blender 607.
Table 1
Table 2
The fluid numbering 653 654 651 661 672 671 676
Temperature ℃ 233.7769 15 220 230 230 230 35
Pressure bar 25.17 25.17 25.17 18.25 18.25 18.25 17.95
Heat release MW -2.6217 -0.006469 -2.5101 -5.5514 -0.13693 -5.4144 -1.2426
The steam mole fraction 1 1 1 0.99172 0 1 1
Total kmol/h 190.9299 84.3338 275.2637 146.281 1.2117 145.0693 78.2589
Total kg/h 2934.6853 170 3104.6854 3104.6994 308.7789 2795.9199 1198.5036
Total standard L m3/h 6.2364 2.4286 8.665 5.0348 0.384 4.6508 2.9014
Total standard V m3/h 4279.44 1890.23 6169.66 3278.69 27.16 3251.53 1754.07
Flow velocity kmol/h
Hydrogen 91.761 84.3338 176.0948 33.7124 0.012 33.7004 33.6744
Carbon monoxide 92.8783 0 92.8783 27.8635 0.0104 27.8531 27.8139
Water 1.0333 0 1.0333 63.7726 0.1997 63.5729 0.2657
Carbon dioxide 0 0 0 0.9005 0.0007 0.8998 0.8806
Methane 3.2116 0 3.2116 12.9638 0.0056 12.9583 12.9137
Ethane 0.0009 0 0.0009 0.4203 0.0004 0.4198 0.4116
Ethene 1.3367 0 1.3367 1.3367 0.0012 1.3355 1.3175
Propane 0 0 0 0.2926 0.0005 0.2921 0.2739
Propylene 0.0035 0 0.0035 0.0035 0 0.0035 0.0033
The N-butane 0 0 0 0.0203 0.0001 0.0203 0.0166
The N-pentane 0 0 0 0.0767 0.0003 0.0763 0.0457
The N-hexane 0 0 0 0.1415 0.001 0.1405 0.0465
The N-heptane 0 0 0 0.223 0.0024 0.2206 0.0319
The N-octane 0 0 0 0.2922 0.0047 0.2875 0.0165
The N-nonane 0 0 0 0.302 0.0074 0.2946 0.0057
The N-decane 0 0 0 0.2829 0.0103 0.2726 0.0018
The N-hendecane 0 0 0 0.2698 0.0144 0.2553 0.0006
The N-dodecane 0 0 0 0.2568 0.02 0.2368 0.0002
The N-tridecane 0 0 0 0.2126 0.0237 0.189 0.0001
The N-tetradecane 0 0 0 0.1876 0.0293 0.1583 0
The N-pentadecane 0 0 0 0.1471 0.0316 0.1155 0
The N-hexadecane 0 0 0 0.1235 0.0376 0.0859 0
The N-heptadecane 0 0 0 0.1062 0.0396 0.0666 0
The N-octadecane 0 0 0 0.1254 0.0564 0.0691 0
The N-nonadecane 0 0 0 0.1024 0.0549 0.0475 0
The N-eicosane 0 0 0 0.1876 0.1242 0.0634 0
The n-docosane 0 0 0 0.1402 0.1105 0.0297 0
The n-lignocerane 0 0 0 0.1197 0.1068 0.013 0
The n-hexacosane 0 0 0 0.0845 0.0798 0.0046 0
The n-octacosane 0 0 0 0.0697 0.0677 0.0019 0
The n-melissane 0 0 0 0.0513 0.0506 0.0007 0
The n-dotriacontane 0 0 0 0.054 0.0536 0.0004 0
Hexatriacontane 0 0 0 0.0478 0.0477 0.0001 0
Methyl alcohol 0 0 0 0.13 0.0005 0.1296 0.0051
Ethanol 0 0 0 0.5201 0.0023 0.5178 0.1664
Isopropyl alcohol 0 0 0 0.0033 0 0.0032 0.0007
The N-propyl alcohol 0 0 0 0.0325 0.0002 0.0323 0.0051
Hydrogen chloride 0.0612 0 0.0612 0.0612 0.0001 0.0611 0.0598
Nitrogen 0.0265 0 0.0265 0.0265 0 0.0265 0.0265
Hydrogen cyanide 0.2035 0 0.2035 0.2035 0.0006 0.2029 0.1449
Hydrogen sulfide 0.0085 0 0.0085 0.0085 0 0.0084 0.0081
Carbonyl sulfide 0.0004 0 0.0004 0.0004 0 0.0004 0.0004
Carbon disulfide 0.0052 0 0.0052 0.0052 0 0.0052 0.0032
Benzene 0.3994 0 0.3994 0.3994 0.0031 0.3963 0.1184
Table 3
The fluid numbering 677 678 681 692 686 691 687
Temperature ℃ 35 35 120.8143 120.8143 120.8143 120.8143 120.8143
Pressure bar 17.95 17.95 17.95 17.95 17.95 17.95 17.95
Heat release MW -5.0226 -0.26163 -0.39856 -0.025453 -0.37262 -0.13048 -0.24245
The steam mole fraction 0 0 0 0.49977 0 0 0.2
Total kmol/h 63.402 3.4085 4.6202 0.4815 4.1387 2.2875 1.8512
Total kg/h 1145.1263 452.2904 761.0694 10.2715 750.7979 251.8024 498.9954
Total standard L m3/h 1.1466 0.6028 0.9869 0.0164 0.9704 0.3397 0.6307
Total standard V m3/h 1421.07 76.4 103.56 10.79 92.76 51.27 41.49
Flow velocity kmol/h
Hydrogen 0.0001 0.0259 0.0379 0.0379 0 0 0
Carbon monoxide 0 0.0391 0.0495 0.0495 0 0 0
Water 63.2365 0.0707 0.2704 0.2704 0 0 0
Carbon dioxide 0.0057 0.0135 0.0142 0.0142 0 0 0
Methane 0.0001 0.0444 0.05 0.05 0 0 0
Ethane 0 0.0082 0.0086 0.0086 0 0 0
Ethene 0 0.0179 0.0191 0.0191 0 0 0
Propane 0 0.0182 0.0187 0.0187 0 0 0
Propylene 0 0.0002 0.0002 0.0002 0 0 0
The N-butane 0 0.0036 0.0037 0.0037 0 0 0
