CN107519828A - Using the alkylation and device of new micro passage reaction - Google Patents
Using the alkylation and device of new micro passage reaction Download PDFInfo
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- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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Abstract
The invention discloses a kind of alkylation using new micro passage reaction, the reactor is designed as micro passage reaction, microchannel reaction zone is made up of tubular type microchannel reaction zone and face the pathway reaction area two parts that decline, tubular type microchannel reaction zone is made up of the inorganic or organic polymer materials of the fine and close hole shape structure with fibre-grade, face decline pathway reaction area be by be easy to heat transfer folded plate form.Alkylation process of the present invention adds considerable amount of propane as cryogen and entrainer, realizes that vaporization takes heat, ensure that reaction temperature is relatively low, and the knockout drum for having rotary filter press function by reactor bottom separates to product using iso-butane and C3 ~ C5 alkene as raw material.The features such as present invention has and can carried out at low temperature, and reaction raw materials need not be pre-mixed, and bed pressure drop is small, good energy-conserving effect, and product quality is high, can be achieved energy-efficient, safety, low-carbon and the continuous production of environmental protection.
Description
Technical field
The invention belongs to petrochemical industry, discloses a kind of alkylation process using new micro passage reaction, and immiscible liquid-phase system reaction unit.
Background technology
Requirement of the every country to gasoline index is more and more stricter in the world at present, and the production technology of high-quality gasoline turns into current focal point, and alkylation process is production high-quality gasoline blend component, the i.e. method of the routine of alkylate oil and maturation.Alkylated reaction is the iso-butane reaction of generation with high octane gasoline component under acid catalyst effect with C3-C5 alkene, and reaction product has the characteristics that low-sulfur and aromatic-free or alkene.
Existing micro passage reaction is tubular type micro passage reaction, and filler has tubular type MCA in micro passage reaction internal-response bed, and the micro-structural makes it have great specific surface area, up to even thousands of times of the hundred times of stirred tank specific surface area.And micro passage reaction has fabulous heat transfer and mass transfer ability, mass-transfer efficiency is more than 10 to 100 times of still reaction kettle, it can greatly improve the mixing efficiency of reactant, it is possible to achieve uniformly mixing and the efficient heat transfer of the moment of material, stable state can be rapidly reached.Compared with conventional method, reduce reaction time and supplies consumption.Be advantageous to the steady control of strong exothermal reaction.But existing tubular type MCA reactor is such as aforesaid alkylization reaction in some reactions, and further lifting, structure of reactor need to further optimize reaction effect needs.
CN
1953804 A disclose the alkylation and system of staged addition of olefin in microchannel.The good heat transfer and mass transfer having using microchannel, obtain higher temperature control.Oligomerization is minimized by microchannel reaction technology precise control of temperature, and the alkene introducing of classification reduces olefin partial concentration, add the boundary area of sour hydrocarbon dispersion, more accurately adjust temperature, compared with traditional handicraft, the octane number of alkylate is improved, improves the quality of alkylates.
But above-mentioned patent paraffin material flow is largely fed, bad initial distribution can be caused, microchannel has less radial diffusion coefficient in itself, rely solely on microchannel and be extremely difficult to nature flow distribution, reaction efficiency is caused drastically to decline, it is too high to easily cause local temperature, conversion zone can produce the temperature difference so that alkyl rate is unbalanced.And hydrogen is filled with a device, increase separating difficulty and operational danger.
Therefore, how micro passage reaction is lifted, invents a kind of new microchannel and alkylation process to overcome drawbacks described above, be those skilled in the art's technical issues that need to address.
Reaction system is that immiscible liquid-phase reaction system is more, and most of organic reaction using liquid acid as catalyst belongs to such more, the esterification such as using liquid acid as catalyst.Material be present and fully contact in such reaction, and reaction effluent separation the problems such as.
The content of the invention
For the deficiency of current alkylation process technology, the invention discloses a kind of alkylation process using new micro passage reaction, and for immiscible liquid-phase system reaction unit.This method makes the mixing of reactant and acid catalyst visibly homogeneous, can reduce side reaction, improves the mass-transfer efficiency of reactant and catalyst, and then improves the quality and yield of reaction product, can realize the purpose for saving energy consumption simultaneously.While cost is reduced, the unstability of the influence to environment and the properties of product produced is also reduced, substitutes the reactor production operation in traditional poorly efficient gap, realizes energy-efficient, safety, low-carbon and the continuous production of environmental protection.
