CN108753342A - Fischer-tropsch process in micro passage reaction - Google Patents

Abstract

Disclosed invention is related to a kind of method for carrying out fischer-tropsch reaction, including the reaction-ure mixture comprising fresh synthesis gas and tail gas is made to be flowed in micro passage reaction, it is contacted with catalyst, to form at least one hydrocarbon products, the catalyst source is in the catalyst precarsor of the catalyst support comprising cobalt and surface modification.

Description

Fischer-tropsch process in micro passage reaction

The application is the applying date to be September in 2013 11, entitled " micro- logical application No. is 201380042156.X The divisional application of the Chinese patent application of fischer-tropsch process in road reactor ".

According to 35 U.S.C. § 119 (e), it is desirable that the U.S. Provisional Application 61/716,772 that on October 22nd, 2012 submits Priority.According to 35 U.S.C. § 119 (d), the UK Patent Application submitted on the 7th of August in 2012 is also required The priority of No.1214122.2.These applications are incorporated herein by reference.

Technical field

The present invention relates to a kind of fischer-tropsch process (Fischer-Tropsch process), and more particularly, are related to The fischer-tropsch process carried out in micro passage reaction.

Background technology

Fischer-tropsch reaction is related to including H in the presence of a catalyst₂It is converted into one or more hydrocarbon productions with the reactant of CO Object.

Invention content

The present invention relates to a kind of method for carrying out fischer-tropsch reaction, it includes：Make reaction-ure mixture in microchannel plate It answers in device and flows, contacted with catalyst, to form the product for including at least one higher molecular weight hydrocarbon products；The catalyst From catalyst precarsor, the catalyst precarsor includes cobalt, such as Pd, Pt, Rh, Ru, Re, Ir, Au, Ag and/or Os promotion The supporter that agent and surface are modified, wherein the surface of the supporter by with silica, titanium dioxide, zirconium oxide, Magnesia, chromium oxide, aluminium oxide or its mixture of two or more are handled to be modified；The wherein described product also includes tail Gas, at least part of the tail gas are detached with the higher molecular weight hydrocarbon products and are combined with fresh synthesis gas to be formed The reaction-ure mixture, in the reaction-ure mixture, the volume ratio of the fresh synthesis gas and the tail gas is about 1: 1 to about 10: 1 or about 1: 1 to about 8: 1 or about 1: 1 to about 6: 1 or about 1: 1 to about 4: 1 or about 3: 2 to about 7: 3 or about 2: 1；The reaction-ure mixture includes H₂And CO, in the reaction-ure mixture, based on CO in the fresh synthesis gas Concentration, H₂Molar ratio with CO be about 1.4: 1 to about 2: 1 or about 1.5: 1 to about 2.1: 1 or about 1.6: 1 to about 2: 1 or About 1.7: 1 to about 1.9: 1；The conversion ratio of the CO of fresh synthesis gas wherein in reaction-ure mixture be at least about 70%, Or at least about 75% or at least about 80% or at least about 85% or at least about 90%；And to the choosing of methane in the product Selecting property be about 0.01 to 10% or about 1% to about 10% or about 1% to about 5% or about 3% to about 9% or about 4% to About 8%.

For CO in reaction-ure mixture (that is, the CO from fresh synthesis gas is added from combining with fresh synthesis gas The CO of tail gas), the conversion per pass of CO can be about 70% to about 90% or about 70% to about 85% or about 70% to about 80%.

For the CO in fresh synthesis gas, the conversion ratio of CO can be about 88% to about 95% or about 90% to about 94% or about 91 to about 93%.

Supporter can include refractory metal oxides, carbide, carbon, nitride or its mixing of two or more Object.Supporter can include aluminium oxide, zirconium oxide, silica, titanium dioxide or its mixture of two or more.

Supporter can include TiO₂Modified silica supporter, wherein supporter contain at least about 11 weight % TiO₂Or about 11 weight % to about 30 weight % TiO₂Or about 15 weight % to about 17 weight % TiO₂Or about 16 weight Measure %TiO₂。

The surface for the supporter that surface is modified can be amorphous.

Catalyst precarsor can include cobalt oxide.Cobalt oxide can include Co₃O₄。

It is at least one process microchannel thermally contacted that micro passage reaction, which can include with heat exchanger, at catalyst In the process microchannel.

Micro passage reaction can include multiple process microchannels and multiple hot switching paths, and catalyst is in the work In skill microchannel.

Micro passage reaction can include multiple process microchannels and multiple hot switching paths, and catalyst is in the work In skill microchannel, each hot switching path is to thermally contact at least one process microchannel；For making reaction-ure mixture flow To at least one of process microchannel manifold；For making product flow out at least one manifold of the process microchannel； For making flow of heat exchange fluid at least one manifold of the hot switching path；With for by the heat-exchange fluid stream Go out at least one manifold of the hot switching path.

Multiple micro passage reactions can be set in a reservoir, each micro passage reaction include multiple process microchannels and Multiple hot switching paths, catalyst are in the process microchannel, each hot switching path and at least one process microchannel For thermo-contact, the container is equipped with for making reaction-ure mixture flow to the manifold of the process microchannel, for making production Logistics goes out the manifold of the process microchannel, for making flow of heat exchange fluid to the manifold of the hot switching path and being used for The heat-exchange fluid is set to flow out the manifold of the hot switching path.

Catalyst can be in granular form the form of solid.Micro passage reaction includes one or more process microchannels, and And catalyst can be coated on the inner wall of the process microchannel or be grown on the inner wall of the process microchannel.Catalyst It can be supported on on the supporter for flowing through formula construction, flow-through configuration or serpentine-like configuration.Catalyst can be supported on tool On the supporter for having foam, felt, agglomerate, fin or the construction of its combination of two or more.

Higher molecular weight aliphatic hydrocarbon product, which may be embodied in, to boil at a temperature of at least about 30 DEG C under atmospheric pressure One or more hydro carbons.Higher molecular weight aliphatic hydrocarbon product may be embodied in the temperature under atmospheric pressure at greater than about 175 DEG C One or more hydro carbons of lower boiling.Higher molecular weight aliphatic hydrocarbon product can include the one of about 5 to about 100 carbon atoms Kind or a variety of alkane and/or one or more alkene.Higher molecular weight aliphatic hydrocarbon product can include one or more alkene Hydrocarbon, one or more n-alkanes, one or more isoparaffins or its mixture of two or more.It can use and divide From, fractionation, hydrocracking, hydroisomerization, dewaxing or its combination of two or more to higher molecular weight aliphatic hydrocarbon Product is further processed.Higher molecular weight aliphatic hydrocarbon product can be further processed to form with lubricant viscosity Oil or centre distillate fuel.Higher molecular weight aliphatic hydrocarbon product can be further processed to form fuel.

Micro passage reaction can include at least one process microchannel and at least one heat exchanger, the heat exchange It is at least one hot switching path thermally contacted that device, which includes at least one process microchannel, the process microchannel tool There are the fluid flowed wherein with a direction, the hot switching path to have with the stream with fluid in the process microchannel The fluid that the dynamic direction in fair current, adverse current or cross-flow is flowed.

Micro passage reaction can include at least one process microchannel and at least one heat exchanger, along the work The length of skill microchannel provides the exchange characteristics of customization, the heat generated by the reaction carried out in the process microchannel Part release matches with the cooling provided by the heat exchanger.

Micro passage reaction can include multiple process microchannels, and the process microchannel passes through between plane sheets Waveform is set to be formed.It is that the multiple heat exchanges thermally contacted are led to that micro passage reaction, which can also include with the process microchannel, Road, the hot switching path are formed by the way that waveform is arranged between plane sheets.

Micro passage reaction can include multiple plates, the multiple plate be in stacking form, define multiple fischer-tropsch process layers and There is neighboring, the neighboring of each plate to be soldered to the neighboring of next adjacent plate for multiple heat exchange layers, each plate, To provide peripheral sealing to stack.

The deactivation rate of catalyst can be less than loss about 0.2%CO conversion ratios daily.

Product can include higher molecular weight hydrocarbon products, H₂O and H₂, the H of product₂O partial pressures are about 3 to about 10 bars, product H₂O/H₂Molar ratio is about 1: 1 to about 5: 1, and the total reactant mixture based on charging to reactor is (that is, fresh synthesis The summation of gas and recycling tail gas), the conversion ratio of CO is about 70 to about 80% or about 70 to about 85% or about 80 to about 85% or about 82 to about 83%.

In one embodiment, the present invention can provide the combination of following advantages and afterclap：

A) total CO conversion ratios very high in the technique of single phase microchannel (are about 90% or more in one embodiment It is high)；

B) in one embodiment, with about 0.45 to about 0.50 recycling tail gas and the ratio reality of fresh synthesis gas Existing (A).

C) this allows to tolerate high CO conversion ratios, this can provide high-moisture pressure and high water and hydrogen ratio.In general, may be used To be expected Co catalysts fast deactivation under these conditions.

D) operation substoichiometric H₂/ CO ratios (i.e. H₂/ CO ratios (may be about less than stoichiometric consumption ratio 2.12)).In one embodiment, tail gas H₂/ CO ratios are smaller than about 1.0, can be with less than typical cobalt FT catalyst The tail gas H that can be operated₂/ CO ratios.In general, Co catalysts under these conditions may fast deactivation.

E) under following the two, these results are realized：(1) relatively low operation temperature is (in one embodiment, about It is 200-210 DEG C), and (2) (in one embodiment, catalyst productivity is typically in or is higher than using high reaction rate 2,000v/v/hr and just about 1gm C5+/gm catalyst/hour or higher).

F low methane (and other light gases) selectivity) is realized, it means that high C₅+ liquid selective (such as one It is about 90% or higher in a embodiment).

One problem of this field relates to the fact that：In order to realize relatively high CO conversion ratios, it is often necessary to use Two benches fischer-tropsch reactor.This generates waste and cost.Using the present invention, on the other hand, single stage reactor may be used with phase The CO conversion ratios of relative high levels are realized to low recycling ratio, this is due to the fact that：It is generated during fischer-tropsch process At least part of tail gas is recycled to reactor, is combined wherein with fresh synthesis gas, and can realize relatively high Every time by (total reactor charging) CO conversion ratios, without the inactivation of accelerator activator.Tail is recycled in reaction-ure mixture The ratio of gas and fresh synthesis gas can be about 0.8 or higher.

Description of the drawings

In the accompanying drawings, similar component has similar reference numeral with feature.Multiple attached drawings are schematic diagram, can be with It is not necessarily drawn to scale.

Fig. 1 is the flow chart for the concrete form for showing the method for the present invention, and this method is included in micro passage reaction will packet Reaction-ure mixture containing fresh synthesis gas and recycling tail gas is converted to one or more hydrocarbon with higher molecular weight.

Fig. 2 is the schematic diagram of the container for accommodating multiple reactors.

Fig. 3 and 4 is the diagram of the reactor core for micro passage reaction used in the method for the present invention.

Figures 5 and 6 are the schematic diagram for the repetitive unit that can be used in micro passage reaction.It is each shown in Figures 5 and 6 Repetitive unit includes Fischer-tropsch process microchannel, and the Fischer-tropsch process microchannel includes the reaction zone containing catalyst and one Or the hot switching path of multiple adjoinings.The heat-exchange fluid flowed in hot switching path shown in Fig. 5 is with micro- relative to technique The flowing of process fluid is flowed in the direction of cross-flow in channel.The heat-exchange fluid flowed in hot switching path shown in Fig. 6 It can be flowed in the direction of fair current or adverse current by the flowing with process fluid in process microchannel.It is every in these embodiments One can provide customization by controlling with number that the different piece of process microchannel is the hot switching path thermally contacted Exchange characteristics.Using the exchange characteristics of these customizations, can be provided in some parts of process microchannel micro- with technique The other parts in channel compare more cooling ducts.For example, can the inlet of reaction zone or its be provided about and react Compare more cooling ducts in the downstream part in area.It can be determined by controlling the flow velocity of heat-exchange fluid in hot switching path Heat exchange features.For example, being the flowing of heat-exchange fluid in the hot switching path thermally contacted with the entrance of reaction zone Relatively high rate can be the stream of heat-exchange fluid in the hot switching path thermally contacted with the downstream part of reaction zone Dynamic relative low speeds rate is in conjunction with using.

Fig. 7-12 is the schematic diagram of the catalyst or catalyst support that can be used in process microchannel.Shown in Fig. 7 Catalyst be in granular form solid bed form.Catalyst shown in fig. 8, which has, flows through formula design.It is urged shown in Fig. 9 Agent has flow through structure.Figure 10-12 is the schematic diagram for the fin component that can be used for supporting catalyst.

Figure 13 is the flow chart for showing test operation used in embodiment 2.

Figure 14 is the diagram for the catalyst insert that can be used in micro passage reaction.

Specific implementation mode

All ranges and ratio limit can be combined in any manner disclosed in specification and claims.It should Understand, unless stated otherwise, refer to "one", "an" and/or when " described ", may include it is a kind of/or be more than A kind of/, and refer to that the project of odd number can also include the plural number of the project.

Phrase "and/or" is understood to mean that " either or both " of connected element, that is, element is in some feelings Connectivity exists and unconnected presence in other cases under condition.It is clearly indicated unless there are opposite, in addition to by "and/or" Except the element that phrase particularly points out, other elements can be optionally present, regardless of its with those of particularly point out element phase It closes or uncorrelated.Therefore, as non-limiting examples, when with open language for example "comprising" is used in combination when, refer to " A And/or B " can refer to A in one embodiment and without B (optionally including the element in addition to B)；In another embodiment Middle finger B and without A (optionally including the element in addition to A)；Refer to A in another embodiment and B (is optionally included other Element)；Deng.

Word "or" is construed as having meaning identical with "and/or" defined above.For example, ought be in lists When separating every, "or" or "and/or" should be understood as include, that is, include at least one in multiple or series of elements It is a, but also include the more than one in multiple or a series of elements, and optionally include other unlisted project.Only It is explicitly shown as opposite term, such as " one in only ... " or " ... in only one ", "or" can refer to Including the only one element in multiple or series of elements.In general, only when there is exclusive term in front, for example, it is " any It is a ", one of " ... ", " one in only ... " or when " ... in only one ", terms used herein "or" just it should be understood that exclusive selection (that is, both " one or the other but be not ").

When referring to a series of one or more elements, phrase "at least one" is understood to mean selected from a system At least one element of any one or more of column element element, and include not necessarily specifically being arranged in this series of element At least one of each element gone out and any combinations of element being not excluded in this series of elements.This definition Other than permission can be optionally present the element in addition to being clearly indicated in the series of elements in phrase "at least one" meaning Element, regardless of these elements to those of to clearly indicate element related or uncorrelated.Therefore, as non-limiting examples, " A At least one of with B " (either equally " at least one of A or B " or equally " at least one in A and/or B It is a ") at least one A can be referred in one embodiment, more than one A is optionally included, there is no B (and to optionally include Other elements other than B)；At least one B can be referred in another embodiment, optionally include more than one B, no There are A (and optionally including other elements other than A)；At least one A can be referred to In yet another embodiment, appointed Selection of land includes more than one A and at least one B, optionally includes more than one B and (and optionally includes other members Element)；Etc..

The transitional word or phrase of "include", "comprise", " carrying ", " having ", " containing ", " being related to ", " possessing " etc. It should be understood as open, that is, look like to include but not limited to.