The N-pentane 0 0.0306 0.0309 0.0093 0.0217 0.0217 0
The N-hexane 0 0.0941 0.0951 0 0.0951 0.0951 0
The N-heptane 0 0.1887 0.1911 0 0.1911 0.1911 0
The N-octane 0 0.271 0.2757 0 0.2757 0.2757 0
The N-nonane 0 0.2889 0.2963 0 0.2963 0.2963 0
The N-decane 0 0.2708 0.2811 0 0.2811 0.2811 0
The N-hendecane 0 0.2547 0.2692 0 0.2692 0.2692 0
The N-dodecane 0 0.2366 0.2566 0 0.2566 0.1026 0.154
The N-tridecane 0 0.1889 0.2126 0 0.2126 0.0213 0.1913
The N-tetradecane 0 0.1583 0.1876 0 0.1876 0.0094 0.1782
The N-pentadecane 0 0.1155 0.1471 0 0.1471 0.0059 0.1412
The N-hexadecane 0 0.0859 0.1235 0 0.1235 0.0049 0.1186
The N-heptadecane 0 0.0666 0.1062 0 0.1062 0.0042 0.102
The N-octadecane 0 0.0691 0.1254 0 0.1254 0.005 0.1204
The N-nonadecane 0 0.0475 0.1024 0 0.1024 0.0041 0.0983
The N-eicosane 0 0.0634 0.1876 0 0.1876 0.0075 0.1801
The n-docosane 0 0.0297 0.1402 0 0.1402 0 0.1402
The n-lignocerane 0 0.013 0.1197 0 0.1197 0 0.1197
The n-hexacosane 0 0.0046 0.0845 0 0.0845 0 0.0845
The n-octacosane 0 0.0019 0.0697 0 0.0697 0 0.0697
The n-melissane 0 0.0007 0.0513 0 0.0513 0 0.0513
The n-dotriacontane 0 0.0004 0.054 0 0.054 0 0.054
Hexatriacontane 0 0.0001 0.0478 0 0.0478 0 0.0478
Methyl alcohol 0.1205 0.0039 0.0043 0 0.0043 0.0043 0
Ethanol 0.0378 0.3136 0.3159 0 0.3159 0.3159 0
Isopropyl alcohol 0 0.0025 0.0025 0 0.0025 0.0025 0
The N-propyl alcohol 0.0003 0.0269 0.0271 0 0.0271 0.0271 0
The fluid numbering 677 678 681 692 686 691 687
Hydrogen chloride 0.0002 0.0011 0.0012 0 0.0012 0.0012 0
Hydrogen cyanide 0.0002 0.0578 0.0583 0 0.0583 0.0583 0
Hydrogen sulfide 0.0001 0.0003 0.0003 0 0.0003 0.0003 0
Carbon disulfide 0.0003 0.0017 0.0017 0 0.0017 0.0017 0
Benzene 0 0.2779 0.281 0 0.281 0.281 0
Embodiment 2
In the micro passage reaction that adopts fixed bde catalyst, carry out Fischer-Tropsch reaction.Described process is carried out under high production capacity (time of contact is on the about 214 milliseconds order of magnitude of about 290-) and is had a high CO conversion ratio (go up to about 80%).Operate described reactor with two phase flow, the change in pressure drop of described reactor is very little, and the standard deviation of pressure drop is less than 3% of whole pressure drops.Described high CO conversion ratio and stable pressure drop also may be with low CH 4Selection rate (for all situations less than 15%, and for most of situation less than 10%) and high C 6+ hydrocarbon selection rate (about 75% for all situations, for most of situation about 80%).
Described micro passage reaction has two and is inserted in three technology repetitives between the cooling agent repetitive.Coolant channel in process microchannel in the described technology repetitive and the described cooling agent repetitive is the direction of cross-flow.This is shown among Figure 29.The area of active reactor nuclear is 15.2cm (6 inches) * 15.2cm (6 inches).The integral stacked of described reactor is of a size of 25.4cm (10 inches) * 19.1cm (7.5 inches) * 6.17cm (2.43 inches).Described coolant channel is made by a plurality of intermediate plates with flow distribution feature.Described process microchannel is made by the copper waveform.This is shown among Figure 30.Such waveform has 19.1cm (7.5 inches) * 15.2cm (6 inches) * 3.18cm (0.125 inch).The thickness of described waveform is 0.15mm (0.006 inch).The micro passage reaction that obtains has and is divided into 276 two-layer process microchannel.Each passage in the described process microchannel has width and is 0.95mm (0.0375 inch), highly is the size of 19.1cm (7.5 inches) for 3.18mm (0.125 inch) and length.Top cover links to each other with process microchannel to provide bigger exterior pipe system to be connected with base and described coolant channel.