The present invention uses the alkylation process of new micro passage reaction, including following content：Using iso-butane and alkene as raw material, using liquid acid as catalyst, it is alkylated reaction and obtains alkylate oil；Alkylated reaction uses following micro passage reaction：Micro passage reaction includes housing and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically set on enclosure interior, and microchannel reaction zone declines pathway reaction area at least provided with a tubular type microchannel reaction zone and a face.Described microchannel reaction zone is vertical to be vertically set on enclosure interior, refers to that reaction channel is vertical and is vertically arranged；Micro passage reaction bottoms material is exported with being connected inside knockout drum, and bottoms material outlet is arranged on the following position in middle part in knockout drum；Fixed swirl vane is set in micro passage reaction bottom shell, and cyclonic action occurs for the material for making to pass through；Axial center setting center drain pipe in micro passage reaction bottom shell, center drain pipe bottom set material inlet, and center drain pipe top sets material to draw branch pipe, and the outlet that material draws branch pipe is arranged on middle part above position in knockout drum.
A kind of immiscible liquid-phase system reaction unit, including micro passage reaction and reacting rear material knockout drum, micro passage reaction includes housing and microchannel reaction zone, microchannel reaction zone is vertical to be vertically set on enclosure interior, and microchannel reaction zone declines pathway reaction area at least provided with a tubular type microchannel reaction zone and a face；Micro passage reaction bottoms material is exported with being connected inside knockout drum, and bottoms material outlet is arranged on the following position in middle part in knockout drum；Fixed swirl vane is set in micro passage reaction bottom shell, and cyclonic action occurs for the material for making to pass through；Axial center setting center drain pipe in micro passage reaction bottom shell, center drain pipe bottom set material inlet, and center drain pipe top sets material to draw branch pipe, and the outlet that material draws branch pipe is arranged on middle part above position in knockout drum.
Tubular type microchannel reaction zone and face the pathway reaction area that declines vertically are arranged in series in housing, and preferably multiple tubular type microchannel reaction zones and face the pathway reaction area that declines alternately are arranged in series.As a rule, preferably 2 ~ 10 tubular type microchannel reaction zones and 1 ~ 10 face decline pathway reaction area alternately be arranged in series.The quantity of microchannel bed is determined with specific reference to treating capacity and residence time.Described is arranged in series, and refers to that reaction mass passes sequentially through tubular type microchannel reaction zone and face declines pathway reaction area.Tubular type microchannel reaction zone and face the spatial volume ratio that pathway reaction area occupies that declines are 0.5：1~10：1, preferably 2:1~5:1.
Case top sets material to introduce structure, and material, which introduces structure, includes liquid inlet opening and gas gas material mouth, sets feed distributor, lower housing portion setting reacting rear material collection structure in housing on the reaction zone of microchannel.Liquid feed distributor ensures that liquid feedstock distribution reaches 30 ~ 200 points/m2, preferably 50 ~ 100 points/m2.In addition, it is arranged as required to level sensing control device, temp detecting controller, pressure detection control device, material gasification situation detection means etc..
Reactor shell profile is preferably cylinder, and reactor is disposed vertically.
Micro passage reaction is vertical reactor, and ratio of height to diameter is 2 ~ 10, preferably 4 ~ 6.
In micro passage reaction, microchannel reaction zone belongs to vertical microchannel, is made up of two kinds of structure microchannel components.Tubular type microchannel reaction zone is made up of tubular type microchannel component.Tubular type microchannel component is made up of the material with fiber densification hole shape structure, can be the materials such as the organic polymers such as glass fibre, polyethylene or inorganic matter, the opening cross-sectional face of tubular type microchannel component can be various suitable shapes, such as polygon, irregular shape, channel diameter（Cross-sectional area is equivalent to justify）Can be micron order or grade, duct average diameter is generally 0.05~10mm, preferably 0.1 ~ 5 mm.Tubular type microchannel component is mainly made up of fibrous material（The structures such as framework, the increase muscle of increase intensity can be included simultaneously）, the component with fine and close hole shape structure is made in fibrous material, and the fine and close hole is the duct average diameter of the tubular type microchannel of tubular type microchannel reaction zone, the i.e. fine and close hole（Cross-sectional area is equivalent to justify）For 0.05~10mm.