Term " microchannel " refers at least one inside dimension of height or width at most about 10 millimeters (mm) Channel, and the height or width are at most in one embodiment about 5mm, and be at most in one embodiment About 2mm, and be at most about 1 mm in one embodiment.Microchannel can include at least one entrance and it is at least one go out Mouthful, wherein at least one entrance is different from least one outlet.Microchannel can not be only hole.It microchannel can be not only For across the channel of zeolite or mesoporous material.The length of microchannel can be at least about twice of height or width, and Be height or at least about five times of width in one embodiment, and be in one embodiment height or width extremely It is about ten times few.The internal height or width of microchannel can be about 0.05 to about 10mm, or about 0.05 to about 5mm, or about 0.05 To about 2mm, or about 0.05 to about 1.5mm, or about 0.05 to about 1mm, or about 0.05 to about 0.75mm, or about 0.05 to about 0.5mm, or about 1 to about 10mm, or about 2 to about 8mm, or about 3 to about 7mm.Height or other inside dimensions of width can be with For any size, for example, at most about 3 meters, or about 0.01 to about 3 meter, and be about 0.1 to about 3 in one embodiment Rice, or about 1 to about 10mm, or about 2 to about 8mm, or about 3 to about 7mm.The length of microchannel can be any size, for example, At most about 10 meters, and be about 0.1 to about 10 meter, and be about in one embodiment in one embodiment 0.2 to about 10 meter, and be about 0.2 to about 6 meter, and in one embodiment in one embodiment, be 0.2 to About 3 meters.It microchannel can be with cross section with any shape, for example, square, rectangle, circle, semicircle, trapezoidal etc..It is micro- The shape and/or size of the cross section in channel can change over its length.For example, in the length of microchannel, height or Width can become narrow gradually from opposite large scale to relative small size, or opposite.

Term " micro passage reaction " refers to the equipment for including one or more process microchannels, is reacted wherein Method.This method can be fischer-tropsch reaction method.Micro passage reaction can include for receiving one or more catalyst to insert One or more slits of part (such as one or more fins or fin component, one or more corrugated plug-in units etc.), wherein Process microchannel includes slit, is arranged in catalyst insert, and/or comprising the opening formed by the wall and plug-in unit of slit. When using two or more process microchannels, process microchannel can be with operation repetitive.Micro passage reaction may include master (header) or manifold component are managed, the flowing for providing the fluid into one or more process microchannels；And tail pipe (footer) or manifold component, the flowing for the fluid for leaving one or more process microchannels is provided.Micro passage reaction can be with Including the one or more for being adjacent to one or more process microchannels and/or being thermally contacted with one or more process microchannels Hot switching path.Hot switching path can provide cooling for the fluid in process microchannel.Hot switching path can be micro- logical Road.Micro passage reaction may include supervisor or manifold component, for providing the stream into the heat-exchange fluid of hot switching path It is dynamic；With tail pipe or manifold component, the flowing for the heat-exchange fluid for leaving hot switching path is provided.

Term " process microchannel " refers to microchannel, carries out method wherein.This method can be the reaction side Fischer-Tropsch (FT) Method.

For the volume in process microchannel, term " volume " may include in process microchannel process fluid may flow All volumes that are logical or flowing through.The volume may include that can be set in process microchannel and suitable for fluid with the side of circulation Formula flows through volume in the surface characteristics that mode flows.

When referring to position of the channel relative to another channel, term " adjoining ", which can refer to, to be abutted directly against so that One or more walls separate the two channels.In one embodiment, two channels can have shared wall.Shared The thickness of wall can change.However, the channel of " adjoining " can not can be hampered by channel partition between two parties, the channel between two parties The heat between channel is hindered to be transmitted.One channel can be adjacent to described another in the only a part of the size in another channel A channel.For example, process microchannel can be longer than the hot switching path of one or more adjoining and extends beyond this Or the hot switching path of multiple adjoinings.

Term " thermo-contact " refers to two main bodys, for example, two channels, can with physical contact with one another or adjacent to each other, Or can not physical contact with one another or adjacent to each other, but still exchange heat each other.One main body connects with another main body for heat Other main bodys can be heated or cooled by touching.

Term " fluid " refer to gas, liquid, mixture of gas and liquid or solid containing dispersion, drop and/ Or the gas or liquid of gaseous state bubble.Drop and/or bubble can have irregular or regular shape and can have Similar or different sizes.

Term " gas " and " steam " can have identical meanings and be used interchangeably sometimes.

Term " residence time " or " mean residence time " refer to space in the channel of the fluid occupancy flowed in space Internal volume divided by the fluid flowed in space under temperature and pressure used average volumetric flowrate.

Term " upstream " and " downstream " refer in channel (such as process microchannel) or in process flow chart relative to The position of the flow direction of fluid in channel or process flow chart.For example, towards a location stream in channel or process flow chart It the position that a part for dynamic liquid stream not yet reaches will be for the downstream of the part of liquid stream.In channel or process flow chart Liquid stream far from the flowing of a position by the position of part will be for the upstream of the part of liquid stream.Term " upstream " " downstream " is not necessarily meant to refer to vertical position, because channel used herein can be horizontal, vertical or be taken with angle of inclination To.

Term " plate " refers to plane or substantially planar sheet material or plate.The plate can be referred to as gasket (shim).Plate Thickness can be the minimum dimension of plate and can be at most about 4mm, or be about 0.05 to about 2mm, or be about 0.05 to about 1mm, or be about 0.05 to about 0.5mm.Plate can have any length and width.

Term " surface characteristics " refers to the protrusion of the recess and/or conduit wall in conduit wall, the stream in interfering channel It is dynamic.Surface characteristics can rounded, spherical, frustoconical, oblong, square, rectangle, angled rectangle, checker board (checks), V-arrangement, blade-shaped, fin shape, waveform etc. and its combination of two or more.Surface characteristics can be with Containing subcharacter, the wherein main wall of surface characteristics also contains smaller surface characteristics, and the smaller surface characteristics can be in recessed The form of mouth, wave, indentation, hole, burr, grid, sector etc..Surface characteristics can have depth and width and right In non-circular surfaces feature, there is length.It is micro- logical that surface characteristics can be formed in used technique according to the method for the present invention On or within one or more inner walls in road, hot switching path and/or burning gallery.Surface characteristics can be referred to as passively Surface characteristics or passive composite character.Surface characteristics can be used for Interference Flow (for example, interference laminar flow streamline) and generate with always The angled convective flow in body flow direction.

Term " hot switching path " refers to the channel for wherein having the heat-exchange fluid for providing heat and/or absorbing heat. Hot switching path can be one thermally contacted from adjacent channel (such as process microchannel) and/or with the hot switching path A or multiple channels absorb heat or provide it heat.Hot switching path can be from adjacent to each other but be not adjacent to the heat The channel of interchange channel absorbs heat or provides it heat.In one embodiment, one, two, three or more Can be adjacent to each other and be set between two hot switching paths in channel.

Term " heat transfer wall " refers to the common wall between process microchannel and the hot switching path of adjoining, at this, heat Amount is transferred to another channel by common wall from a channel.

Term " heat-exchange fluid " refers to the fluid that can be released heat and/or absorb heat.

Term " waveform " refers to the adjoining smallclothes of material (such as Heat Conduction Material), and three-dimensional article is transformed by planar object Body.Waveform can be used for being formed one or more microchannels.Waveform can include the corrugated plug-in unit in right angle, can be sandwiched in Between opposite plane sheets or gasket.The corrugated plug-in unit in right angle can have rounded edge.In this way, one or more Microchannel can on three sides be defined by waveform and be defined on the 4th side by one of plane sheets or gasket.Wave Shape can be made of any material disclosed herein that can be used for preparing micro passage reaction.These materials may include copper, Aluminium, stainless steel etc..The thermal conductivity of waveform can be about 1W/m-K or higher.

Term " overall flow direction " can refer in channel that fluid can pass through the vector of traveling in open approach.

Term " bulk flow region " can refer to the open area in microchannel.Adjacent bulk flow region can be permitted Perhaps across the rapid fluid stream of microchannel without notable pressure drop.In one embodiment, the flowing in bulk flow region can Think stratiform.Bulk flow region can account for microchannel internal volume and/or cross-sectional area at least about 5%, or account for micro- The internal volume in channel and/or about the 5% of cross-sectional area to about 100% or about 5% to about 99% or about 5% to about 95%, Or about 5% to about 90% or about 30% to about 80%.

Term " open channel " or " flowing through formula channel " or " open approach " refer to having at least about gap of 0.01 mm Channel (such as microchannel) passes through entire channel to extend so that fluid can be flowed by channel without meeting with to flowing Obstacle.Gap can extend at most about 10mm.

The term " cross-sectional area " in channel (such as process microchannel) refers to the overall flow of the fluid in channel The area of orientation measurement and may include all areas in channel, including any surface characteristics that may be present, but do not include Conduit wall.For the channel being bent along its length, cross-sectional area can be perpendicular to the direction of overall flow along being parallel to length It spends and is measured at institute's reconnaissance of the line at the center (centre of area) in channel.Height and the size of width can be from one Conduit wall to opposite conduit wall measures.These sizes can not change because applying coating to the surface of wall.These sizes can To allow for the average value changed caused by surface characteristics, surface roughness etc..

The term " open cross sectional " in channel (such as process microchannel) refers to the totality of the fluid stream in channel The area of the orientation measurement of flowing opened in the channel for bulk flow of fluid.Open cross sectional can not include internal barrier Hinder object, such as surface characteristics that may be present etc..

Speed for the fluid flowed in channel, term " superficial velocity " refer to fluid in the inlet temperature in channel and Volume flow rate under pressure divided by the speed obtained by the cross-sectional area in channel.

Term " free stream speed " refer to stream in the channel with a distance from the side wall from channel is enough flowing so that Speed is the speed of maximum value.If without applicable moving boundary condition, the speed of the stream flowed in channel is in side It is zero at wall, but increases with increasing with a distance from side wall, until reaches steady state value.The steady state value is " free stream speed Degree ".

The term as used herein " process fluid " refers to the reactant that can be flowed in process microchannel, product and appoints What diluent or other fluid.

Term " reaction zone " refers to the space in microchannel, wherein chemical reaction occurs or in which at least one object occurs The chemical conversion of matter.Reaction zone can contain one or more catalyst.

Term " time of contact " refer to the reaction zone in microchannel volume divided by reactant in 0 DEG C of temperature and one Volume feed flow rate under the pressure of atmospheric pressure.

Term " fresh synthesis gas " refers to the conjunction for the reactant for flowing in micro passage reaction and being used as fischer-tropsch reaction At gas.

The gaseous products that term " tail gas " generates during referring to fischer-tropsch reaction.Tail gas can contain CO and H₂。

Term " reaction-ure mixture " refers to fresh synthesis gas and the tail gas or exhaust gas composition that are recycled from fischer-tropsch reaction (such as CO and H₂) mixture.

Term " conversion ratio of CO " refers to the fresh synthesis gas in reaction-ure mixture and the CO molal quantitys between product Change divided by fresh synthesis gas in CO molal quantity.

Term " conversion per pass of CO " refers to from general reaction object mixture (that is, fresh synthesis gas is plus recycling Tail gas or recycling exhaust gas composition) CO pass through the conversion ratio after micro passage reaction in one way.

Term " methane selectively " refers to that the molal quantity of methane in product subtracts the molal quantity of methane in reaction-ure mixture The molal quantity of the CO consumed again divided by reaction.

Term " yield " refer to the product for leaving micro passage reaction molal quantity divided by enter micro passage reaction it is anti- Answer the molal quantity of object.

Term " cycle " refers to the once-through that reactant passes through micro passage reaction.

Term " grading catalyst " refers to the catalyst of one or more gradients with catalytic activity.Grading catalyst It can be with the different concentration or surface area of catalytically-active metals.Grading catalyst can have active site not Same turnover rate.Grading catalyst can have the physical property and/or form with distance change.For example, grading catalyst can To have such active metal concentrations：It is relatively low in the inlet of process microchannel and in the outlet of process microchannel Higher concentration is nearby increased to, or opposite；Or catalytically-active metals are at the center (i.e. midpoint) closer to process microchannel Concentration it is lower, and the concentration higher near process microchannel wall, or opposite, etc..The thermal conductivity of grading catalyst can With in process microchannel a position be varied to another position.It can be by changing in constant surface area supporter On catalytically-active metals site size or by change supporter surface area for example by change supporter type or Grain size, to change the surface area of grading catalyst.Grading catalyst can have porous supporting body, the wherein surface of supporter Product is higher or lower in the different piece of process microchannel with volume ratio, then throughout applies identical catalyst and applies Layer.The combination of two or more foregoing embodiments can be used.Grading catalyst can have single catalyst component or More catalyst components (for example, bimetallic or trimetallic catalyst).Grading catalyst can in process microchannel from a position It sets the distance of another position and gradually changes its property and/or composition.Grading catalyst can include with frame Grain, the particle with frame catalytically-active metals in each particle are distributed in " egg-shell type ".Grading catalyst can be along work The length direction of skill microchannel is classified in the axial direction or in the horizontal.Grading catalyst can have different catalyst to form, no Same useful load and/or active catalyst sites number, can occur from a position to another location in process microchannel Variation.The number of active site can be changed by the variation of the porosity of catalyst structure.This can be by using The washcoated technique of the catalysis material of variable quantity can be deposited to realize.One example can be the length along the process microchannel Degree uses different porous catalyst thickness, and thicker porous structure is left on the position to need greater activity.It can also To the porosity of fixed or variable porous catalyst thickness application variation.Can for flowing open area or The first pore size is used near gap, and at least one second pore size can be used near process microchannel wall.

Term " chain growth " refers to that the molecule from following reaction increases：In the reaction, molecule is with new molecule knot The addition of structure and increase (e.g., in F- T synthesis, methylene group adds to hydrocarbon chain).

Term " aliphatic hydrocarbon " refers to aliphatic compound, such as alkane, alkene, alkynes etc..

Term " higher molecular weight aliphatic hydrocarbon " refer to have 2 or more carbon atoms or 3 or more carbon atom or The aliphatic hydrocarbon of 4 or more carbon atoms or 5 or more carbon atom or 6 or more carbon atom.Higher molecular weight aliphatic Hydrocarbon can have at most about 200 carbon atoms or more, or at most about 150 carbon atoms, or at most about 100 carbon atoms, or At most about 90 carbon atoms, or at most about 80 carbon atoms, or at most about 70 carbon atoms, or at most about 60 carbon atoms, or At most about 50 carbon atoms, or at most about 40 carbon atoms, or at most about 30 carbon atoms.Example may include ethane, third Alkane, butane, pentane, hexane, octane, decane, dodecane etc..

Term " Fischer-Tropsch " or " FT " refer to the chemical reaction represented by following equation：

n CO+2n H₂→(CH₂)_n+n H₂O

The reaction is exothermic reaction.N can be any number, for example, 1 to about 1000, or about 2 to about 200, or about 5 to About 150.

Term " Fischer-Tropsch product " or " FT products " refer to the hydrocarbon products prepared by fischer-tropsch process.FT product liquids can be with At atmosheric pressure with about 30 DEG C or more of boiling point.

Term " FT tail gas " or " tail gas " refer to the gaseous products prepared by fischer-tropsch process.Tail gas can be in atmospheric pressure There is the boiling point below about 30 DEG C under power.Tail gas can contain H₂And CO.

Term " Co useful loads " can refer to the weight of Co divided by the total weight of catalyst in catalyst, that is, Co, which is added, to be appointed The total weight of what co-catalyst or accelerating agent and any supporter.If catalyst support is in the supporting body structure of engineering On (such as foam, felt, agglomerate or fin), then the weight of the supporting body structure of the engineering can not be included in the calculating In.Similarly, if catalyst is attached on conduit wall, the weight of conduit wall can not be included in the calculating.