Catalyst bed is loaded in micro passage reaction as described below.Described assembly is included in the Process Control System (PCS).Described catalyst bed comprises SiC particle and FT catalyst granules.
Described SiC particle is provided by the Atlanta plant engineering company (AtlanticEquipment engineers of Bergen New Jersey) of New Jersey Bergen, and classification number is SI-312.Adopt Malvern Hydro 2000G light scattering particle size analyzer to measure volume averaging d (50) diameter of described SiC particle.Described SiC particle has 281 microns average diameter.The loose filling bulk density (PABD) of described SiC is every cubic centimetre 1.62 gram (g/cc), and the voidage at PABD place is 0.31.
Described FT catalyst is provided by Oxford Catalysts Ltd. (Oxford Catalyst limited).Described catalyst comprises cobalt and carrier.The volume averaging particle size of the described catalyst granules that employing Malvern Hydro 2000G analyzer side gets is 261 microns.The screening that described catalyst is carried out subsequently shows that most catalyst quality is more than the catalyst that obtains at the catalyst that obtains under the higher screen size between the 215-250 micron under lower screen size.The PABD of catalyst is 1.08g/cc.The voidage of PABD is 0.362.Use pipette to add 100 microlitre deionized waters until the described surface of described water destruct.To be placed on the vibration mechine under medium intensity vibration 30 seconds to remove the air that contains, to leave standstill this bed by moistening catalyst, then excessive water be introduced described surface.Use pipette to remove excessive water.Sample shown in making is at air drying, then under 200 ℃ the temperature under normal pressure dry one hour.
Determine the volume of described reactor by the methyl alcohol of at room temperature introducing.Make the methyl alcohol of 151.1cc be full of described reactor undulating path until the top.
With thickness is the bottom that the 100ppi foams of 0.635cm (0.25 inch) insert described reactor.
Described FT catalyst is added into described waveform and uses the described catalyst of rubber hammer compacting.The all-mass that adds is 143.22 grams.Measure the degree of depth of filling at each undulating path with measured length pin, use the thin slice and the digital camera of classification to measure the distance of described length pin above described wave shed.Difference between the desirable packed height of FT catalyst packed height and 17.415cm (6.75 inches) is 0.467cm (0.184 inch), is lower than desirable level.The standard deviation of described packed height is 0.483cm (0.190 inch).The volume of supposing described technology undulating path is identical on whole piling height, and then bulk density is 1.068g/cc, or be lower than measured 1.08g/cc PABD 1.1%.Whole volumes of described catalyst are 134.1cc.
Described SiC catalyst is added into the top of described reactor, and the described catalyst of compacting is to fill described reactor.With thickness is the top that the 100ppi foams of 0.635cm (0.25 inch) insert described reactor.
Use the control of Brooks (Brooks) 5850E mass flow controller to be admitted to the flow and the composition of the synthesis gas of described micro passage reaction.Hydrogen, carbon monoxide and nitrogen are repaiied three gas companies (Matheson Tri-gas) and are got rel (Delille) company by Praxair company (Praxair), Ma Xi and provides.Make above-mentioned gas simultaneously by activated carbon and Molsieve 13X catcher.The downstream that sample point is arranged on mixing point is formed to measure inlet gas.Before described gas is sent into described micro passage reaction, in the stainless steel micro channel heat exchanger, described gas is heated to＞300 ℃, heat described heat exchanger with nitrogen.
Adopt the JA430A-H of Yokogawa Electric Corporation (Yokogawa) type pressure sensor to measure described inlet pressure.Adopt the EJA110A-H of Yokogawa Electric Corporation differential pressure sensor to measure the pressure drop of described technology fixed bed.Employing is equipped with more gas-chromatography (GC) the analysis entrance and exit stream of the Agilent of the additional channels of higher hydrocarbon (Agilent) 3000A RGA refining gas analyzer.Collect the tail gas sample by the sample point that is arranged on the reactor downstream and the first product feeder upstream.The sample adjuster is made up of Neptune SC-316 sample cooler and Swagelok 300cc condensate liquid catcher.Set the flow that passes through described sample adjuster by pressure regulator and needle valve, only in the process of sampling, open.When gasmetry each time, collect five to seven GC samples, abandon preceding two samples and get the average of residue sample.
The route of setting described product stream make its under elevated pressure by three collection containers, and it is cooled off step by step so that lighter hydrocarbon products and the heavier hydrocarbon products and the crude separation of water to be provided.Heating first drum with two Watlow Band heaters is 120 ℃-135 ℃ until the local surfaces temperature.Water and heavier hydrocarbon products bottom are extracted out and weigh.Gas leaves described first drum of temperature between 120 ℃ and 140 ℃, and makes described gas cooled to being lower than 30 ℃ in a Sentry type 1253C57-EW6-H35X heat exchanger, uses the described heat exchanger of Dow DoeforstHD coolant cools.Second drum is in room temperature and is used in collects water and transparent liquid hydrocarbon phase.Make remaining gas flow to the 2nd Sentry type 1253C57-EW6-H35X heat exchanger, ℃ flow to the 3rd feeder then with propane diols coolant cools to 10, described feeder is collected and is less than 1% of whole condensate liquids.After described three-flute, described tail gas arrives the pressure control device that is used for described method side (side).Described device is for blocking not (Kammer) type 030000 ball valve.Employing is equipped with the dry tester of 100 liters/resolution ratio of U.S. Mitt USA Corporation of the relay that is used for the signal propagation and measures described product.The downstream that second exhaust sampling point is arranged on described dry tester is used for other sampling.