The face pathway reaction area that declines is made up of the face channel component that declines.The face channel component that declines is made up of multigroup plate of vertical installation, and the structure of plate is flat, ring-plate or folded plate type.Formula path clearance in face is micron order or grade between two plates, generally 0.1~10mm, preferably 0.5~2mm, and the gap between two plates forms face and declined pathway reaction space.During using folded structure, the angle between two plates is between 5 ° ~ 180 °, between preferably 10 ° ~ 60 °.
Face declines pathway reaction area（Board-like microchannel reaction zone）It is made up of the face channel component that declines.The face channel component that declines is made up of multigroup plate of vertical installation（Multigroup plate fingerboard face of vertical installation is perpendicular to horizontal plane）, can be the concrete structure such as ring-plate, folded plate type, face formula path clearance be micron order or grade between two plates, generally 0.1~10mm, preferably 0.5~2mm, and the gap composition face between two plates declines pathway reaction space.During using folded structure, the angle a between two plates is between 5 ° ~ 180 °, between preferably 10 ° ~ 60 °.
The face pathway reaction area that declines is made up of the face channel component that declines, and the face channel component that declines is multigroup plank frame, and the gap between two plates forms face and declined passage；The tubular type microchannel of tubular type microchannel reaction zone is set perpendicular to horizontal plane, and decline decline passage and the horizontal plane of face in pathway reaction area of face is set.Decline the decline plane width of passage of face in pathway reaction area of face is generally 5 more than cm, preferably 10 more than cm, most preferably 15 more than cm.I.e. face declines passage as 30 ~ 200cm of height, more than the cm of width 5,0.1~10mm of thickness pancake " face formula " reaction channel.
Preferably, wherein described face declines, channel component is arranged to indirect heat exchange type structure.The decline part of channel design of face is reaction channel.It is adjacent with reaction channel, set heat transferring medium to flow passage, i.e. structure is similar to conventional board-like heat exchanger type structure, introduces the taking-up that cooling medium is advantageous to reaction heat.Heat transferring medium flowing passage is also face formula passage, but is not limited between two plates the MCA for micron or millimeter, and the passage of reaction mass circulation declines channel design for the face of design structure of the present invention.The decline structure of channel component of face is referred to plate type heat exchanger formula structure, and parameter presses above-mentioned parameter decision design.Above-mentioned micron order or grade are not limited to for face formula passage between being passed through two plates of cooling medium（I.e. cooling duct is not limited to MCA）, can be designed and determined by technical staff according to heat transferring medium and heat exchange amount.
Knockout drum is horizontal knockout drum, and overflow baffle is set inside horizontal knockout drum, and recycle acid outlet is separately positioned on the tank body of overflow baffle both sides with reacting product outlet.The outlet of micro passage reaction bottoms material is positioned at the knockout drum region where recycle acid outlet.
Micro passage reaction bottom shell at least partially inversed taper platform shape structure, swirl vane are arranged on inversed taper platform shape structure, and fixed swirl vane is fixed on micro passage reaction bottom shell inwall, and center drain pipe is fixed by fixed swirl vane；Center drain pipe bottom material inlet exports higher than micro passage reaction bottoms material.
Liquid level gauge is installed at the housing exterior walls between micro passage reaction distributor and reaction bed, detects whether sour hydrocarbon mixed liquor has liquid layer on filler surface, with the sour inlet amount of adjustment.
Gas phase sampler is installed at the housing exterior walls between micro passage reaction reaction bed, determines whether to have vapour lock.
Every section of microchannel bed height of micro passage reaction is 30 ~ 200cm, preferably 50 ~ 150cm.
Isolated between every section of microchannel top and bottom of micro passage reaction with stephanoporate steel plate, steel plate percent opening（Steel plate perforated area accounts for the ratio of steel plate）For 10% ~ 60%, preferably 15% ~ 30%.
The alkylation process that the present invention uses, it is that, using iso-butane and alkene as raw material, propane is cryogen and entrainer, using liquid acid as catalyst, is alkylated reaction and obtains alkylate oil using the micro passage reaction of the present invention.Alkene is C3 ~ C5 alkene, preferably butylene.