Term " mm " can refer to millimeter.Term " nm " can refer to nanometer.Term " ms " can refer to millisecond.Term " μ s " can To refer to microsecond.Term " μm " can refer to micron (micron or micrometer).Term " micron (micron) " and " micron (micrometer) " there is same meaning and be used interchangeably.

Unless otherwise indicated, all pressure is indicated with absolute pressure.

Method

Term " fresh synthesis gas " refers to a kind of gaseous mixture, contains CO and H₂And not in the method for the present invention A part for the tail gas for the recycling that period uses.Synthesis gas is properly termed as syngas.During the method for the present invention, fresh conjunction Contain at gas and also H₂It is combined with the tail gas of the recycling of CO, to form the reaction-ure mixture that the method for the present invention uses.Reaction Object mixture can include H₂And CO, wherein H₂It can be about 1.4: 1 to about 2.1: 1, or about 1.5: 1 to about with the molar ratio of CO 2: 1: 1, or about 1.6: 1 to about 2: 1, or about 1.7: 1 to about 1.9: 1.Fresh synthesis gas can include H₂And CO, wherein H₂With The molar ratio of CO is about 1.9: 1 to about 2.1: 1, or about 1.95: 1 to about 2.05: 1, or about 1.98: 1 to about 2.02: 1.At this It generates during inventive method and is combined with fresh synthesis gas to form the tail that the tail gas of reaction-ure mixture is properly termed as recycling Gas.The tail gas of recycling can include H₂And CO, wherein H₂Molar ratio with CO be about 0.5: 1 to about 2: 1, or about 0.6: 1 to About 1.8: 1, or about 0.7: 1 to about 1.2: 1.The volume ratio of fresh synthesis gas and tail gas can be about 1 in reaction-ure mixture: 1 to about 10: 1, or about 1: 1 to about 8: 1, or about 1: 1 to about 6: 1, or about 1: 1 to about 4: 1, or about 3: 2 to about 7: 3, or about 2: 1。

In the embodiment of illustration, it will be described with reference to Figure 1 the method for the present invention first.Referring to Fig. 1, method 100 uses Micro passage reaction 110.Micro passage reaction 110 can be referred to as Fischer-Tropsch microchannel reactor.In operation, fresh synthesis Gas 120 is combined with the tail gas 130 of recycling to form reaction-ure mixture 140.Fresh synthesis gas can be with micro passage reaction The tail gas combination (as shown in fig. 1) of the recycling of 110 upstreams, or combined in micro passage reaction 110.

In micro passage reaction 100, reaction-ure mixture passes through one or more process microchannels to flow, with catalysis Agent contacts, to form product.Catalyst can be referred to as fischer-tropsch catalysts, and be formed by being contacted with fischer-tropsch catalysts Product can include one or more higher molecular weight aliphatic hydrocarbons and tail gas.The reaction is exothermic.The reaction can make It is controlled with the heat-exchange fluid of such as arrow 170 and 180 instruction flowed across micro passage reaction 110.In a reality It applies in scheme, heat-exchange fluid can include steam.If arrow 150 indicates, products therefrom flows out micro passage reaction 110. If arrow 130 indicates, tail gas is detached from product, and recycled to be combined with fresh synthesis gas.If it is desired to adjust anti- Answer the ratio of the fresh synthesis gas and tail gas in object mixture, then it, can be by a part for tail gas from side as arrow 135 indicates It is detached in method.In the case where tail gas is detached from product, (it includes one or more higher moleculars for the remainder of product Measure hydrocarbon products and indicated by arrow 160) it is suitable for being further processed.

One or more micro passage reaction cores 110 can be accommodated in container 200.Container 200 has institute in Fig. 2 The construction shown.Referring to Fig. 2, container 200 is containing there are three Fischer-Tropsch microchannel reactor cores 110.Although disclosed in figure three it is micro- Channel reactor core, it is to be understood that, the micro passage reaction core of any required number can be set in container 200. For example, container 200 can contain 1 to about 100 micro passage reaction 110 or 1 to about 10 or 1 to about 3 microchannel Reactor 110.Container 200 can be pressurisable container.Container 220 includes an inlet and an outlet 112, allows reaction stream in a subtle way Channel reactor 110, product outflow micro passage reaction 110 and heat-exchange fluid flow in and out micro passage reaction.

When container 200 is when Fischer-Tropsch microchannel reactor 110 is used together, one in entrance 112 is connected to and is provided For making reaction-ure mixture flow to the manifold of the Fischer-tropsch process microchannel in micro passage reaction 110.In entrance 112 One is connected to that be provided for making heat-exchange fluid (such as steam) to flow to the heat exchange in micro passage reaction 110 logical The manifold in road.One in entrance 112 is connected to the Fischer-Tropsch work for being provided for making product to flow out in micro passage reaction 110 The manifold of skill microchannel.One in entrance 112 be connected to be provided make heat-exchange fluid flow out micro passage reaction 110 in Hot switching path manifold.

Container 200 can be constructed using any suitable material, and the material is enough in operation Fischer-Tropsch micro passage reaction It is operated under pressure and temperature needed for 110.For example, the shell 202 of container 200 can be constructed by cast steel.Flange 204, Connector and pipeline can be constructed by 316 stainless steels.Container 200 can have any desired diameter, for example, about 10 to About 1000cm, or about 50 to about 300cm.The axial length of container 200 can be any desired value, and for example, about 0.5 to about 50 meters, or about 1 to about 20 meter.

Micro passage reaction 110 can include the multiple Fischer-tropsch process microchannels for overlieing one another or being set up in parallel and Re Jiao Change channel.Micro passage reaction 110 can be in the form of cube block.This shows in Fig. 3 and 4.These cube blocks can be with It is referred to as micro passage reaction core 111.The length that each cube block can have is about 10 to about 1000cm, or about 20 to About 200cm.Width can be about 10 to about 1000cm, or about 20 to about 200cm.Height can be about 10 to about 1000cm, or About 20 to about 200cm.

Micro passage reaction 110 and container 200 can be sufficiently small and compact to can be easily transported.As a result, these The miscellaneous equipment used in reactor and container and the method for the present invention may be easy to transport to remote location, such as military base Ground etc..These reactors and container can be used on ship, oil drilling platform etc..

Micro passage reaction 110 can contain multiple repetitive units, and each repetitive unit includes one or more Fischer-Tropsch works Skill microchannel and one or more hot switching paths.The repetitive unit that can be used includes the repetition being shown respectively in Figures 5 and 6 Unit 210 and 210A.Micro passage reaction 110 can contain 1 to about 1000 repetitive unit 230 or 230A, or about 10 to about 500 this repetitive units.The catalyst used in repetitive unit 210 and 210A can be in any form, including graininess is solid The bed of body and various structured forms described below.

Repetitive unit 210 is shown in Figure 5.Referring to Fig. 5, process microchannel 212 is adjacent to containing hot switching path 216 Heat exchange layers 214 and be arranged.Hot switching path 216 can be microchannel.Common wall 218 is by process microchannel 212 and heat exchange Layer 214 separates.Catalyst is arranged in the reaction zone 220 of process microchannel 212.Reaction-ure mixture is (that is, fresh synthesis The tail gas of gas and recycling) it is flowed into the reaction zone 220 in process microchannel 212 with the direction that arrow 222 indicates, and it reacts Catalyst contact in area, and react to form product.Product (that is, one or more higher molecular weight aliphatic hydrocarbons and Tail gas) outflow process microchannel 210, as arrow 224 indicates.Heat-exchange fluid is with mixed with the reactant in process microchannel 212 The flowing of object and product is closed in the direction of cross-flow, hot switching path 216 is passed through to flow.The Fischer-Tropsch carried out in process microchannel 212 Reaction is exothermic, and heat-exchange fluid provides cooling for reaction.

Alternatively, as provided in repetitive unit 210A, process microchannel and hot switching path can be aligned.In addition to Except below, repetitive unit 210A shown in Fig. 6 is identical as repetitive unit shown in Fig. 5 210：Hot switching path 216 revolves Turn 90 ° and the heat-exchange fluid that flows across hot switching path 216 is with can be with reactant and production in process microchannel 212 Direction of the flowing in adverse current or the direction relative to reactants and products in process microchannel 212 of object are flowed in the direction of fair current It is dynamic.

Process microchannel 212 can be with cross section with any shape, for example, square, rectangle, circle, semicircle Deng.It is believed that the internal height of each process microchannel 212 is less than passes through process microchannel stream perpendicular to reactants and products The inside dimension in dynamic direction.The internal height that each process microchannel 212 can have is at most about 10mm, or at most about 6mm, or at most about 4mm, or at most about 2mm.Height can be about 0.05 to about 10mm, or about 0.05 to about 6mm, or about 0.05 to about 4mm, or about 0.05 to about 2mm.It is considered that the width of each process microchannel 212 is perpendicular to reactant and production Object passes through other inside dimensions in the direction of process microchannel flowing.The width of each process microchannel 212 can be any ruler It is very little, for example, at most about 3 meters, or about 0.01 to about 3 meter, or about 0.1 to about 3 meter.The length of each process microchannel 210 can be Any size, for example, at most about 10 meters, or about 0.1 to about 10 meter, or about 0.2 to about 6 meter, or about 0.2 to about 3 meter, or about 0.5 to about 2 meter.

Hot switching path 216 can with when microchannel or they can have they can not be classified as to the big of microchannel Size.Each hot switching path 216 can be with cross section with any shape, for example, square, rectangle, circle, semicircle etc.. It is believed that the internal height of each hot switching path 216 is less than perpendicular to the side that heat-exchange fluid flows in hot switching path To inside dimension.The internal height that each hot switching path 216 can have is at most about 10mm or at most about 5mm or extremely More about 2mm, or about 0.05 to about 10mm or about 0.05 to about 5mm or about 0.05 to about 2mm or about 0.05 to about 1.5mm. (it can be perpendicular to other inside of the heat-exchange fluid across the direction of hot switching path flowing to the width in these each channels Size) can be any size, for example, at most about 3 meters, or about 0.1 to about 3 meter.The length of each hot switching path 216 can be with For any size, for example, at most about 10 meters, or about 0.1 to about 10 meter, or about 0.2 to about 6 meter or 0.5 to about 3 meter, or about 0.5 to about 2 meter.

The number of repetitive unit 210 or 210A can be required number in micro passage reaction 110, for example, one, Two, three, four, six, eight, ten, it is hundreds of, thousands of, tens thousand of, hundreds thousand of a, millions of etc..

In the design of Fischer-Tropsch microchannel reactor, along process microchannel length provide customization exchange characteristics with Just optimization reaction can be advantageous.This can pass through the heat for making to be released by the fischer-tropsch reaction carried out in process microchannel Part release is removed with the heat provided by the heat-exchange fluid in the hot switching path in micro passage reaction or cooling phase With realizing.Compared with the rear portion of reaction zone or downstream part, the front of reaction zone or upstream portion in process microchannel In, the degree of fischer-tropsch reaction and the subsequent heat release of reaction offer may highers.Therefore, with the downstream part of reaction zone It compares, matched cooling requirement may higher in the upstream portion of reaction zone.It can be by providing the downstream portion with reaction zone Split-phase more heat exchanges or the flowing of cooling fluid and process microchannel than more heat exchanges or cooling duct and therefore In the upstream portion of reaction zone thermally contacted, to realize the heat exchange of customization.Alternatively or except this it Outside, the exchange characteristics of customization can be provided by changing the flow velocity of heat-exchange fluid in hot switching path.It is less with needs The region of heat exchange or cooling is compared, and in needing the region of additional heat exchange or cooling, can increase the stream of heat-exchange fluid Speed.For example, and with the downstream part of the reaction zone be thermo-contact hot switching path compared with, in process microchannel with institute The upstream portion for stating reaction zone is in the hot switching path of thermo-contact, and the higher flow rate of heat-exchange fluid can be advantageous.Cause This, it is logical with the heat exchange close to the possible smaller process microchannel 212 of flow velocity or the outlet of reaction zone 220 for example, see Fig. 5 Road 216 is compared, and higher can be being used in the hot switching path 216 of process microchannel 212 or the entrance of reaction zone 220 Flow velocity.It, can be by selecting best hot switching path size and/or each individually heat exchange logical for optimum performance The flow velocity of the heat-exchange fluid of road or every group of hot switching path, to design the heat transmission from process microchannel to hot switching path. Other design alternative solutions for customizing heat exchange can be related to the choosing of the fischer-tropsch catalysts of specific position in process microchannel Select and design (such as the use or other chemically or physically special of grain size, catalyst formulation, loading density, grading catalyst Property).These design alternative solutions can be influenced to discharge from the heat of process microchannel and be transmitted to the heat of heat-exchange fluid. The temperature difference (it can provide driving force for heat transmission) between process microchannel and hot switching path can be constant or can edge It the length of process microchannel and changes.

Fischer-tropsch process microchannel and hot switching path can have rectangular cross section and in parallel type vertical orientation planes Or it is aligned in horizontal alignment stacking plane.These planes can be tilted horizontal by degree of tilt.These constructions can be referred to as Parallel plate configuration.These channels can be arranged by Modular compact unit to scale up.These can be the institutes of Fig. 3 and 4 The form for the cube block shown.

Micro passage reaction 110 can be made of any material, the material provide sufficient intensity, dimensional stability and Heat transfer characteristic is to allow the operation of required method.These materials may include aluminium；Titanium；Nickel；Platinum；Rhodium；Copper；Chromium；It is any of above The alloy of metal；Brass；Steel (such as stainless steel)；Quartz；Silicon；Or its combination of two or more.Each micro passage reaction It can be by stainless steel construction, wherein using one or more copper or aluminium waveform to form channel.

Micro passage reaction 110 can be manufactured using known technology, including electro-discharge machining, conventional machining, laser cutting, Photochemistry processing, electrical-chemistry method, molding, water spray, coining, etching (for example, chemistry, photochemistry or plasma etching) and A combination thereof.

Micro passage reaction 110 can be constructed by forming gasket (its part is removed to allow for flowing through).Pad The stacking of piece can form integrated apparatus via diffusion bonding, laser welding, diffusion brazing and similar approach assembling.It can Micro passage reaction is assembled to use the combination of gasket or thin slice and local sheet material or band.In the method, can pass through Band or local sheet material are assembled to form channel or void area, to reduce the amount of material requested.

Micro passage reaction 110 can contain multiple plates or gasket, and the multiple plate or gasket are stacking form, with fixed Adopted multiple fischer-tropsch process layers and multiple heat exchange layers, each plate or gasket have the neighboring quilt of neighboring, each plate or gasket The neighboring of next adjacent plate is soldered to provide peripheral sealing to stack.This was submitted on October 18th, 2011 It is shown in U. S. application 13/275,727, this application is incorporated herein by reference.

Micro passage reaction 110 can be constructed using the waveform of rectangular corrugated card format.These right angle ripples Shape sheet material can have rounded edge rather than sharp edge.These plug-in units can be sandwiched in opposite plane sheets or pad Between piece.This is shown in Figure 4.In this way, microchannel can be defined by corrugated plug-in unit and be passed through plane on three sides One of sheet material defines on the 4th side.Process microchannel and hot switching path can be formed in this way.Use waveform system Standby micro passage reaction is disclosed in WO 2008/030467, and this application is incorporated herein by reference.