Heat described reactor and 400 ℃ and near the condition of normal pressure under under hydrogen reducing atmosphere, carry out the activation of catalyst.Make described reactor cooling then and, open the flow of cooling agent gradually by the pressure in the reactor is increased to the operating pressure start-up operation, and the flow of reactant feed mixtures, temperature of reactor improved simultaneously.Described reactant feed mixtures contains H 2With the mol ratio of CO be H 2: CO=2: 1.Described reactant feed mixtures also contains the N of by volume 16.6% 2When be 290ms time of contact, gradually described temperature of reactor is increased to 210 ℃ with obtain stable state greater than 70% CO conversion ratio.
When reaching reaction condition, the standard deviation of described pressure drop is high, and the standard deviation of described pressure drop drops to lower value when system stability then.Pressure drop under selecteed time conditions shows the stability of short-term time and long-term time:
When the operating time is approximately 1500 hours, described reactor operating condition is set at described charging contains 4% N by weight under the time of contact of the inlet temperature of the inlet pressure of 350psig and 222 ℃ and 214ms 2And inlet H 2: the CO ratio is 2.01.Such condition was kept 190 hours.Described reactor performance shows stable 68.8 ± 0.3% CO conversion ratio.CH 4Average selection rate be 13.3 ± 0.1% and C 6The selection rate 74.8 ± 0.2% of+hydrocarbon.
Standard deviation in the drop measurement is little, and the pressure drop that this shows described reactor is stable.Average pressure drop in such operating process is 1.75 ± 0.01psi.
When the operating time is approximately 1890 hours, reduce described catalyst once more, and described reactor is at H 2: the CO ratio be 2.0 and described charging contain 16.6%N 2Goal condition under restart.Described inlet pressure is 350psig, and average inlet temperature is 211 ℃.Be 290ms described time of contact.Such reaction condition is provided with to be kept 420 hours.CO conversion ratio in the described reactor is at the beginning up to about 75%, and is stable gradually to stationary value 68.8 ± 0.3% in the process of hundreds of hour then.CH 4Average selection rate be 8.9 ± 0.1% and C 6The selection rate 77.8 ± 0.2% of+hydrocarbon.
Corresponding to the stabilization process of aforesaid CO conversion ratio, described pressure drop is risen at the beginning, and when the CO conversion ratio was reduced to its final stationary value, described pressure drop tended towards stability then.Standard deviation in the drop measurement is little, this shows in reactor pressure decrease described in such operating process to keep stable.Average pressure drop in such operating process is 1.46 ± 0.04psi.
Before collecting data, use normal pressure to detect, detect the seepage between coolant side and fixed bed (technology) side.From that time forward, under the pressure that is higher than described method side, operate coolant side, thereby seepage is for to enter the aqueous water or the steam of described method side from described coolant side arbitrarily.Therefore than before operation, the standard deviation that the described method side pressure that illustrates is fallen bigger (two to four times).
The details of described micro passage reaction in the performance of its whole operation life period is summarized as follows.
After finishing initial start-up, obtained H under the time of contact of 210 ℃ temperature of reactor and 290ms 2: the CO ratio is that 2: 1 and described charging contain 16.6%N 2Goal condition, under such condition, obtain 71.7% CO average conversion.Make such process conditions from starting the operating time that keeps about 1140 hours.Described CO conversion ratio stable gradually extremely about 71.7% mean value and corresponding average CH 4Selection rate is 8.9%.
Then be reduced to 214ms described time of contact, and described temperature of reactor is risen to 222 ℃ so that described CO conversion ratio is increased to its aforesaid stationary value.Under such condition, has 77.2% C 6+ hydrocarbon selection rate and 71.9% CO average conversion.The pressure drop of corresponding stable state is 1.843 ± 0.004psi.
When the operating time is about 1500 hours, described charging diluent is reduced to the N of by volume 4% 2, make described temperature of reactor remain on 222 ℃, and described CO average conversion is 68.8%.Corresponding average pressure drop is 1.75psi.
Then by described temperature is reduced to 210 ℃, with N 2Diluent increases to 16.6% and increased to 290ms described time of contact, makes described reactor condition return to the initial start-up condition.Described CO average conversion is 66.4%.This is compared with beginning performance low about 5%.This has shown the importance of minimal catalysqt deactivation in the operating time.The pressure drop of 1.46 corresponding ± 0.01psi is higher than the initial 1.41 ± 0.01psi that sees.This increase in the pressure drop and the minimizing in the conversion ratio are suitable.In fact the standard deviation of the described pressure drop of the stability of the mobile transmission in the expression process microchannel remains unchanged in the process of 1880 hours operating time.
When the operating time is 1890 hours, reduce described catalyst once more, described catalyst is consuming half an hour and is consuming about 2 hours more than 390 ℃ more than 400 ℃.After reduction, between described coolant side and described method side, found cross leaks.In operating process, coolant pump is failed to form an internal lock and is shut down (interlock shut down).When described reactor reaches target temperature, the CO conversion ratio only is 39%, far below aforesaid value.Reduce described catalyst once more.
Restart described catalyst then to reach H under the time of contact of 210 ℃ average reactor temperature and 290ms 2: the CO ratio is that 2: 1 and described charging contain 16.6%N 2Condition, described condition meets first stable condition after initial start-up.Conversion ratio during a little higher than aforementioned start of initial CO conversion ratio, but described conversion ratio is stable at low value 69.5% slightly.Corresponding average pressure drop is 1.47 ± 0.04psi.Value when starting than reactor is initial, the standard deviation of described pressure drop increases.This is also corresponding with the increase of the deactivation rate of described catalyst.The increase of standard deviation may be the result of aforesaid leakage.