Alkylation process of the present invention, sour consumption is reduced, improve the selectivity and yield of course of reaction, while alkylate oil octane number gets a promotion.Reaction pressure（Gauge pressure）Maintain 0MPa ~ 1.0MPa, preferably 0MPa ~ 0.5MPa.Residence time of the reaction mass in reactor is 1 ~ 200min, preferably 30 ~ 90min.
The mol ratio of alkylation process of the present invention, iso-butane and alkene（Alkane alkene mol ratio）For 1:1~50:1, preferably 5:1~20:1.
In alkylation reaction method of the present invention, sour hydrocarbon volume ratio is 0.1:1~5:1, preferably 0.5:1~3:1.Acid refers to the liquid catalyst including various acid and ionic liquid.
Alkylation process of the present invention, iso-butane are 1 with propane mol ratio:1~100:1, preferably 10:1~30:1.Micro passage reaction of the present invention, the bed pressure drop of microchannel alkylation reactor is smaller, is advantageous to the heat absorption vaporization of propane, reduces the focus of reaction.
Alkylation process of the present invention, the acid catalyst of Reaction Separation can be recycled, and greatly reduce the loss of acid.During the course of the reaction, supplement acid catalyst ensures concentration range at any time.Reaction uses nitrogen, inert gas or carbon dioxide to carry out device flushing after terminating.
Alkylation process of the present invention is by using suitable micro passage reaction, and reactor bed pressure drop is smaller, is advantageous to mass transfer and heat transfer, makes reaction more balanced, it is possible to achieve reactant and product efficiently separate, and side reaction is few.The present invention has operating condition gentle, react easily controllable, feed distribution is good, the features such as product quality is high, it effectively prevent the single microchannel plate of structure and answer the unbalanced problem of mass-and heat-transfer, it is huge to solve equipment size simultaneously, the problems such as low space utilization, energy-efficient, safety, low-carbon and the continuous production of environmental protection can be achieved.Result of the test shows, tubular type microchannel component and face are declined, and alternately combination is set channel component, for immiscible alkylation reaction system be there is more efficient reaction mass to contact mixed effect, is advantageous to improve reaction efficiency, side reaction is reduced, effectively reduces catalyst attrition amount.
Present invention process uses the alkylation process of micro passage reaction, extra power need not be provided to be pre-mixed catalyst and raw materials for production, bed pressure drop is smaller, is advantageous to the heat absorption vaporization of alkane, the focus of reaction is reduced, solves and is difficult to separation problem caused by reaction mass emulsification.Considerable amount of propane is added in reaction raw materials as cryogen and entrainer, reaction temperature is reduced, reduces side reaction.Rotary filter press is realized by horizontal tank, efficiently separating for sour hydrocarbon is realized, reduces equipment corrosion.The purity of recycle sulfuric acid improves, and reacts that the alkylate oil octane number of generation is higher, and sulfuric acid consumption is lower.
The immiscible liquid-phase system reaction unit of the present invention can be used for the course of reaction of various immiscible liquid-phase systems, have the advantages that material contact is abundant, reaction temperature is easily controllable, reaction effluent is easily isolated.
Brief description of the drawings
Fig. 1 is the micro passage reaction and knockout drum structural representation that the present invention uses.Wherein：1 is knockout drum, and 2 be transition bed, and 3 be distribution grid, 4 be microchannel bed, and 5 be microchannel module, and 6 be acid spreader, 7 be hydrocarbon distributor, and 8 be nitrogen inlet tube, and 9 be sour inlet tube, 10 be hydrocarbon inlet tube, and 11 be top bed, and 12 be level meters, 13 be sampling pipe, and 14 be cryogen entrance, and 15 be thermocouple sheath, 16 be gas phase outlet port, and 17 be hydrocarbon outlet port, and 18 be sour outlet port.
Fig. 2 is alkylation reaction technique schematic flow sheet of the present invention.
Fig. 3 is the micro passage reaction and knockout drum binding site structural representation of the present invention.Wherein：19 be that material draws branch pipe, and 20 be fixed swirl vane, drain pipe centered on 21, and 22 be the outlet of micro passage reaction bottoms material, and 23 be micro passage reaction.
Fig. 4 is tubular type microchannel reaction zone sectional view.24 be fibrous material, and 25 be brace rod, and 26 be constraint framework.