Process microchannel can contain one or more surface characteristics, the surface characteristics be one of process microchannel or The form of recess and/or protrusion on multiple inner walls.Surface characteristics can be used for interfering the stream of the fluid flowed in the channel It is dynamic.These can enhance mixing to the interference of flowing and/or heat is transmitted.Surface characteristics can be the form of patterned surface.It is micro- Channel reactor can be made by the way that multiple pads are compressed together by.One or two main surface of gasket can contain Surface characteristics.Alternatively, micro passage reaction can be assembled using some sheet materials or gasket and some bands or local sheet material, with Reduce the total amount for constructing the metal needed for the device.Gasket containing surface characteristics can (on two offsides of microchannel) with Another gasket pairing containing surface characteristics.Compared with the channel with surface characteristics in only one main surface, pairing can To generate the enhancing of more preferably mixing or heat transmission.Patterning can include the recess with twill, and recess is arranged in microchannel table On the substantially entire width in face.The patterned surface characteristic area of wall can account for a part or entire long for microchannel surface Degree.Surface characteristics can be arranged channel surface length at least about 10% or at least about 20% or at least about 50% or At least about 80%.Can include respectively one or more angles relative to flow direction with twill recess.Relative to other recessed Sunken surface characteristics, the feature being continuously recessed can include similar or alternate angle.

The feature of Fischer-tropsch process microchannel can be with bulk flow path.Term " bulk flow path " refers to Open approach (adjacent bulk flow region) in process microchannel or burning gallery.Adjacent bulk flow region allows Rapid fluid stream across channel, without big pressure drop.In one embodiment, in bulk flow region fluid stream It moves as laminar flow.The cross-sectional area of bulk flow region in each process microchannel or burning gallery can be about 0.05 to about 10, 000mm²Or about 0.05 to about 5000mm²Or about 0.1 to about 2500mm².Bulk flow region can account for process microchannel or About the 5% to about 95% of the cross section of burning gallery or about 30% to about 80%.

The time of contact of reactant and fischer-tropsch catalysts can be at most about 2000 milliseconds (ms), or about 10 to about 2000ms, or about 10ms is to about 1000ms, or about 20ms is to about 500ms, or about 200 to about 400ms, or about 240 to about 350ms。

The air speed (or gas per hour air speed (GHSV)) of the flowing of fluid in Fischer-Tropsch microchannel can be at least about 1000hr^-1(volume in liters in standard litres/hour/process microchannel of charging), or about 1000 to about 1,000,000hr^-1, or about 5000 to about 20,000hr^-1。

Pressure can be at most about 100 atmospheric pressure in Fischer-tropsch process microchannel, or about 1 to about 100 atmospheric pressure, or About 1 to about 75 atmospheric pressure, or about 2 to about 40 atmospheric pressure, or about 2 to about 10 atmospheric pressure, or about 10 to about 50 air Pressure, or about 20 to about 30 atmospheric pressure.

When being flowed in Fischer-tropsch process microchannel, the pressure drop of fluid can be that every meter of passage length is at most about 30 big Air pressure (atm/m), or at most about 25atm/m, or at most about 20atm/m.Pressure drop can be about 10 to about 20atm/m.

The Reynolds number that fluid flows in Fischer-tropsch process microchannel can be about 10 to about 4000 or about 100 to about 2000.

Mean temperature in Fischer-tropsch process microchannel can be about 150 to about 300 DEG C, or about 175 to about 225 DEG C, or about 190 to about 220 DEG C, or about 195 to about 215 DEG C.

Into the hot switching path of micro passage reaction 110 heat-exchange fluid may be at about 100 DEG C to about 400 DEG C, Or at a temperature of about 200 DEG C to about 300 DEG C.The heat-exchange fluid for leaving hot switching path may be at about 150 DEG C to about 450 DEG C or about 200 DEG C to about 350 DEG C at a temperature of.Residence time of the heat-exchange fluid in hot switching path can be about 1 to About 2000ms or about 10 to about 500 ms.When being flowed across hot switching path, the pressure drop of heat-exchange fluid can be at most about 10atm/m, or about 1 to about 10atm/m, or about 3 to about 7atm/m, or about 5atm/m.Heat-exchange fluid can be steam, liquid The form of the mixture of body or steam and liquid.The Reynolds number that heat-exchange fluid flows in hot switching path can be about 10 To about 4000 or about 100 to about 2000.

Heat-exchange fluid used can be to be put suitable for cooling Fischer-Tropsch in hot switching path in micro passage reaction 110 Any heat-exchange fluid of thermal response.These fluids may include air, steam, liquid water, gaseous nitrogen, including inert gas, Other gases including carbon monoxide, the oil of such as mineral oil, and such as it is available from Dow-Union Carbide's The heat-exchange fluid of Dowtherm A and Therminol.

Hot switching path used can include process channel in micro passage reaction 110, wherein carrying out endothermic process.This A little heat exchange process channels can be microchannel.The example for the heat absorption technique that can be carried out in hot switching path includes steam weight Whole and dehydrogenation reaction.The steam reformation of the alcohol occurred at a temperature of about 200 DEG C to about 300 DEG C is the heat absorption work that can be used The example of skill.Merge the endothermic reaction simultaneously to provide improved cooling, it is substantially higher than convection current cooling that typical heat flux may be implemented One magnitude.

When being flowed in the hot switching path in micro passage reaction 110, heat-exchange fluid can be undergone partially or completely Phase transformation.Except the heat that convection current cooling provides removes, which can provide additional from the shifting of the heat of process microchannel It removes.For the liquid heat-exchange fluid of vaporization, the additional heat shifted from Fischer-tropsch process microchannel can be by heat-exchange fluid Caused by the latent heat of required vaporization.In one embodiment, the heat-exchange fluid of about 50 weight % can be by vapour Change, or about 35 weight % can be vaporized, or about 20 weight % can be vaporized, or about 10% weight % or about 5 weight % It can be vaporized, or about 2 to about 3 weight % can be vaporized.

In micro passage reaction, the heat flux of heat exchange can be the one of process microchannel in micro passage reaction 110 About 0.01 to about 500 watt of (W/cm on the surface area every square centimeter of a or multiple heat transfer walls²), or about 0.1 to about 250W/cm², or about 1 to about 125W/cm², or about 1 to about 100W/cm², or about 1 to about 50W/cm², or about 1 to about 25W/ cm², or about 1 to about 10 W/cm².0.2 be can range from about to about 5W/cm², or about 0.5 to about 3W/cm², or about 1 to about 2W/cm²。

During fischer-tropsch reaction method control heat exchange can be conducive to control the selectivity to required product, this be by On the fact that：This additional cooling can be reduced or eliminated by with the undesirable parallel reaction shape compared with overactivity energy At undesirable by-product.

It can be come using hot switching path upstream or in channel passive structure (such as barrier), hole and/or mechanism Control the pressure in each individually hot switching path in micro passage reaction 110.By controlling the pressure in each hot switching path Power can control the temperature in each hot switching path.For each hot switching path, higher inlet pressure can be used, wherein Pressure is down to required pressure by passive structure, hole and/or mechanism.By controlling the temperature in each hot switching path, can control Temperature in Fischer-tropsch process microchannel processed.Thus, for example, by being adjacent to process microchannel or being heat with process microchannel Specific pressure is used in the hot switching path of contact, can operate each Fischer-tropsch process microchannel at desired temperatures.This is provided The advantages of accurately controlling each Fischer-tropsch process microchannel temperature.The use for accurately controlling each Fischer-tropsch process microchannel temperature carries Temperature profile and this method for customization is in whole the advantages of reducing on energy requirement.

In scaled device, for certain applications, it may be required that the quality of process fluid is equal in microchannel One distribution.The application can be when process fluid needs heat together with adjacent hot switching path or be cooled It waits.It can be obtained by changing cross-sectional area from a parallel microchannels to the uniform mass flow distribution of another microchannel ?.The homogeneity of mass flow distribution can be defined with the index of quality factor (the Q- factors) shown below.0% Q- because Son means absolutely uniform distribution.

The variation of cross-sectional area can lead to the difference of the shear stress on wall.In one embodiment, microchannel plate Answer the Q- factors of device 110 that can be less than about 50% or less than about 20% or less than about 5% or less than about 1%.

The superficial velocity of the fluid flowed in Fischer-tropsch process microchannel can be at least about 0.01 meter per second (m/s), or extremely Few about 0.1m/s, or about 0.01 to about 100m/s, or about 0.01 to about 10m/s, or about 0.1 to about 10m/s, or about 1 to about 100m/s, or about 1 to about 10m/s.

The free stream speed of the fluid flowed in Fischer-tropsch process microchannel can be at least about 0.001 m/s, or at least About 0.01m/s, or about 0.001 to about 200m/s, or about 0.01 to about 100m/s, or about 0.01 to about 200m/s.

The conversion ratio of the CO of fresh synthesis gas can be about 70% or higher or about 75% or more in reaction-ure mixture It is high or about 80% higher or about 90% higher or about 91% higher or about 92% or higher or about 88% to about 95% or about 90% to about 94% or about 91% to about 93%.Reaction-ure mixture (is followed again that is, fresh synthesis gas adds Ring tail gas) in CO, the conversion per pass of CO can be about 65% to about 90% or about 70% to about 85%.

0.01 to about 10% or about 1% to about 5% or about can be about to the selectivity of methane in Fischer-Tropsch (FT) product 1% to about 10% or about 3% to about 9% or about 4% to about 8%.

The Fischer-Tropsch product formed in micro passage reaction 110 can include gaseous products fraction and product liquid fraction.Gas State product fraction may include at atmosheric pressure boiling point be about 350 DEG C of hydro carbons below (such as tail across intermediate distillate Gas).Product liquid fraction (condensate fraction) may include hydro carbons that boiling point is about 350 DEG C or more (such as across heavy paraffin hydrocarbon Decompressed wax oil (vacuum gas oil)).

Using the combination of such as high pressure and/or low temperature vapour-liquid separator or low pressure separator or separator, can will boil Point is that about 350 DEG C of Fischer-Tropsch product fractions below are separated into tail gas fraction and condensate fraction, for example, about 5 to about 20 carbon originals The n-alkane and high-boiling hydrocarbon of son.After removing one or more fractions that boiling point is about 650 DEG C or more, it can incite somebody to action The fraction (condensate fraction) that boiling point is about 350 DEG C or more is separated into the wax slope that boiling point is about 350 DEG C to about 650 DEG C.Wax evaporates Part can contain about 20 to about 50 linear paraffins of carbon atom and the higher boiling branched paraffin of relatively small amount.It can use Fractionating process realizes separation.

The Fischer-Tropsch product formed in micro passage reaction 110 may include methane, wax and other heavy macromolecule volume productions Object.Product may include alkene, positive structure and isomery-alkane of such as ethylene and combinations thereof.These may include being fired in distillate Expect the hydrocarbon in range, the range includes jet or diesel fuel range.

Particularly, when needing to improve octane number and/or reduce pour point, branched can have for a variety of final applications Profit.Isomery degree can be the isoparaffin or every mole of n-alkane isomery about 3 of more than every mole about 1 mole of n-alkane Mole isoparaffin.When for diesel fuel composition, product can include that the hydrocarbon that Cetane number is at least about 60 mixes Object.

Fischer-Tropsch product can be further processed to form lubricating base oil or diesel fuel.For example, micro passage reaction Product obtained can be hydrogenated cracking in 110, then experience fractionation and/or isoversion, with provide lubricating base oil, Diesel fuel, aviation fuel etc..Fischer-Tropsch product can use disclosed in United States Patent (USP) 6,103,099 or 6,180,575 Method carries out hydroisomerization；It is carried out using the method disclosed in United States Patent (USP) 4,943,672 or 6,096,940 plus hydrogen is split Solution and hydroisomerization；It is dewaxed using the method disclosed in United States Patent (USP) 5,882,505；Or use is special in the U.S. Method disclosed in profit 6,013,171,6,080,301 or 6,165,949 carries out hydroisomerization and dewaxing.In these patents For the method for handling F- T synthesis hydrocarbon and the side using the disclosure of products therefrom made from these methods to quote Formula is incorporated herein.

Hydrocracking reaction can carry out in hydrocracking micro passage reaction, and can be related to hydrogen and lead to from micro- The Fischer-Tropsch product that is flowed out in road reactor 210 or the one or more hydrocarbon for being isolated from the Fischer-Tropsch product (such as it is a kind of or more Kind of liquid or wax Fischer-Tropsch hydrocarbon) between reaction.Fischer-Tropsch product can include one or more long chain hydrocarbons.In hydrocracking processes In, it can be by by C₂₃₊Fraction is cracked into C₁₂To C₂₂Intermediate range carbon number, to increase example fraction of diesel oil as required.Fischer-Tropsch The wax slope that micro passage reaction 110 generates can be fed to the hydrocracking micro passage reaction with excessive hydrogen and be used for Phase reaction.Under the reaction condition for increasing temperature and pressure, a part of of liquid feedstock can be converted to gas phase, and remain Under liquid portion can be flowed along catalyst.In conventional hydro cracking system, liquid stream is formed.For hydrocracking The use of the micro passage reaction of reaction can realize unique advantage in many aspects.These may include dynamics, pressure Drop, heat transfer and mass transfer.

Can the Fischer-Tropsch hydrocarbon products of hydrocracking can include that can be hydrogenated cracking in hydrocracking micro passage reaction Any hydrocarbon.These hydrocarbon may include the hydrocarbon containing the one or more C-C keys that can be broken in hydrocracking processes.It can Hydrocarbon to be hydrogenated cracking may include saturated fat compounds of group (such as alkane), unsaturated fat compounds of group (such as Olefine, alkine), alkyl (such as alkyl) substitution aromatic compound, alkylene (hydrocarbylene) (such as Alkylidene (alkylene)) substitution aromatic compound etc..

The feed composition of hydrocracking micro passage reaction may include one or more diluent materials.It is this dilute The example for releasing agent may include non-reacted hydrocarbon diluent etc..The concentration of weight based on Fischer-Tropsch product, diluent can be Zero to about 99 weight % or zero to about 75 weight % or zero to about 50 weight %.Diluent can be used for reducing thick liquid The viscosity of reactant.The viscosity of feed composition can be about 0.001 to about 1 centipoise in hydrocracking micro passage reaction, or About 0.01 to about 1 centipoise, or about 0.1 to about 1 centipoise.

Ratio into hydrogen and Fischer-Tropsch product in the feed composition of hydrocracking micro passage reaction can be about 10 To about 2000 standard cubic centimeter (sccm) hydrogen (ccm) Fischer-Tropsch products per cubic centimeter, or about 100 to about 1800sccm/ccm, Or about 350 to about 1200sccm/ccm.Hydrogen charging can also include water, methane, carbon dioxide, carbon monoxide and/or nitrogen.

H in hydrogen charging₂It can come from other method, such as steam recombination method (H₂The molar ratio of/CO is about 3 Product stream), method for partical oxidation (H₂The product stream that the molar ratio of/CO is about 2), self-heating recombination method (H₂The molar ratio of/CO About 2.5 product stream), CO₂Recombination method (H₂The product stream that the molar ratio of/CO is about 1), coal gasification method (H₂/ CO's rubs The product stream of your ratio about 1) and combinations thereof.For each in these feeding flows, routine techniques (such as film can be used Separation or absorption) make H₂It is detached with remaining component.

The Fischer-Tropsch product of hydrocracking can include the intermediate distillate that boiling point is about 260-700 °F (127-371 DEG C). Term " intermediate distillate " be intended to include diesel oil, jet fuel and kerosene boiling spread fraction.Term " kerosene " and " jet Fuel " boiling spread is intended to refer to the temperature range of 260-550 °F (127-288 DEG C), and " diesel oil " boiling spread is intended to refer to about The hydrocarbon boiling point of 260 to about 700 °F (127-371 DEG C).The Fischer-Tropsch product of hydrocracking can include gasoline or naphthalene fraction.These It is considered C₅To 400 °F of (204 DEG C) end points of fraction.