Make then to be reduced to 214ms time of contact, and make described temperature of reactor increase to 223 ℃ gradually.This has obtained 70.4% CO average conversion and 76.0% C 6+ selection rate.
Make H then 2: the CO ratio becomes 1.5: 1 and makes and increases to 255ms described time of contact.Make reactor pressure increase to 384psig then and make described temperature of reactor be increased to 228 ℃ gradually, obtained 60.9% CO average conversion and 7.1% CH 4Selection rate.When the CO conversion ratio rose under higher pressure, described pressure drop descended.
Make H 2: the CO ratio becomes 1.5 and make described diluent N 2Increase to 40%.Make described reactor pressure increase to 420psig and make described temperature of reactor increase to 232 ℃.When increased to 250ms by 184ms described time of contact, described CO conversion ratio increased to 64.0% by 56.1%.Corresponding pressure drop is reduced to 1.545psi from 2.256psi.When increased described time of contact, described pressure drop descended, thereby has reduced flow and improved the CO conversion ratio.
Make described reaction condition return to H then 2: the CO ratio becomes 2: 1 and described charging contains 16.6%.Described average reactor temperature is that 211 ℃ and described time of contact are 290ms.Described CO conversion ratio drops to 59.6% mean value.Described average pressure drop is 1.52 ± 0.04psi.Because the inactivation of catalyst is so described pressure drop is higher than the pressure drop when restarting.
And then reduce described catalyst, and at H 2: the CO ratio became 2: 1 and described charging contain 16.6% and described average reactor temperature be 211 ℃ and described time of contact to be to restart under the identical reaction condition of 290ms.Described CO conversion ratio reaches about 69.2% stationary value, and described stationary value is similar with the conversion ratio that obtains after aforementioned reduction.Corresponding average pressure drop is 1.50 ± 0.04psi.
In fact the standard deviation (being the index of flow stability) of the pressure drop of the steady flow in the expression process microchannel remains unchanged in the process of 1800 hours operating times.
Though described the present invention, be understandable that for for reading those skilled in the art of the present invention, various adjustment of the present invention are conspicuous in conjunction with various embodiments.Therefore, be appreciated that the present invention includes all falls into the interior such adjustment of the claimed scope of claim of the present invention.

Claims (95)

1. one kind is converted into the method that contains one or more hydrocarbon or one or more pure target products with carbonaceous material, and described method comprises:
(A) under at least about 700 ℃ temperature, gasify described carbonaceous material to form synthesis gas; And
(B) making described synthetic air go into micro passage reaction contacts with catalyst so that described synthesis gas is converted into target product.
2. method according to claim 1 is characterized in that described carbonaceous material comprises the mixture of coal, oil, living beings, solid waste or above-mentioned two or more materials.
3. according to claim 1 or the described method of claim 2, it is characterized in that described carbonaceous material comprises the mixture of life solid waste, bazardous waste, garbage derivatived fuel, tire, rubbish, sewage sludge, animal excrements, petroleum coke, rubbish, refuse, agricultural wastes, maize straw, switchgrass, wood chip, timber, grass bits, building waste material, plastic material, ginning discarded object, landfill gas, biogas, natural gas or above-mentioned two or more materials.
4. according to each the described method in the aforementioned claim, it is characterized in that the described carbonaceous material of gasification in adverse current fixed-bed gasification furnace, co-current flow fixed bed gasification furnace, fluidized-bed gasification furnace, airflow bed gasification furnace, molten reactant metal device or plasma gasification system.
5. according to each the described method in the aforementioned claim, it is characterized in that the described carbonaceous material of gasification in the presence of gasifying agent.
6. method according to claim 5 is characterized in that described gasifying agent comprises the mixture of steam, oxygen, air or above-mentioned two or more materials.
7. according to each the described method in the aforementioned claim, it is characterized in that, contact with motlten metal with steam and react at carbonaceous material described in the molten reactant metal device and generate described synthesis gas.
8. according to each the described method in the aforementioned claim, it is characterized in that described synthesis gas comprises H 2And CO.
9. method according to claim 8 is characterized in that H 2With the ratio of CO in the scope of about 0.5-about 4.
10. according to each the described method in the aforementioned claim, it is characterized in that the synthesis gas that makes comprises H in step (A) 2With CO, and in step (B) before with the H of additional quantity 2Be added into described synthesis gas.
11. each the described method according in the aforementioned claim is characterized in that the synthesis gas that makes further comprises solid particle in step (A), remove described solid particle before in step (B) from described synthesis gas.
12. each the described method according in the aforementioned claim is characterized in that the synthesis gas that makes further comprises water in step (A), at least a portion of removing described water before in step (B) from described synthesis gas.
13. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one and the process microchannel that heat exchanger thermodynamics contacts, described catalyst is present in the described process microchannel.
14. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises a plurality of process microchannel and a plurality of hot switching path, described catalyst is present in the described process microchannel.
15. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises a plurality of process microchannel and a plurality of hot switching path, described catalyst is present in the described process microchannel, each hot switching path contacts with at least one process microchannel thermodynamics, at least one manifold that makes synthesis gas flow into described process microchannel, at least one manifold that makes product flow out described process microchannel, at least one manifold and at least one manifold that makes described heat-exchange fluid flow out described hot switching path that makes heat-exchange fluid flow into described hot switching path.