Catalyst

Catalyst precarsor

Catalyst precarsor is the material that can be activated to be formed catalyst.Term " catalyst " and " catalyst precarsor " Interchangeably in this specification using and will be understood according to its specific context.

Catalyst precarsor includes at least one catalyst metals, such as cobalt, can in the form of an oxide, as simple substance Metal exists using its carbide form or as any of these mixtures.Particularly, catalyst precarsor can include about 10 To the cobalt of about 60% cobalt (weight based on metal accounts for the percentage of the total weight of catalyst precarsor), or about 35 to about 50%, Or the cobalt of about 40 to about 44%, or about 42% cobalt.Cobalt can be used as CoO and/or Co₃O₄In the presence of.

Catalyst precarsor can include supporter on noble metal, can be Pd, Pt, Rh, Ru, Re, Ir, Au, Ag and It is one or more in Os.Noble metal can be one or more in Pd, Pt, Rh, Ru, Ir, Au, Ag and Os.Noble metal can Think one or more in Pt, Ru and Re.Noble metal can be Ru.As an alternative, or additionally, noble metal can be with For Pt.Catalyst precarsor can include the noble metal of a total of about 0.01 to about 30% (based on the total of existing all noble metals Weight accounts for the percentage of the total weight of catalyst precarsor) or a total of about 0.05 to about 20% noble metal or a total of about 0.1 to About 5% noble metal or a total of about 0.2% noble metal.

If desired, catalyst precarsor may include one or more components based on other metals as accelerating agent or Conditioning agent.These components based on metal can also be present at least partly as carbide, oxide or elemental metals urges In agent precursor.For one or more components based on other metals suitable metal can be Zr, Ti, V, Cr, Mn, Ni, It is one or more in the area Cu, Zn, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg, Tl and 4f- lanthanide series.The suitable areas 4f- Lanthanide series can be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or Lu.For a kind of or more The metal of component of the kind based on other metals can be one or more in Zn, Cu, Mn, Mo and W.For one or more The metal of component based on other metals can be one or more in Re and Pt.Catalyst precarsor can include a total of about (total weight based on all other metal accounts for the percentage of the total weight of catalyst precarsor to 0.01 to about 10% other metals Than) or a total of about by 0.1 other metals to about 5% or a total of about by 3% other metals.

Catalyst precarsor can contain the at most 10% carbon (weight based on the carbon (no matter any form) in catalyst Account for the percentage of the total weight of catalyst precarsor), or about 0.001 to about 5% carbon, or about 0.01% to about 1% carbon.Or Person, the feature of catalyst precarsor can be that carbon is not present.

Optionally, catalyst precarsor can contain organic compounds containing nitrogen, such as urea；Or organic ligand, such as ammonia or all Such as citric acid or the carboxylic acid of acetic acid (it can be in the form of salt or ester).

Precursor can be activated to generate fischer-tropsch catalysts, for example, by hydrogen and/or appropriate hydrocarbon gas or with another Heatable catalyst precursor in kind of gas (such as nitrogen and/or methane) diluted hydrogen, by carbide or oxide extremely Some are converted into elemental metals less.In the active catalyst, cobalt can optionally at least partly its carbide or oxide shape Formula.

Reducing agent

The rupture of catalyst precarsor is can be minimized or reduced using carboxylic acid as reducing agent and is crushed, to allow more More catalyst precarsors is brought into fischer-tropsch reaction in the catalyst of activation to be used, because generating less less than realizing Acceptable reactor pressure decrease (such as<340kPa (or 50psi)) minimum grain size standard catalyst precursor particles.One In the case of a little, it can eliminate and the threshold value grain size limit (for example, about 125 microns) is less than to remove for screening catalyst precarsor The needs of particle.It is not wishing to be bound by theory, it is believed that this is because compared with other reducing agents (such as urea), carboxylic acid and catalysis Reaction between agent metal precursor is less violent, but still valid provide high activity, the stablize and selectivity of the reaction Catalyst.

It can select carboxylic acid so that it minimizes the rupture of catalyst precarsor, but still finally generates effective catalyst.It can To use the mixture of two or more carboxylic acids.Carboxylic acid can be alpha-hydroxy carboxylic acid compounds, such as citric acid, glycolic, lactic acid or Mandelic acid.

The term as used herein " reducing agent " can also include the medicament for additionally serving as complexing agent.

Catalyst metal precursor

Catalyst metal precursor can be containing cobalt precursors.May include suitably benzoyl pyruvic acid cobalt, carbon containing cobalt precursors Sour cobalt, cobaltous cyanide, cobalt hydroxide, cobalt oxalate, cobalt oxide, cobalt nitrate, cobalt acetate, acetopyruvic acid cobalt and carbonyl cobalt.These cobalts Precursor can be used alone or can be applied in combination.These cobalt precursors can be hydrate form or anhydrous form.In some feelings Under condition, when cobalt precursors are not soluble in water, such as cobalt carbonate or cobalt hydroxide, a small amount of nitric acid or carboxylic acid can be added so that preceding Body can be dissolved completely in solution or suspension.Solution or suspension can contain very little water or not aqueous, in this situation Under, it can ignore drying steps in the method for forming catalyst precarsor.

Catalyst metal precursor can be cobalt nitrate.Cobalt nitrate can react during calcining with reducing agent, generate Co₃O₄。

Solution or suspension can contain at least one preliminary catalytic agent metal precursor, such as above-mentioned containing one of cobalt precursors Or the mixture containing cobalt precursors, and at least one secondary catalysts metal precursor.There may be this secondary catalysts metals Precursor, to provide accelerating agent and/or conditioning agent in the catalyst.Suitable secondary catalysts metal may include noble metal, example Such as Pd, Pt, Rh, Ru, Ir, Au, Ag and Os；Transition metal, for example, Zr, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Hg and Ti；And the areas 4f- lanthanide series, such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and/or Lu.

Secondary catalysts metal can be Pd, Pt, Ru, Ni, Co (if not preliminary catalytic agent metal), Fe (if not To remove grade catalyst metals), it is one or more in Cu, Mn, Mo, Re and W.

Catalyst support

Catalyst can be dispersed on the supporter of surface modification with anchor catalyst particle and provide mechanical strength. Supporter can include refractory metal oxides, carbide, carbon, nitride or its mixture of two or more.Support Body can include aluminium oxide, zirconium oxide, silica, titanium dioxide or its mixture of two or more.Supporter It surface can be by with silica, titanium dioxide, zirconium oxide, magnesia, chromium oxide, aluminium oxide or its two or more Mixture it is handled and is modified.It is used to support the material of body and material for being modified supporter can be different. It is not wishing to be bound by theory, it is believed that surface treatment provided herein helps Co in the operation phase of the fischer-tropsch process of the present invention Between avoid being sintered.

Supporter can include silica and silica surface can use oxide refractory soild oxide, Especially titanium dioxide-coated.Catalyst support can be the form of structured shape, pellet or powder.

Supporter can include titania modified silica supporter.Titanium dioxide (TiO₂) can be used for increasing Add the stability (such as being inactivated by reducing) of the catalyst of silica support.

Therefore, the deactivation rate of catalyst can be such：It can be in F- T synthesis using being greater than about 300 hours or greater than about 3,000 hour or greater than about 12,000 hour or greater than about 15,000 hour, institute's having time was Before needing catalyst regeneration.

At elevated temperatures, catalyst material can be reacted with the surface Si-OH groups on silica supporter, To generate silicate material, the silicate material is without fischer-tropsch activity and may be not easy to be reduced.This can lead to catalyst Active surface area loss, and therefore cause FTS activity decline.

It is not wishing to be bound by theory, it is believed that via the consumption of surface Si-OH groups, titanium dioxide occurs in silica Dispersion on surface is subsequently formed the Ti-O-Si keys of bridge joint.Therefore, silica supporter is carried out with layer of titanium dioxide Modification can remove Si-OH groups, and therefore prevent the formation of silicate.

TiO₂At least 11 weight % of the total weight of catalyst support can be accounted for or be more than 11 weight %.Particularly, Catalyst support can be in silica (SiO₂) on comprising 11-30 weight %, 11-25 weight %, 11-20 weight % or The TiO of 12-18 weight % or 15-17 weight % or about 16 weight %₂。

In one embodiment, catalyst precarsor can include the Co of about 40 to about 44 weight %, and about 0.1 to about 0.3 The Re of weight %, and about 0.01 to about 0.05 weight % Pt (being indicated with the percentage of the total weight of catalyst precarsor)；With And TiO₂Modified SiO 2 catalyst supporter, it includes the TiO of about 11 to about 30 weight %₂(with catalyst support Total weight percentage indicate).

Catalyst precarsor can include the Pt of the Re and 0.03 weight % of the Co of 42 weight %, 0.2 weight % (to urge The percentage of the total weight of agent precursor indicates)；And TiO₂Modified SiO 2 catalyst supporter, it includes 16 weights Measure the TiO of %₂(being indicated with the percentage of the total weight of catalyst support).

Catalyst can be the form of pellet type catalyst, and particle diameter distribution is that d10 is more than 90 μm and d90 less than 325 μ m.Average particle size distribution can be about 180 to about 300 μm.

Because titanium dioxide is more acid than silica, therefore the effect of dispersion of the titanium dioxide on silica surface Power can be characterized by the measurement of the surface acidity to modified supporter.In addition, earth silicon/titanic oxide interface Four-coordination Ti⁴⁺The presence of ion can further generate especially strong Lewis-acid sites.

The surface acidity of modified supporter can use the lewis base of such as ammonia real using temperature programmed desorption (TPD) It tests to measure.

In one embodiment, the surface acidity of catalyst support can be：It neutralizes and needs 0.20 μm of ol NH₃/m² Or more, such as 0.22 μm of ol NH₃/m²Or more.

For measure the Ti-O-Si on the supporter that Si-OH keys are modified replacement another method be by using FT-IR spectrum.In FT-IR, the bands of a spectrum of Si-OH groups are it is contemplated that about 980cm^-1Frequency at.In addition, Ti-O-Si groups Bands of a spectrum it is contemplated that about 950cm^-1Frequency at.Therefore, when the Si-OH keys of certain amount are replaced by Ti-O-Si groups, 980cm^-1Locate the strength reduction of bands of a spectrum, and 950cm^-1The intensity for locating bands of a spectrum increases.980cm^-1And 950cm^-1Locate the strong of bands of a spectrum The ratio between degree indicates that how many Si-OH group is replaced by Ti-O-Si groups.

FT-IR spectrum can be corrected by subtracting the spectrum of silica.Therefore, in these corrected spectrum, 980cm^-1The bands of a spectrum at place can be used as recess (dip) to occur." FT-IT intensity ratio " can be used and be seen in corrected spectrum The 980cm observed^-1And 950cm^-1The intensity of bands of a spectrum calculates, wherein use 950cm^-1Locate band maximum intensity divided by 980cm^-1Locate the intensity of bands of a spectrum minimum value.

Modified catalyst support is 950: 980cm^-1The FT-IR intensity ratio at place can be 1.2 or higher, such as 1.3 or Higher, 1.4 or higher or 1.5 or higher.

Deactivation rate

Catalyst can use for a long time (such as > 300 hours), and deactivation rate is less than about 1.4%/day or small In about 1.2%/day, or about 0.1% to about 1.0%/day, or about 0.03 to about 0.15%/day.

In fixed bed composite reaction device or high flux screening reactor, the deactivation rate of catalyst can be measured as The percent loss of every 24 hours CO conversion ratios, wherein CO conversion ratios can be greater than about 70% or greater than about 75% or be more than About 80%, the wherein loss is to be measured within 200 hours or longer time, and wherein 200 hours time started from When run time (TOS) less than 500 hours.

In micro passage reaction, catalyst can use for a long time (such as > 300 hours), and deactivation rate is small In about 0.25%/day, or about 0.001% to about 0.20%/day, or about 0.01 to about 0.10%/day, or about 0.08%/day.

In micro passage reaction, the deactivation rate of catalyst can be measured as every 24 hours CO loss of conversion Percentage is less than about 0.25, and wherein CO conversion ratios are greater than about 70%, or greater than about 75%, or greater than about 80%, the wherein loss It is to be measured within 200 hours or longer time, and wherein 200 hours time started from the operation less than 500 hours When time (TOS).

Co₃O₄Average grain diameter and particle diameter distribution

The Effects of Density in the activity and selectivity of cobalt-base catalyst possible receptor 1 activity site, very small grain size is advantageous 's.However, the inactivation of Co catalysts may generally follow opposite trend, maximum particle may be most stable.

Co₃O₄Number average bead diameter can be less than about 12nm (be measured by powder X-ray diffractometry, for example, use Siemens D5000 θ/θ powder diffractometers and CuK_αRadiation).Cobalt oxide particle diameter distribution may influence catalyst activity and stabilization Property, to which particle diameter distribution as narrow as possible may be useful.The width of particle diameter distribution can pass through lognormal particle diameter distribution C values measure.C is dimensionless ratio, and characterizes the width of particle diameter distribution.Co₃O₄The c of the lognormal particle diameter distribution of particle Value can be less than about 0.31.Co₃O₄Average grain diameter can be below about 11nm, or be about 8 to about 10nm.C values can be about 0.19 to about 0.31, or it is below about 0.25, or be about 0.19 to about 0.25.In Co₃O₄Number average bead diameter be about 8 to about 10nm In the case of, c can be less than 0.31.

Number average bead diameter can be about 8 to about 10nm, and c- values can be about 0.31 or smaller, such as 0.29 or smaller, 0.26 or Smaller or 0.25 or smaller.Alternatively or additionally, c- values can be about 0.19 or more, such as 0.20 or It is more or 0.235 or more.C- values can be about 0.19≤c≤0.31；0.19≤c≤0.29；0.19≤c≤0.26；0.19 ≤c≤0.25；0.20≤c≤0.31； 0.20≤c≤0.29；0.20≤c≤0.26；0.20≤c≤0.25；0.235≤c≤ 0.31；0.235≤c ≤0.29；0.235≤c≤0.26；Or 0.235≤c≤0.25.

(assuming that being equal to the spheric granules of crystal grain or there is lognormal Unimodal Distribution in the sample of calcined catalyst Crystal grain), the form of particle diameter distribution can be written as：

Wherein

Formula 1

Wherein R_oFor the equal particle radius of number, and the width of c (known its be dimensionless ratio) characterization particle diameter distribution.R_oMultiply Number average bead diameter is obtained with 2.

Characterize Co₃O₄The another way of relationship is by D- values between particle diameter distribution and the activity and stability of catalyst. D- values can be referred to as the recombination of the particle diameter distribution described by c- values, and not represent any new data.Therefore, c- values and D- values are mathematically related, but it can be seen that improved correlation between activity and stability of the D- values with catalyst.

D- values are by Co₃O₄Particle diameter distribution of the particle in fresh, unreduced catalyst (i.e. in catalyst precarsor) Parameter calculates.

For the Co with substantially the same number average bead diameter₃O₄Particle, it can be seen that trend between c- values and deactivation rate. D- values can be the improvement to c- values, because while D- values still consider Co₃O₄The width and number average bead diameter of particle diameter distribution this two Person, but the equal Co of its logarithm₃O₄The weight bigger of grain size, without maintaining substantially the same number average bead diameter to observe data Trend.This allows record and more single scale (D- values) rather than two scales (c- values and number average bead diameter).

D- values can draw lognormal particle diameter distribution to calculate by using formula 1 (seeing above).It can be by the logarithm Frequency (f under the pattern of normal distribution_Pattern) it is considered as measurement to the width of distribution.In order to illustrate FTS catalyst stabilities pair The accordance with tolerance of number average bead diameter can use following formula, wherein f_PatternIt is weighted by particle diameter distribution median to generate " grain size-weighting The dispersion of distribution " or D- values：

D=f_Pattern ^yxR_ox2

Formula 2

Wherein f_PatternFor the frequency under the pattern of logarithm normal distribution, R_OFor the equal particle radius of number, and y is to be seen based on experiment The empirical value examined.There is substantially similar composition via more selected (at least about 5 kinds to 10 kinds) but in Co₃O₄Grain size With the stability for the catalyst for having small variation on particle diameter distribution width, the value of y is determined.These variations can be via synthetic method Small change and realize, such as increase dipping solution dilution (in an example, show that this leads to the subtle of particle diameter distribution Change).Then, the FTS stability datas of these catalyst are collected under the same test conditions.Then, it is organized at this similar In catalyst, y is manually adjusted to generate the distribution of D- values so that the catalyst that FTS stablizes can be with unstable catalyst zone It separates.Catalyst is formed：16%TiO₂/SiO₂On 42%Co- 0.2%Re-0.03%Pt, y values be 1.15.

Therefore, D- values increase can representative diameter distribution constriction or number average bead diameter increase.

Co₃O₄Particle diameter distribution can influence catalyst FTS activity and stability so that preferably, Co₃O₄The logarithm of particle The D- values of normal state particle diameter distribution are about 19 or more.19.2 D- values are about 0.31 corresponding to c- values and number average bead diameter is about The particle diameter distribution of 10nm.19.8 D- values correspond to the particle diameter distribution that c- values are about 0.31 and average grain diameter is about 8nm.It is in office One in the case of these, and the reduction (constriction of such as particle diameter distribution) of c can lead to the increase of D.Therefore, in the average grain diameter of 8-10nm The specification of c≤0.31 in range corresponds to distribution of particles defined in the D- values greater than or equal to about 19.

In one embodiment, D- values can be about 19 or higher, such as 19.2 or higher, 20.4 or higher, 21.0 or Higher or 21.35 or higher or 21.4 or higher.Alternatively or additionally, D- values can be 23.5 or more It is low, such as 22.2 or lower.Within the scope of application, any of these upper and lower bounds are combined so that D- values can be about 19≤ D≤23.5；19≤D≤22.2； 19.2≤D≤23.5；19.2≤D≤22.2；20.4≤D≤23.5；20.4≤Dc≤ 22.2；21.0≤D ≤23.5；21.0≤Dc≤22.2；21.35≤D≤23.5；Or 21.35≤D≤22.2.

Catalyst or catalyst precarsor can include 16%TiO₂Modified silica supporter, on supporter Including Co₃O₄, average grain diameter is that about 9.6nm, c- value are about 0.31 and D- values are about 19.2.Alternatively, catalyst or catalyst Precursor can include 16%TiO₂Modified silica supporter includes Co on supporter₃O₄, average grain diameter is about 6.2nm, c- value are about 0.14 and D- values are about 29.1.

Co₃O₄The characteristic of particle can be influenced by the synthetic method of generation catalyst precarsor and catalyst.

Particularly, include TiO in catalyst₂It is (such as different using Titanium alkoxides in the case of modified silica supporter Titanium propanolate) it can be provided comprising the Co with above-mentioned property to be modified supporter₃O₄Catalyst.In this embodiment, Catalyst precarsor can contain less than 10% less than 5% or preferably smaller than 1% crystallization TiO₂(with all TiO₂It is being catalyzed Percentage in agent precursor indicates).Alternatively, all TiO present in catalyst precarsor₂Can be amorphous or noncrystal (being at most detectable limit).

Alternatively, including TiO in catalyst₂In the case of modified silica supporter, aqueous process can be used (as used two (2 hydroxy propanoic acid) two hydroxide diammonium conjunction titanium (IV)) is modified supporter, without the use of Titanium alkoxides.It is preferred that water Property method following article is described in entitled " aqueous treatment of catalyst support " part.The supporter that gained is modified also can It is enough to provide comprising the Co with above-mentioned property₃O₄Catalyst.

Similarly, it uses citric acid as fuel/reducing agent in the preparation of catalyst precarsor, can provide comprising tool There is the Co of above-mentioned property₃O₄Catalyst precarsor and catalyst.

In addition, the number for being used to form the dipping of catalyst can influence particle diameter distribution, and therefore influence c values.Specifically For, the increase of dipping time can lead to the increase of the increase of c values and the deactivation rate of catalyst.It is therefore preferable that dipping step Rapid number is reduced.Three impregnation steps can be used.

In one embodiment, catalyst can be formed using 4 dippings, generates 0.25 c values, preferably Co₃O₄'s Number average bead diameter is about 8 to about 10nm.

In one embodiment, catalyst can be formed using 6 dippings, generates 0.27 c values, preferably Co₃O₄'s Number average bead diameter is about 8 to about 10nm.

In one embodiment, catalyst can be formed using 8 dippings, generates 0.30 c values, preferably Co₃O₄'s Number average bead diameter is about 8 to about 10nm.

It is prepared by catalyst precarsor

Catalysis can be prepared by method as defined above or any method by being discussed in WO 2008/104793 Agent precursor.By spraying, dipping or dip-coating, apply solution or suspension to catalyst support.If solution or suspension are complete It is complete not aqueous, then step and calcining step can need not be dried after and then deposition step.

However, if using the catalyst metal precursor for being hydrate, solution or deposition can contain some hydrations Water.The water can be enough some components of solvent soln or suspension, such as carboxylic acid (if being at room temperature solid).However, In some situations, it may be necessary to some water be added to solution or suspension, to ensure catalyst metal precursor and other components It can dissolve or become to suspend.In this case, the amount of water used is usually to allow catalyst metal precursor and other components It dissolves or suspends required minimum.

Deposition, drying and calcination step may be repeated one or more times.It is molten used in deposition step for repeating every time Liquid or suspension can be identical or different.If the solution or suspension in repeating every time are identical, the repetition of step allows to urge The amount of agent metal reaches the required level in catalyst support step by step in repeating every time.If in repeating every time Solution or suspension are different, then the repetition of step allows the amount for making different catalysts metal in the series of steps to be carried out Horizontal plan needed for reaching.

Program heat protocol can be used during drying and calcination, gradually increase temperature to control by catalyst Other components of metal precursor and solution or suspension generate gas and heat.

During heating process, catalyst support can reach at atmosheric pressure no more than about 500 DEG C or be not more than About 375 DEG C or the maximum temperature no more than about 250 DEG C.

Temperature can be with about 0.0001 to about 10 DEG C/min or about 0.1 to about 5 DEG C/rate gradual change per minute (ramp).The rate can be about 10 to about 30 DEG C/min.

Illustrative program heat protocol can include：

(a) solution or suspension will deposited with about 1 to about 5 DEG C/min or about 2 DEG C/min of rate thereon Catalyst support is heated to the temperature of about 80 to about 120 DEG C or about 100 DEG C, and be maintained at this temperature about 1 to About 10 hours, or about 5 hours；

(b) about 150 to about 400 DEG C or about are heated to the rate of about 1 to about 5 DEG C/min or about 2 DEG C/min 200 to about 350 DEG C or about 250 DEG C of temperature, and be maintained at about 0.5 to about 6 hour or about 1 to about 6 at this temperature Hour or about 3 hours.

Heating stepses can be in rotary furnace, in static baking oven or in a fluidized bed carry out.

Once calcining step is completed, whether after the step carries out for the first time or at the end of repetition, you can will Other catalyst metals are optionally loaded into catalyst support.

Especially if to form metallic catalyst oxide, then calcining step can be at oxygen-containing atmosphere (such as air) Middle progress.

Activation of catalyst

Catalyst precarsor can be activated by any conventional activation method.For example, catalyst precarsor can use also Originality gas activates, the reducibility gas for example hydrogen, gaseous hydrocarbon, hydrogen and gaseous hydrocarbon (such as methane) mixture, The mixture of gaseous hydrocarbon, the mixture of hydrogen and a variety of gaseous hydrocarbons, hydrogen and nitrogen mixture, synthesis gas or synthesis gas and The mixture of hydrogen.

The pressure of gas can be 1 bar (atmospheric pressure) to about 100 bars or less than about 30 bars.Pressure can be about 5 to About 20 bars or about 10 to about 15 bars.

Catalyst precarsor can be heated to its activation temperature with about 0.01 to about 20 DEG C/min of rate.Activation temperature 600 DEG C can be not greater than about or no more than about 400 DEG C.Activation temperature can be about 300 DEG C to about 400 DEG C or about 325 DEG C extremely About 375 DEG C or about 350 DEG C.

Catalyst precarsor can be maintained under activation temperature about 2 to about 24 hours or about 8 to about 12 hours.

After the activation, catalyst can be cooled to required reaction temperature.

After the activation, catalyst can be used in above-mentioned fischer-tropsch process.

What is carried out in micro passage reaction includes using disclosed catalyst or before disclosed catalyst In the fischer-tropsch reaction of the catalyst of body, the performance of catalyst can substantially maintain about 5000 hours or longer reaction time, Without catalyst regeneration so that time of contact can be less than 500 milliseconds, and CO conversion ratios can be greater than about 70% and methane Selectivity can be less than about 10%.

" performance of catalyst substantially maintains " refers to mean exposure during 24 hours each data collection intervals Time, average CO conversion ratios and average methane selectively parameter can be within the above range.The duration of data collection intervals It can be 12 hours, 6 hours, 3 hours or 1 hour.By this method, although there may be small variation, catalyst for these parameters Overall performance between at the time of contact, in terms of CO conversion ratios and methane selectively can maintain.

Reaction time can be about 8000 hours or longer.Comprising use disclosed catalyst or from institute it is public In the fischer-tropsch reaction of the catalyst for the catalyst precarsor opened, within about 5000 hours or longer reaction time, with daily CO The deactivation rate for the catalyst that loss of conversion percentage measures can be about 0.09% or smaller.

The geometrical construction that catalyst can be suitble to any size and in process microchannel.Catalyst can be Median particle diameter is about 1 to about 1000 μm (micron) or about 10 to about 500 μm or about 25 to about 250 μm of granular solids shape Formula (such as bead, powder, fiber etc.).Median particle diameter can be about 125 to about 400 μm or about 170 to about 300 μm.? In one embodiment, catalyst can be the fixed bed form of granular solids.

Catalyst can be the fixed bed form (as shown in Figure 7) of granular solids.With reference to figure 7, the bed of granular solids The catalyst 261 of form is contained in process microchannel 260.If arrow 262 indicates, reactant enters fixed bed, and experience is anti- It answers, and such as the instruction of arrow 263, product outflow fixed bed.

Catalyst can be supported in catalyst support structure, the structure for example foam, felt, agglomerate or its Combination.Catalyst support structure can include the fin component or ripple being adapted for insertion into the slit in micro passage reaction Shape plug-in unit.Catalyst cobalt load can be at least about 20 weight % or at least about 25 weight % or at least about 28 weight %, Or at least about 30 weight % or at least about 32 weight % or at least about 35 weight % or at least about 38 weight %.

The term as used herein " foam " refers to the structure for having continuous wall, which defines through the hole of the structure. The term as used herein " felt " refers to the structure of the fiber with void space therebetween.The term as used herein " agglomerate " is Refer to the structure for the strand (such as steel wool) being entangled with.Catalyst can be supported on honeycomb.Catalyst can be supported on It flows through on formula supporting body structure, the felt for flowing through formula supporting body structure for example with adjacent segment, with adjacent segment Foam, the fin structure with gap, any washing coating (washcoat) being inserted on substrate are parallel to flow direction And with the gauze in the correspondence gap for flowing.

The example for flowing through formula structure is shown in Figure 8.In fig. 8, catalyst 266 is contained in process microchannel 265.Such as Arrow 268 and 269 indicates that open access 267 allows fluid to be flowed across process microchannel 265.Reactant contacts catalyst simultaneously And experience reaction is to form product.

Catalyst can be supported on flow type supporting body structure, the flow type supporting body structure such as foam, group Block, bead, powder or gauze.One example of flow through structure is shown in Figure 9.In fig.9, flow type catalyst 271 holds It is contained in process microchannel 270, if arrow 272 and 273 indicates, reactant is flowed across catalyst 271, and undergoes reaction To form product.

For flow type catalyst supporting body structure can by comprising silica gel, foam copper, sintering stainless steel fibre, The material of steel wool, aluminium oxide or its combination of two or more is formed.Supporting body structure can be passed by the heat of such as metal It leads material to be made, to enhance the heat transfer to catalyst or from catalyst.

Catalyst can be supported on fin component, which includes one be arranged in process microchannel Or multiple fins.Example is shown in Figure 10-12.With reference to figure 10, fin component 280 includes fin 281, is mounted on fin branch On support body 283, the basal wall 284 of 283 covering process microchannel 285 of the fin supporter.Fin 281 is from fin supporter 283 On protrude into the inside of process microchannel 285.Fin 281 may extend into the inner surface of the upper wall 286 of process microchannel 285 And it contacts.Fin channels 287 between fin 281 provide for reactants and products is parallel to the length of process microchannel 285 Spend the access flowed across process microchannel 285.Each fin 281 has outer surface on it is per one side.Outer surface is catalysis Agent provides supporter substrate.Reactant can pass through fin channels 287 to flow, and be supported on urging on the outer surface of fin 281 Agent contacts, and reacts to form product.Fin component 280a shown in Figure 11 is similar to fins set shown in Figure 10 Part 280, unlike, fin 281a does not extend to the inner surface of the upper wall 286 of microchannel 285.Shown in Figure 12 Fin component 280b is similar to fin component 280 shown in Figure 10, the difference is that the fin 281b tools in fin component 280b There is the cross-sectional shape of tapered in form.The height of each fin can be about 0.02mm to the height of at most process microchannel 285 Degree or about 0.02 to about 10 mm or about 0.02 to about 5mm or about 0.02 to about 2mm.The width of each fin can be about 0.02 to about 5mm, or about 0.02 to about 2mm, or about 0.02 to about 1mm.The length of each fin can be at most to lead to for technique is micro- Any length of the length in road 285, or at most about 10m, or about 0.5 to about 10m, or about 0.5 to about 6m, or about 0.5 to about 3m.Gap between each fin can be any value and can be about 0.02 to about 5mm or about 0.02 to about 2mm or about 0.02 to about 1mm.The number of fin can be the width about 1 of process microchannel 285 per cm to about in process microchannel 285 50 fins, or about 1 to about 30 fin are per cm, or about 1 to about 10 fin is per cm, or about 1 to about 5 fin is every Centimetre, or about 1 to about 3 fin is per cm.Each fin can have the rectangular or square form as shown in Figure 10 or 11 Cross section, or as shown in Figure 12 tapered in form cross section.When checking along its length, each fin can be straight line, Taper has serpentine-like configuration.Fin component can be by offer sufficient intensity, dimensional stability and heat transfer characteristic to allow work The expected any material operated in skill microchannel is made.These materials include：Steel (such as stainless steel, carbon steel etc.)；Aluminium；Titanium； Nickel；Platinum；Rhodium；Copper；Chromium；The alloy of any of above metal；Monel alloys；Inconel alloys；Brass；Polymer (such as thermosetting Property resin)；Ceramics；Glass；Quartz；Silicon；Or its combination of two or more.Fin component can be by Al₂O₃Or Cr₂O₃Shape It is made at material, wherein when fin component is heat-treated in air, Al is formed on the surface of fin component₂O₃Or Cr₂O₃ Layer.Fin component can be made of the alloy comprising Fe, Cr, Al and Y or the alloy comprising Ni, Cr and Fe.