16. according to each the described method in the aforementioned claim, it is characterized in that, a plurality of described micro passage reactions are arranged in the container, each micro passage reaction comprises a plurality of process microchannel and a plurality of hot switching path, described catalyst is present in the described process microchannel, each hot switching path contacts with at least one process microchannel thermodynamics, is provided with to make the manifold of described synthetic air to described process microchannel in described container, make described product flow out the manifold of described process microchannel and make described heat-exchange fluid flow to the manifold of described hot switching path and make heat-exchange fluid flow out the manifold of described hot switching path.
17. method according to claim 16 is characterized in that, each micro passage reaction comprises about 50,000 process microchannel of about 100-, and described container comprises about 1000 micro passage reactions of 1-.
18. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, on the width of the inside dimension of described process microchannel or the height to about 10mm.
19. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, on the length of described process microchannel to about 10 meters.
20. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one hot switching path, and described process microchannel and hot switching path are made by following material: the combination of the alloy of any metal in aluminium, titanium, nickel, copper, the aforementioned metal, steel, monel metal, Inconel, brass, quartz, silicon or aforementioned two or more materials.
21. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises at least one process microchannel, the fluid that flows in described process microchannel contacts with the surface characteristics in the described process microchannel, with contacting the described fluid of interfering mobile introducing of described surface characteristics.
22. each the described method according in the aforementioned claim is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one hot switching path, and described hot switching path comprises the microchannel.
23. according to each the described method in the aforementioned claim, it is characterized in that, the catalyst that uses in step (B) is Fischer-Tropsch catalyst, the reaction of carrying out in described micro passage reaction in the process of step (B) is Fischer-Tropsch reaction, and described target product comprises one or more hydrocarbon.
24. method according to claim 23 is characterized in that, described Fischer-Tropsch catalyst comprises one or more and/or its oxide among Co, Fe, Ni, Ru, Re, the Os, or the mixture of above-mentioned two or more materials.
25. method according to claim 24, it is characterized in that, described Fischer-Tropsch catalyst further comprises one or more and/or its oxide in I A, II A, III B or the IV B family metal of the periodic table of elements, lanthanide series metal and/or its oxide, actinide metals and/or its oxide, or the mixture of above-mentioned two or more materials.
26. method according to claim 24, it is characterized in that, described Fischer-Tropsch catalyst further comprises one or more and/or its oxide among Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, Ce or the Th, or the mixture of above-mentioned two or more materials.
27. method according to claim 24, it is characterized in that, described Fischer-Tropsch catalyst further comprises carrier, described carrier comprises one or more in aluminium oxide, zirconia, silica, aluminum fluoride, fluorided alumina, bentonite, cerium oxide, zinc oxide, silica-alumina, carborundum, the molecular sieve, or the mixture of above-mentioned two or more materials.
28. method according to claim 23 is characterized in that, described Fischer-Tropsch catalyst comprises the composition of representing with following formula
CoM 1 aM 2 bO x
Wherein
M 1It is the mixture of Fe, Ni, Ru, Re, Os or above-mentioned two or more materials;
M 2Be Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, Ce or Th, or the mixture of above-mentioned two or more materials;
A is the number in about 0.5 scope of 0-;
B is the number in about 0.5 scope of 0-; And
X is the number that satisfies the required oxygen of element valence balance in the formula.
29. method according to claim 23 is characterized in that, described Fischer-Tropsch catalyst comprises the Co that is supported on the aluminium oxide, and described Co useful load is at least about 5% by weight.
30. method according to claim 29 is characterized in that, described Fischer-Tropsch catalyst further comprises Re, Ru or its mixture.
31. according to each the described method among the claim 1-22, it is characterized in that, the catalyst that uses in step (B) is for generating the catalyst of alcohol, the reaction of carrying out in described micro passage reaction in the process of step (B) is the reaction that generates alcohol, and described target product comprises one or more alcohol.
32. method according to claim 31 is characterized in that, the described catalyst that generates alcohol comprises catalyst metals Nb, Ta, Mo, W, Tc, Re or by the mixture of above-mentioned two or more materials with free form or combining form.
33. method according to claim 32 is characterized in that, described catalyst further comprises synergistic catalyst metallic yttrium, lanthanide series metal, actinide metals or above-mentioned two or more materials mixture with free form or combining form.
34. each the described method according in the aforementioned claim is characterized in that described catalyst is the form of granular solids.
35. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises one or more process microchannel, and described catalyst-coated is on the inwall of described process microchannel or be grown on the inwall of described process microchannel.
36. each the described method according in the aforementioned claim is characterized in that, described catalyst loading has the configuration of flowing through, is flowing through on the carrier of configuration or snakelike configuration.
37. each the described method according in the aforementioned claim is characterized in that described catalyst loading is on the carrier of the combination of the configuration with foams, felt rug body, agglomerate body, fin or above-mentioned two or more configurations.
38. each the described method according in the aforementioned claim is characterized in that, described catalyst loading is on the carrier of the fin component form that contains a plurality of parallel alternate fins.
39. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises at least one process microchannel, and the heat flux that described process microchannel has at least one heat exchange walls and be used for heat exchange in described micro passage reaction is on every square centimeter of surface area of described at least one heat exchange walls in the scope between about 500 watts of about 0.01-.
40. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, in the temperature of described process microchannel porch in about 80 ℃ of the exit of described process microchannel temperature.