Catalyst can be supported in the slit being set in micro passage reaction one or more corrugated plug-in units On.This is shown in FIG. 14, and wherein micro passage reaction 110 includes the corrugated plug-in unit 300 being inserted into slit 302.Slit 302 can include microchannel, and with the size being illustrated above as microchannel.Keep it big alternatively, slit 302 can have Size in microchannel.The process microchannel of micro passage reaction can include slit 302, or can be arranged corrugated In plug-in unit 300 and/or pass through slit 302 madial wall and plug-in unit 300 between opening formed.Each corrugated plug-in unit 300 Height can be about 0.02mm to the at most height of slit 302 or about 0.02 to about 10mm or about 0.02 to about 5mm or About 0.02 to about 2mm.The width of each corrugated plug-in unit 300 can be about 0.02mm to the at most width of slit 302 or about 0.02 to about 10mm or about 0.02 to about 5mm or about 0.02 to about 2mm.Each the length of corrugated plug-in unit can be at most For any length of the length of slit 302, or at most about 10m, or about 0.5 to about 10m, or about 0.5 to about 6m, or about 0.5 To about 3m.Corrugated plug-in unit 300 can be by offer sufficient intensity, dimensional stability and heat transfer characteristic to allow microchannel plate The expected any material operated of device is answered to be made.These materials include：Steel (such as stainless steel, carbon steel etc.)；Aluminium；Titanium；Nickel； Platinum；Rhodium；Copper；Chromium；The alloy of any of above metal；Monel alloys；Inconel alloys；Brass；Polymer (such as thermosetting property Resin)；Ceramics；Glass；Quartz；Silicon；Or its combination of two or more.Corrugated plug-in unit 300 can be made of alloy, The alloy forms Al when being heat-treated in air on the surface of plug-in unit₂O₃Or Cr₂O₃Layer.Corrugated plug-in unit 300 can be with It is made of the alloy comprising Fe, Cr, Al and Y or the alloy comprising Ni, Cr and Fe.

Catalyst can be directly on the inner wall of process microchannel and/or in one or more above-mentioned catalyst supports Washing coating or growth from solution in structure.Catalyst can be one block of porous continuous (contiguous) material or be object Manage many pieces of form of contact.Catalyst can include continuous material and have continuous porosity so that molecule can expand It dissipates across catalyst.In this embodiment, fluid can pass through catalyst to flow, rather than around its flowing.The cross of catalyst Sectional area can account for about the 1 to about 99% or about 10 to about 95% of the cross-sectional area of process microchannel.

Catalyst can include supporter, the boundary layer on supporter, and mixed on boundary layer or with boundary layer Catalyst material.Supporter may include above-mentioned foam, felt, agglomerate, fin structure or one kind or more in corrugated plug-in unit Kind.Boundary layer can be the solution being deposited on supporter or it can be by chemical vapor deposition or physical vapor deposition To deposit.Catalyst can include supporter, buffer layer, boundary layer and catalyst material.Supporter can be porous.Appoint What above-mentioned layer can be continuous or discontinuous, such as in the form of spot or dot, or in the shape with gap or the layer in hole Formula.Supporter can at least about 5% porosity (being measured by mercury porosimetry) and about 1 to about 2000 micron or About 1 to about 1000 micron of average pore size (number in bore dia sum divided by hole).Supporter can be porous ceramics or metal Foam.Workable other supporters include carbide, nitride and composite material.Supporter can be with about 30% to about 99% or about 60% to about 98% porosity.Supporter can be foam, felt, agglomerate, or combinations thereof form.Metal The open cell of foams can be about 20 holes/inch (ppi) to about 3000ppi, and be about in one embodiment 20 to about 1000ppi, and is about 40 to about 120ppi in one embodiment.Term " ppi " refer to the hole of per inch most (in isotropic material, measurement direction is unimportant for big figure；However, in anisotropic material, make number of perforations most It is measured on the direction of bigization amount).

When there are buffer layer, buffer layer can have the composition and/or density different from supporter and boundary layer, and And in one embodiment, coefficient of thermal expansion is the median of the coefficient of thermal expansion of porous supporting body and boundary layer.Buffering Layer can be metal oxide or metal carbides.Buffer layer can include Al₂O₃、TiO₂、SiO₂、ZrO₂, or combinations thereof. Al₂O₃Can be α-Al₂O₃、γ-Al₂O₃Or combinations thereof.Buffer layer can include by carrying out hot place to supporter in air Manage oxide skin(coating) (such as the Al formed₂O₃Or Cr₂O₃).Buffer layer can be by two or more layers different Asia in composition Layer is formed.For example, when porous supporting body is the metal of such as stainless steel foam, can use different in composition by two layers Sub-layer composition buffer layer.First sub-layer (being contacted with porous supporting body) can be TiO₂.Second sub-layer can be to be placed in TiO₂On α-Al₂O₃.In one embodiment, α-Al₂O₃Sub-layer is compacted zone, and guarantor is provided for following metal surface Shield.Then the boundary layer of less fine and close, high surface area, such as aluminium oxide, the supporter as catalytic active layer can be deposited.

Supporter can have the coefficient of thermal expansion different from boundary layer.In this case, buffer layer may be needed two Transition between a coefficient of thermal expansion.Its coefficient of thermal expansion can be customized by controlling the composition of buffer layer, with obtain with it is porous The compatible coefficient of expansion of the coefficient of expansion of supporter and boundary layer.Buffer layer should be free of opening and pin hole to be following Supporter provides excellent protection.Buffer layer can be non-porous.The thickness of buffer layer can be less than being averaged for porous supporting body The half in aperture.The thickness of buffer layer can be about 0.05 to about 10 μm or about 0.05 to about 5 μm.

In one embodiment, enough adhesive force and chemical stability can be obtained, without buffer layer.At this In embodiment, buffer layer can be omitted.

Boundary layer may include nitride, carbide, sulfide, halide, metal oxide, carbon, or combinations thereof.Interface Layer provides high surface area and/or provides desired catalyst-supporter interaction for the catalyst of support.Boundary layer can be with Any material by being conventionally used as catalyst support is constituted.Boundary layer can include metal oxide.The metal that can be used The example of oxide includes α-Al₂O₃、 SiO₂、ZrO₂、TiO₂, tungsten oxide, magnesia, vanadium oxide, chromium oxide, manganese oxide, oxidation Iron, nickel oxide, cobalt oxide, copper oxide, zinc oxide, molybdenum oxide, tin oxide, calcium oxide, aluminium oxide, lanthanide oxide, zeolite And combinations thereof.Boundary layer can serve as catalytic active layer, and deposited thereon without any other catalytically-active materials.Interface Layer can be applied in combination with catalytic active layer.Catalyst can be mixed with boundary layer.Boundary layer can also be by two or more layers Different sub-layers is formed in composition.The thickness of boundary layer can be less than the half of the average pore size of porous supporting body.Boundary layer Thickness can be about 0.5 to about 100 μm, and be about 1 to about 50 micron in one embodiment.Boundary layer can be knot It is brilliant or unbodied.The BET surface area of boundary layer can be at least about 1m²/g。

Catalyst can be deposited on boundary layer.Alternatively, catalyst can simultaneously be deposited with boundary layer.Catalyst layer can To be closely dispersed on boundary layer.Catalyst layer " dispersion " or " deposition " include general understanding on boundary layer, i.e., microcosmic Catalyst granules is dispersed in：On carrier layer (i.e. boundary layer) surface, in the gap of carrier layer and in the open bore of carrier layer.

Catalyst can be classified in composition or with the catalyst bed of the inert material classification of heat transfer.Heat transfer is lazy The material of property can be spread in the active catalyst.The example for the inert material of heat conductivity that can be used includes diamond Powder, silicon carbide, aluminium, aluminium oxide, copper, graphite etc..The share of catalyst bed can be about the active catalyst of 100 weight % To less than 50 weight % active catalyst.The share of catalyst bed can be about 10 weight % to the activity of about 90 weight % Catalyst, and be about 25 weight % to about 75 weight % in one embodiment.In another embodiment, heat transfer Inert material can be deployed at the center of catalyst or in catalyst particles intragranular.Active catalyst can be deposited over packet Include the composite construction of the inert material of heat transfer outside, within or between.Obtained catalyst composite structure, which is worked as, is placed in work There can be effective thermal conductivity when in skill microchannel or burning gallery, 0.3W/m/K is at least about, in an embodiment In at least about 1W/m/K, in one embodiment at least about 2W/m/K.

Catalyst bed can only in process microchannel local hierarchical.For example, process microchannel, which can contain, has first The catalyst bed of reaction zone and second reaction zone.The top of catalyst bed or bottom (or front or rear portion) can form Aspect is classified, and the catalyst that activity is higher or lower is thus used in all or part of first or second reaction zone.One The composition of reduction can generate the less heat of per unit volume in a conversion zone, and reduce hot spot and generation with this The possibility of undesirable by-product (methane in such as fischer-tropsch reaction).Catalyst can be first and/or second reaction zone All or part in be classified with inert material.First reaction zone can be containing catalyst or inert material the first composition, And second reaction zone can be containing catalyst or inert material the second composition.

Different grain sizes can be used in the different axial regions of process microchannel, to provide the catalyst of classification Bed.For example, very small particle can be used in the first conversion zone, and can be used in second reaction zone larger Particle.Average particle diameter can be less than the height of process microchannel or the half in gap.Very small particle can be less than The height of process microchannel or a quarter in gap.Larger particle can cause on the per unit length of process microchannel Lower pressure drop, and catalyst efficiency can also be reduced.For the particle of large-size, the effective thermal conductivity of catalyst bed Rate may decrease.During smaller particle can be used in entire catalyst bed needing to be improved the region of heat transfer, or Person, larger particle can be used for reducing the rate of heat production of part.

The relatively low deactivation rate of relatively short time of contact, the highly selective and catalyst to desired product can be with It is realized by the diffusion path needed for limiting catalyst.This can be in catalyst in the engineering of such as metal foam It is achieved when the form of the thin layer on carrier or on process microchannel wall.This can allow to improve air speed.Chemistry can be used Vapor deposition method generates the thin layer of catalyst.The thickness of the thin layer can be at most about 1 micron, and in an embodiment party It is about 0.1 to about 1 micron in case, and is about 0.1 to about 0.5 micron in one embodiment, and in an embodiment party It is about 0.25 micron in case.These thin layers can reduce reactant in active catalyst structure by shortening diffusion path Time.This can shorten the time that reactant expends in the active part of catalyst.The result can be improved to product Selectivity simultaneously reduces undesirable by-product.The advantages of catalyst distribution of this pattern can be, and in conventional catalyst The binder that the active part of catalyst can be bound by inert lower thermal conductivity is different, and active catalyst film can be with engineering The structure of change or the wall of process microchannel are in close contact.This can realize high heat transfer rate simultaneously in micro passage reaction Allow precise control of temperature.This can bring the ability (faster dynamics) to work at elevated temperatures without promoting not The generation of desired by-product, therefore generate higher productivity and yield and extend catalyst life.

The construction of micro passage reaction 110 can be customized to matching kinetics.First in process microchannel is anti- Answer the entrance or near top in area, microchannel height or gap can be less than in second reaction zone the outlet of process microchannel or Height near bottom or gap.Alternatively, reaction zone can be less than the half of process microchannel length.For example, anti-for first Initial 25%, 50%, 75% or 90% of the length of the process microchannel in area are answered, the first process microchannel height can be used Or gap, and the second height or the gap of bigger can be used in the second reaction zone in the first reaction zone downstream.The setting It may be adapted to carry out fischer-tropsch reaction.The height of process microchannel or other hierarchy plans in gap can be used.For example, micro- The entrance in channel can make using the first height or gap to provide the first reaction zone in the first reaction zone downstream With the second height or gap to provide second reaction zone, and third height or gap can be used so as in the outlet of microchannel It is provided about third reaction zone.First and third height or gap can be identical or different.First and third height or gap can To be less than or greater than the second height or gap.Third height or gap can be less than or greater than the second height or gap.Second Height or gap can be more than or less than third height or gap.

It can make catalyst by making regenerative fluid that the process microchannel burning gallery contacted with catalyst be passed through to flow Regeneration.Regenerative fluid may include hydrogen or diluted hydrogen stream.Diluent can include nitrogen, argon gas, helium, methane, two Carbonoxide, steam or its mixture of two or more.The temperature of regenerative fluid can be about 50 to about 400 DEG C, and It is about 200 to about 350 DEG C in one embodiment.During regeneration step, the pressure in channel can be about 1 to about 40 A atmospheric pressure, and be about 1 to about 20 atmospheric pressure in one embodiment, and be about 1 in one embodiment To about 5 atmospheric pressure.The residence time of regenerative fluid is about 0.01 to about 1000 second in channel, and in an embodiment In be about 0.1 second to about 100 seconds.

Catalyst can regenerate in the following manner：By H in reactant composition₂Increase at least about with the molar ratio of CO 2.5: 1 or at least about 3: 1, and at a temperature of about 150 DEG C to about 300 DEG C or about 180 DEG C to about 250 DEG C, make gained Adjusted feed composition about 0.5 to about 20 hour through about 0.1 to about 100 hour or in one embodiment when Between, it passes through process microchannel to flow, is contacted with catalyst, to provide regenerated catalyst.It can be by interrupting in addition to hydrogen The flowing of all feed gas and make hydrogen pass through process microchannel, contacted with catalyst, to adjust feed composition.It can be with Increase H₂Flowing, with provide with include H₂Identical time of contact used in reactant composition with CO.It is adjusted into Feed composition can include H₂And it is characterized by and CO is not present.Once catalyst is reproduced, you can with by making regenerated urge Agent and include H₂It is contacted with the initial reaction compositions of CO, to continue fischer-tropsch process.It can be by being removed from catalyst Wax and other hydro carbons are (usually by with H₂Stripping), with air or it is other contain O₂Gas makes catalyst oxygen at elevated temperatures Change, catalyst is made to restore and then make activation of catalyst and make catalyst regeneration.

Embodiment 1

Catalyst precarsor is prepared using following reagent：

	Supplier	Coding	Purity
Cobalt(II) nitrate hexahydrate	Sigma-Aldrich	230375	98%
				Tetramine platinic hydroxide	Alfa Aesar	38201-97-7	9.3%Pt w/w
Silica (SG432)	Grace Davison	(180-300μm)
				Citric acid monohydrate closes object (CA)	Sigma Aldrich	C1909	ACS reagents
Cross rehenic acid	Sigma Aldrich	70 weight % solution in water	99.99%

It is prepared by supporter

100g 16%TiO are prepared by following substance₂Modified silica is (with the weight percent of catalyst support Than indicating)：

Silica (180-300 μm)	84g
		Citric acid monohydrate closes object	25g
Two (2 hydroxy propanoic acid) two hydroxide diammonium closes titanium (IV) solution (TALH)	118g(97mL)
		Approximate liquor capacity	130-135mL

It will only be the catalyst support material of silica at 100 DEG C dry 2 hours and before impregnation to allow It is cooled to room temperature.25g citric acids are dissolved in minimal amount of water at 40 to 45 DEG C and are cooled to less than 30 DEG C.Then, will Citric acid solution is added to two hydroxide diammoniums of 118g (97ml) two (2 hydroxy propanoic acid) and closes in titanium (IV) solution (TALH), and And it is supplemented to required dipping volume with water (it is about 130 to 135ml).Pass through the citric acid-TALH dipping solutions obtained by It sprays to impregnate the desired amount of silica (84g, the dry weight measured later).

Then, be dried with 2 DEG C/100 DEG C/5h (gradual change/temperature/holding), and with 2 DEG C/250 DEG C/5h (gradual change/ Temperature/holding) it is calcined.After drying and calcination, the yield of modified catalyst support is about 120g.Modified urges The color of agent supporter is dark-brown.

The preparation of first dipping solution

25g Cobalt(II) nitrate hexahydrates (Sigma Aldrich, 98% purity) is soluble in water, then solution is heated to 40 to 45 DEG C, until salt is completely dissolved.Clear solution is obtained using minimal amount of required water.0.048g is crossed into rehenic acid (Sigma Aldrich, 70 weight % solution in water, 99.99% purity) are added in cobalt nitrate solution and mix.It will The solution of gained is cooled to room temperature (being less than 30 DEG C) and is supplemented to 19ml with water.

Dipping-first step

The catalyst support of 20g modifications is impregnated by using cobalt nitrate/mistake rehenic acid solution of 19ml, and is changed Property catalyst support first time dipping.Then by the catalyst support of the modification of gained with the gradual change speed of 2 DEG C/min Rate increases to 100 DEG C of temperature to be dried.Temperature is kept for 5 hours at 100 DEG C.The then modified supporter of calcining Temperature is increased to 200 DEG C using the fade rates of 2 DEG C/min and temperature is kept 3 hours at 200 DEG C, so by catalyst It is 1 small that the fade rates of 2 DEG C/min are used afterwards, temperature is further increased to 250 DEG C and keep at 250 DEG C temperature When.

For second to the dipping solution of four steps preparation

It is soluble in water that 12g citric acid monohydrates are closed into object (Sigma Aldrich, ACS reagent).It is added to clear solution 81.4g Cobalt(II) nitrate hexahydrates (Sigma Aldrich, 98% purity), are then heated to 40 to 45 DEG C by solution, until salt It is completely dissolved.Clear solution is obtained using minimal amount of required water.0.14g is crossed into rehenic acid (Sigma Aldrich, in water 70 weight % solution, 99.99% purity) it is added in cobalt nitrate and citric acid solution and mixes.By the stock solution of gained It is cooled to room temperature (being less than 30 DEG C) and is supplemented to 66 to 67ml with water.

- the second is impregnated to four steps

By using the catalyst support of modification of the stock solution dipping derived from the first impregnation steps of about 22ml (27.20g) carries out the second impregnation steps.Then modified catalyst support is increased to the fade rates of 2 DEG C/min 100 DEG C of temperature is dried.Temperature is kept for 5 hours at 100 DEG C.Then by using the fade rates of 2 DEG C/min Temperature is increased to 250 DEG C and keeps temperature 3 hours at 250 DEG C, with the modified support body catalyst of calcining.

By using modified catalyst supporter of the stock solution dipping derived from the second impregnation steps of about 22ml (34.40g) carries out third impregnation steps.Then modified catalyst support is increased to the fade rates of 2 DEG C/min 100 DEG C of temperature is dried.Temperature is kept for 5 hours at 100 DEG C.Then by using the fade rates of 2 DEG C/min Temperature is increased to 250 DEG C and keeps temperature 3 hours at 250 DEG C, with the modified support body catalyst of calcining.

By using modified catalyst supporter of the stock solution dipping derived from third impregnation steps of about 22ml (41.60g) carries out the 4th impregnation steps.Then modified catalyst support is increased to the fade rates of 2 DEG C/min 100 DEG C of temperature is dried.Temperature is kept for 5 hours at 100 DEG C.Then by using the fade rates of 2 DEG C/min Temperature is increased to 250 DEG C and keeps temperature 3 hours at 250 DEG C, with the modified support body catalyst of calcining.

Four impregnation steps are summarized in table 1.Total value in table 1 only relates to the total value of step 2 to 4.

Accelerating agent adds the-the five impregnation steps

Then, it using the catalyst precarsor of 20g obtained after four impregnation steps, carries out accelerating agent and adds step. 0.06g tetramines platinic hydroxide (tetraammine platinum hydroxide, Alfa Aesar, 9.3%Pt w/w) is added Enter into 9ml water to prepare diluted solution and the solution is used for further impregnation catalyst agent precursor.After immersion, Catalyst is then increased into 100 DEG C of temperature to be dried with the fade rates of 2 DEG C/min.Temperature is protected at 100 DEG C It holds 5 hours.Temperature is then increased to 250 DEG C by using the fade rates of 2 DEG C/min and protects temperature at 250 DEG C It holds 3 hours, with calcined catalyst.The catalyst of gained has 0.03%Pt.

Embodiment 2

Use the catalyst of embodiment 1, this series of fischer-tropsch reaction fresh using reactant in a series of fischer-tropsch reactions The mixture of synthesis gas or fresh synthesis gas and tail gas carries out in micro passage reaction.Figure 13 is to show method used Process flow chart.Results are shown in Table 2.Data in table 2 are generated using single micro passage reaction.Use the quality of calibration Flow controller, by carbon monoxide (CO), hydrogen (H₂) and nitrogen (N₂) it is individually delivered to reactor, so as to independently The flow for changing each gas, to simulate different process setting, such as the single reactor stage with recirculation circuit.With it is anti- Answer chamber not be fluid communication two adjacent microchannels in, with the deep fat controlling reaction temperature of co-current flow.With between grade In a series of three separators of heat exchanger, reaction product and unreacting gas are separated into the stream and steam material of condensation Stream, and at a temperature of each separator flask maintained successively decreasing.In the end of separator series, tail gas (produce by steam phase reaction Object adds unreacted unstripped gas) leave system via pressure-control valve (setting to control the pressure at reactor inlet).

Stream is exported by characterization to determine reactivity worth；Drying is analyzed using the micro- gas chromatographs of Agilent 3000A Tail gas form and using gas gauge measure rate of discharge.The calculating of the rate of discharge of any substance is by making moles hundred Divide than being multiplied by total gas stream, is normalized to the same datum condition used in calibrating quality flow controller.Pass through the conversion ratio of CO (at most C is added with the selectivity to methane₈Other hydrocarbon materials) judge the performance of reactor.Pass through the entrance stream from calibration Amount subtracts outlet CO flows to determine the amount for the CO being converted.Convert CO's by the CO throughputs from reactor inlet Amount, the percent conversion of calculating.Methane (C₁) calculating of selectivity is the amount by methane caused by making divided by is converted CO amount.

Abbreviation

To the CO flows of reactor：CO_Enter

Substance mole % in tail gas is measured through micro- GC：[substance], such as [CO]

Total offgas outlet flow：Flow_{Go out}

CO_inIt is set by the MFC of calibration

CO_out=[CO] x flows_{Go out}

CO conversion ratios=100%x (CO_Enter-CO_{Go out})/CO_Enter

C1 selectivity=100%x flows_{Go out}x[C1]/(CO_Enter-CO_{Go out})

The FT reaction products condensed from three separator collections weigh to determine throughput rate, and use Agilent 7890 gas chromatographs are using the method from ASTM D2887 come independent analysis.Based on the throughput rate of each phase, by GC data It combines in proportion, to generate full carbon number distribution shown in associated documents.

Although relatively describing the present invention with various embodiments, it is to be understood that, read specification it Afterwards, various modifications will become apparent to one skilled in the art.It will thus be appreciated that disclosed herein Invention includes any this modification that may be fallen within the scope of the appended claims.

Claims (42)

1. a kind of method for carrying out fischer-tropsch reaction, it includes：

So that the reaction-ure mixture formed by fresh synthesis gas and tail gas is flowed in micro passage reaction, contacted with catalyst, To form the product for including at least one higher molecular weight hydrocarbon products with 5 or more carbon atoms, the microchannel plate Device is answered to include at least one process microchannel and be at least one heat exchange thermally contacted at least one process microchannel Channel, the catalyst are at least one process microchannel, at least one hot switching path there is heat to hand over Change of current body, for carrying out heat exchange at least one process microchannel；

The wherein described product also includes tail gas, and the tail gas includes H₂And CO, at least part of the tail gas is with described compared with high score Son amount hydrocarbon products are detached and are combined with fresh synthesis gas to form the reaction-ure mixture, in the reaction-ure mixture In, the volume ratio of the fresh synthesis gas and the tail gas is 1:1 to 10:1；

The reaction-ure mixture includes H₂And CO, in the reaction-ure mixture, H₂Molar ratio with CO is 1.4:1 to 2.1:1；

Wherein based on the CO in the fresh synthesis gas in the reaction-ure mixture, the conversion ratio of CO is 88% to 95%； And

It is 0.01 to 10% to the selectivity of methane in the product.

2. according to the method described in claim 1, the wherein described micro passage reaction includes multiple process microchannels and multiple heat Interchange channel.

3. according to the method described in claim 1, the wherein described micro passage reaction includes multiple process microchannels and multiple heat Interchange channel, each hot switching path are to thermally contact at least one process microchannel；For making the reaction-ure mixture stream Move at least one of process microchannel manifold；For making product flow out at least one discrimination of the process microchannel Pipe；For making flow of heat exchange fluid at least one of hot switching path manifold；With for making the heat exchange flow Body flows out at least one manifold of the hot switching path.

4. according to the method described in claim 1, multiple micro passage reactions, each microchannel are wherein arranged in a reservoir Reactor includes multiple process microchannels and multiple hot switching paths, and each hot switching path is at least one process microchannel Thermo-contact, the container is equipped with for making the reaction-ure mixture flow to the manifold of the process microchannel, for making Product flows out the manifold of the process microchannel, for making flow of heat exchange fluid to the manifold of the hot switching path and being used for The heat-exchange fluid is set to flow out the manifold of the hot switching path.

5. according to the method described in claim 4, the wherein described container contains 1 to 1000 micro passage reaction.

6. according to the method described in claim 1, the width or height of the inside dimension of wherein described at least one process microchannel Degree is at most 10mm.

7. according to the method described in claim 1, wherein described at least one process microchannel has at most 10 meters of length.

8. according to the method described in claim 1, wherein described at least one process microchannel and at least one heat exchange Channel comprising material below by being made：Aluminium；Titanium；Nickel；Copper；The alloy of any of above metal；Steel；Quartz；Silicon；Or its two kinds or More kinds of combinations.

9. according to the method described in claim 1, the wherein described reaction-ure mixture is at least one process microchannel It flows and is contacted with the surface characteristics in the process microchannel, the contact of the surface characteristics is mixed to the reactant Object applies interference flowing.

10. according to the method described in claim 1, wherein described at least one hot switching path includes microchannel.

11. according to the method described in claim 1, the wherein described catalyst is in granular form the form of solid.

12. according to the method described in claim 1, the wherein described catalyst is coated at least one process microchannel On inner wall or it is grown on the inner wall of at least one process microchannel.

13. according to the method described in claim 1, the wherein described catalyst, which is supported on to have, flows through formula construction, flow type structure Make or the supporter of serpentine-like configuration on.

14. according to the method described in claim 1, the wherein described catalyst be supported on foam, felt, agglomerate, fin, Or on the supporter of the construction of its combination of two or more.

15. according to the method described in claim 1, the wherein described catalyst is supported in the fin component for including multiple fins Supporter on.

16. described corrugated according to the method described in claim 1, the wherein described catalyst is supported on corrugated plug-in unit Plug-in unit is arranged in the slit in the micro passage reaction.

17. according to the method described in claim 1, wherein described at least one process microchannel has at least one heat transfer wall And in the micro passage reaction ranging from described at least one heat transfer wall of the heat flux of heat exchange often put down Square upper 0.01 to 500 watt of cm surface product.

18. according to the method described in claim 1, the pressure in wherein described at least one process microchannel is at most 50 air Pressure.

19. according to the method described in claim 1, the temperature in wherein described at least one process microchannel is 150 to 300 ℃。

20. according to the method described in claim 1, the wherein described reaction-ure mixture with the catalyst described at least one Time of contact in process microchannel is at most 2000 milliseconds.

21. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products are included in atmospheric pressure Lower boiling point is at least 30 DEG C of one or more hydrocarbon.

22. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products are included in atmospheric pressure Lower boiling point is one or more hydrocarbon higher than 175 DEG C.

23. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products include 2 to 200 carbon The one or more alkane and/or one or more alkene of atom.

24. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products include one or more Alkene, one or more n-alkanes, one or more isoparaffins or its mixture of two or more.

25. according to the method described in claim 1, wherein using separation, fractionation, hydrocracking, hydroisomerization, dewaxing or At least one higher molecular weight hydrocarbon products are further processed in its combination of two or more.

26. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products be further processed with The oil or centre for forming lubricant viscosity distillate fuel.

27. according to the method described in claim 1, wherein described at least one higher molecular weight hydrocarbon products be further processed with Form fuel.

28. according to the method described in claim 1, the wherein described process microchannel has the stream flowed wherein with a direction Body, at least one hot switching path have with the flowing with fluid at least one process microchannel in fair current or inverse The fluid of the direction flowing of stream.

29. according to the method described in claim 1, wherein described at least one process microchannel has wherein with a direction The fluid of flowing, at least one hot switching path have wherein with fluid at least one process microchannel The fluid that flowing is flowed in the direction of cross-flow.

30. according to the method described in claim 1, wherein providing customization along the length of at least one process microchannel Exchange characteristics, by carried out at least one process microchannel reaction generate heat part release with by it is described extremely The cooling that few heat exchange microchannels provide matches.

31. according to the method described in claim 1, the wherein described catalyst includes grading catalyst.

32. according to the method described in claim 1, the index of quality factor of the wherein described micro passage reaction is less than 50%.

33. according to the method described in claim 1, the surface of the fluid wherein flowed at least one process microchannel Speed is at least 0.01m/s.

34. according to the method described in claim 1, the air speed of the fluid wherein flowed at least one process microchannel It is at least 1000hr^-1。

35. according to the method described in claim 1, the pressure drop of the fluid wherein flowed at least one process microchannel At most 10 atmospheric pressure/rice.

36. according to the method described in claim 1, the Reynolds number that wherein fluid flows in the process microchannel be 10 to 4000。

37. according to the method described in claim 1, the wherein described micro passage reaction includes multiple process microchannels, the work Skill microchannel is formed by the way that waveform is arranged between plane sheets.

38. according to the method for claim 37, wherein the micro passage reaction also includes to be with the process microchannel Multiple hot switching paths of thermo-contact, the hot switching path are formed by the way that waveform is arranged between plane sheets.

39. according to the method described in claim 1, the wherein described micro passage reaction includes multiple plates, the multiple plate is in heap Folded form, defines multiple fischer-tropsch process layers and multiple heat exchange layers, and each plate has neighboring, the neighboring quilt of each plate It is soldered to the neighboring of next adjacent plate, to provide peripheral sealing for the stacking.

40. according to the method described in claim 1, the deactivation rate of the wherein described catalyst is less than daily 0.2%CO conversion ratios Loss.

41. according to the method described in claim 1, the wherein described product includes H₂O and H₂, the H of the product₂O partial pressure for 3 to 10 bars, the H of the product₂O/H₂Molar ratio is 1:1 to 5:1.

42. according to the method described in claim 1, wherein, the weight based on metal accounts for the percentage of the total weight of the catalyst Than the catalyst includes the cobalt of 10 to 60 weight %.