41. method according to claim 23 is characterized in that, the pressure in the described micro passage reaction is in last extremely about 50 atmospheric scopes.
42. method according to claim 23 is characterized in that, the temperature in the described micro passage reaction is in the about 300 ℃ scope of about 150-.
43. method according to claim 23 is characterized in that, be last to about 2000 milliseconds the time of contact in the described micro passage reaction.
44. method according to claim 23 is characterized in that, the CO conversion ratio in the described micro passage reaction is in the scope of about 10-about 99%.
45. method according to claim 23 is characterized in that, the methane selection rate in the described target product is last to about 25%.
46. method according to claim 23 is characterized in that, the boiling point that described target product comprises under one or more normal pressures is at least about 30 ℃ hydrocarbon.
47. method according to claim 23 is characterized in that, described target product comprises boiling point under one or more normal pressures greater than about 175 ℃ hydrocarbon.
48. method according to claim 23 is characterized in that, described target product comprises one or more alkane and/or one or more contain the alkene of about 100 carbon atoms of the 5-that has an appointment.
49. method according to claim 23 is characterized in that, described target product comprises the mixture of one or more alkene, one or more normal alkanes, one or more isoparaffins or above-mentioned two or more materials.
50. method according to claim 23 is characterized in that, adopts separation, fractionation, hydrocracking, hydroisomerization, dewaxing or above-mentioned two or more combination further to handle described target product.
51. method according to claim 23 is characterized in that, further handles described target product has lubricant viscosity with formation oil or midbarrel fuel.
52. method according to claim 23 is characterized in that, further handles described target product to form fuel.
53. method according to claim 31 is characterized in that, the pressure in the described micro passage reaction is in last extremely about 100 atmospheric scopes.
54. method according to claim 31 is characterized in that, the temperature in the described micro passage reaction is in the about 500 ℃ scope of about 200-.
55. method according to claim 31 is characterized in that, described target product comprises one or more alcohol that contains about 10 carbon atoms of 1-.
56. method according to claim 31 is characterized in that, described target product comprises methyl alcohol.
57. method according to claim 31, it is characterized in that described target product comprises the mixture of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol, 1-amylalcohol, 2-amylalcohol or above-mentioned two or more materials.
58. according to each the described method in the aforementioned claim, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, described heat exchanger comprises at least one hot switching path that contacts with described at least one process microchannel thermodynamics, described process microchannel contains in described process microchannel the fluid that flows according to a direction, described hot switching path contain according to described process microchannel in the fluid that fluid flows and the direction of stream or adverse current flows.
59. according to each the described method among the claim 1-57, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, described heat exchanger comprises at least one hot switching path that contacts with described at least one process microchannel thermodynamics, described process microchannel contains in described process microchannel the fluid that flows according to a direction, described hot switching path contain according to described process microchannel in the fluid fluid that the direction of cross-flow flows that flows.
60. according to each the described method among the claim 1-57, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, described at least one process microchannel contacts with at least one hot switching path thermodynamics, the length of described process microchannel and the same length of described hot switching path.
61. according to each the described method among the claim 1-57, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, described heat exchanger comprises the heat exchange area that contacts with described at least one process microchannel thermodynamics, described heat exchange area comprises one or more hot switching paths, described hot switching path is vertical angle longitudinal extension with the longitudinally with respect to described process microchannel, described heat exchange area is longitudinal extension on the direction identical with described process microchannel, the length that is shorter in length than described process microchannel of described heat exchange area, described process microchannel contains entrance and exit, described heat exchange area is arranged on or near the porch of described process microchannel.
62. according to each the described method among the claim 1-57, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, described heat exchanger comprises two heat exchange area that contact with described at least one process microchannel thermodynamics, each heat exchange area comprises one or more hot switching paths, described hot switching path is vertical angle longitudinal extension with the longitudinally with respect to described process microchannel, described process microchannel contains entrance and exit, described heat exchange area is longitudinal extension on the direction identical with described process microchannel, the length that is shorter in length than described process microchannel of described heat exchange area, the length that is shorter in length than another heat exchange area in a zone in the described heat exchange area is arranged on described heat exchange area or near the porch of described process microchannel.
63. according to each the described method among the claim 1-57, it is characterized in that, described micro passage reaction comprises at least one process microchannel and at least one heat exchanger, provide the heat exchange performance of adjusting along described process microchannel length, the part of the heat that reaction produced that carries out in described process microchannel discharges with the cold that is provided by described heat exchanger and is complementary.
64. each the described method according in the aforementioned claim is characterized in that described catalyst comprises the catalyst of classification.
65. each the described method according in the aforementioned claim is characterized in that the quality index factor of described micro passage reaction is less than about 50%.
66. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, the apparent speed of the fluid that flows in described process microchannel is at least about 0.01m/s.
67. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, the air speed of the fluid that flows in described process microchannel is at least about 1000hr -1
68. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, on the pressure drop of the fluid that flows in described process microchannel is every meter to about 10 atmospheric pressure.
69. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises at least one process microchannel, the Reynolds number of the fluid that flows in described process microchannel is in the scope of about 10-about 4000.
70. according to each the described method in the aforementioned claim, it is characterized in that, in the process of step (B), in described micro passage reaction, steam is used as the heat-exchange fluid and the described carbonaceous material that gasifies in the process of step (A) in the presence of gasifying agent, will be used as the gasifying agent in the process of step (A) from the steam of step (B).
71. according to each the described method in the aforementioned claim, it is characterized in that, in the nitrogen separation device, make nitrogen and air separation oxygen-enriched air or purified oxygen to be provided and in the process of step (A), in the presence of described oxygen-enriched air or purified oxygen, to gasify described carbonaceous material before in step (A).
72. according to the described method of claim 71, it is characterized in that, in the separator of microchannel, use ionic liquid to make nitrogen and air separation as absorbing liquid.
73. each the described method according in the aforementioned claim is characterized in that, makes described carbonaceous material pyrolysis before in step (A), generates pyrolysis oil, the described pyrolysis oil of gasification in the process of step (A).
74. according to each the described method in the aforementioned claim, it is characterized in that, in the process of step (A), in gasification furnace, form synthesis gas and in the process of step (B), make Fischer-Tropsch tail gas, in the steam methane reforming micro passage reaction, described Fischer-Tropsch tail gas is converted into synthesis gas, will mixes with synthesis gas from the synthesis gas of described steam reformation micro passage reaction from gasification furnace.
75. each the described method according in the aforementioned claim is characterized in that the described synthesis gas that forms contains carbon dioxide in the process of step (A), in step (B) described carbon dioxide is separated with described synthesis gas.
76. according to the described method of claim 74, it is characterized in that, the described synthesis gas that forms in the process of step (A) contains carbon dioxide, described carbon dioxide is separated with described synthesis gas and described carbon dioxide is mixed with described Fischer-Tropsch tail gas.
77. each the described method according in the aforementioned claim is characterized in that described carbonaceous material comprises polyethylene or polyvinyl chloride, and the described synthesis gas that forms in the process of step (A) comprises the synthesis gas of ethylene-rich.
78. each the described method according in the aforementioned claim is characterized in that, at step (B) the described synthesis gas that cooling forms in the process of step (A) in one or more heat exchangers before.
79., it is characterized in that described one or more heat exchangers are micro channel heat exchanger according to the described method of claim 78.
80. each the described method according in the aforementioned claim is characterized in that, described synthesis gas contains impurity and uses before in step (B) and contains ion liquid microchannel separator described impurity is separated with described synthesis gas.
81. each the described method according in the aforementioned claim is characterized in that, described synthesis gas comprises impurity and uses alternating temperature absorption or transformation absorption microchannel separator that described impurity is separated with described synthesis gas before in step (B).
82. each the described method according in the aforementioned claim is characterized in that, described synthesis gas comprises impurity and uses the microchannel separator that contains nanofiber or nano composite membrane that described impurity is separated with described synthesis gas before in step (B).
83. each the described method according in the aforementioned claim is characterized in that, described synthesis gas comprises impurity and uses before in step (B) that ZnO is guard bed to make described impurity separate with described synthesis gas.
84. each the described method according in the aforementioned claim is characterized in that described carbonaceous material comprises non-food carbonaceous material.
85., it is characterized in that described carbonaceous material comprises food source according to the described method of claim 1-83.
86. each the described method according in the aforementioned claim is characterized in that described micro passage reaction comprises a plurality of process microchannel, makes described process microchannel between the plane lamina by waveform is arranged on.
87. 6 described methods is characterized in that according to Claim 8, described micro passage reaction further comprises the hot switching path that a plurality of and described process microchannel thermodynamics contacts, and makes described hot switching path between the plane lamina by waveform is arranged on.
88. according to each the described method in the aforementioned claim, it is characterized in that, the catalyst that uses in step (B) is Fischer-Tropsch catalyst, and described catalyst comprises cobalt and carrier, and the concentration of described cobalt is by weight between about 35%-about 60% of described catalyst.
89. according to each the described method in the aforementioned claim, it is characterized in that, the catalyst that uses in step (B) is Fischer-Tropsch catalyst, by preparing described catalyst with containing the catalyst precarsor that gas activation at least about the hydrocarbon of 5mol% contains cobalt compound and carrier.
90. according to each the described method among the claim 1-88, it is characterized in that, the catalyst that uses in step (B) is Fischer-Tropsch catalyst, prepare described catalyst by the following method: (a) preparation (i) at least a catalyst carrier or catalyst carrier precursor, the (ii) at least a compound that contains metal, wherein said metal comprises V, Cr, Mn, Fe, Co, Ni, Cu, Mo and/or W, and the liquefied mixture of (iii) at least a polarity of solvent organic compound as the described compound that contains metal, described liquefied mixture comprises the water based on the about 20wt% of 0-of the total weight of described mixture; (b) described mixture is converted into lotion or solid residue; And (c) containing under the atmosphere of oxygen the described residue of burning at least in part described organic compound be converted into carbon and form catalyst or the catalyst precarsor that is supported.
91., it is characterized in that described metal comprises cobalt according to the described method of claim 90.
92. according to each the described method in the aforementioned claim, it is characterized in that, the described target product that makes in step (B) is the Fischer-Tropsch product, and described method further is included in the micro passage reaction carries out hydrocracking at least a portion in the described Fischer-Tropsch product.
93., it is characterized in that the micro passage reaction that is used to carry out described hydrocracking is exactly the micro passage reaction that is used to form described Fischer-Tropsch product according to the described method of claim 92.
94. each the described method according in the aforementioned claim is characterized in that, the catalyst that uses in step (B) comprises catalyst and the dehydrogenation that generates alcohol, and described target product comprises one or more unsaturated hydrocarbons.
95. each the described method according in the aforementioned claim is characterized in that described micro passage reaction is made by the stainless steel with one or more copper that are used to form the microchannel in the described micro passage reaction or aluminium waveform.
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