Fig. 5 is that face declines pathway reaction area sectional view.27 be microchannel panel.
Fig. 6 is that face declines pathway reaction area another embodiment structural representation（Microchannel is set to separate panel in the passage of reaction mass circulation, the passage for making reaction mass circulate forms face and declined passage）.
Embodiment
Microchannel reaction zone in micro passage reaction is vertical to be vertically arranged, and microchannel reaction zone declines pathway reaction area at least provided with a tubular type microchannel reaction zone and a face（Or referred to as board-like microchannel reaction zone）.Described microchannel reaction zone is vertical to be vertically arranged, and is referred to that reaction channel is vertical and is vertically arranged.When reaction channel is face formula passage, refer to that face formula passage is set with horizontal plane.
A kind of alkylation process and equipment using new micro passage reaction provided by the invention, micro passage reaction and knockout drum structural representation according to Fig. 1, Fig. 3, micro passage reaction include liquid inlet opening, gas access, feed distributor, microchannel reaction zone, settling section（Decanting zone）Etc. structure.After raw material enters reactor, it can be realized and be uniformly distributed by feed distributor, distributor ensures that liquid feedstock distribution reaches 30 ~ 200 points/m2, preferably 50 ~ 100 points/m2.Microchannel reaction zone is set below distributor, microchannel reaction zone belongs to vertical microchannel, it is made up of two parts, upper end belongs to tubular type microchannel, it is made up of the material with fiber densification hole shape structure, lower end belongs to face and declined passage, is made up of the folded plate of vertical installation, the angle between two plates is between 10 ° ~ 60 °.Redistribution is served, is mixed, reaction and other effects.
Knockout drum is together with combination of reactors, as shown in figure 3, by fixed swirl vane 20 cyclonic separation occurs for reaction effluent, light component is discharged by 21 and 19 from top, and heavy constituent is discharged by 22 from bottom, realizes that weight component separates.
Reference picture 2, Fig. 2 are the alkylation process provided in an embodiment of the present invention using micro passage reaction.
In micro passage reaction, microchannel reaction zone is set, microchannel reaction zone belongs to vertical microchannel, is made up of two kinds of structure microchannel components below distributor.Tubular type microchannel reaction zone is made up of tubular type microchannel component.Tubular type microchannel component is made up of the material with fiber densification hole shape structure, can be the materials such as the organic polymers such as glass fibre, polyethylene or inorganic matter, hole between material forms the MCA needed for reaction, the opening cross-sectional face of tubular type microchannel component can be various suitable shapes, such as polygon, irregular shape.In order to increase intensity, the component of the increase intensity such as brace rod can be set in the component of tubular type microchannel or using structures such as multilayer constraint frameworks.It is shown in Figure 4（Schematic diagram, fibrous material is full of constraint frame interior space）, 24 be fibrous material；25 be brace rod；26 be constraint framework（According to reactor shell structure setting suitable configurations）.Fibrous material 24 has fine and close hole shape structure, can be the organic polymers such as glass fibre, polyethylene or inorganic matter etc., have corrosion-resistant, it is ensured that service life.There is low cost, material good mixing effect using the material construction MCA of fiber densification hole shape structure, and the tubular type MCA of appropriate alkylated reaction is advantageously formed under reactiveness（Mechanism is probably under the influence of logistics souring and different material and fibrous material adsorption difference, and tubular type MCA is formd in acid and the immiscible reaction environment of hydrocarbon）, reaction raw materials contacted with catalyst it is more abundant, further promote reaction progress.Fibrous material can be processed into the fiber cloth of suitable shape, be loaded on constraint framework.
Face declines pathway reaction area（Board-like microchannel reaction zone）It is made up of the face channel component that declines.The face channel component that declines is made up of multigroup plate of vertical installation（Multigroup plate fingerboard face of vertical installation is perpendicular to horizontal plane）, can be the concrete structure such as ring-plate, folded plate type, face formula path clearance be micron order or grade between two plates, generally 0.1~10mm, preferably 0.5~2mm, and the gap composition face between two plates declines pathway reaction space.During using folded structure, the angle a between two plates is between 5 ° ~ 180 °, between preferably 10 ° ~ 60 °.It is shown in Figure 5.Preferably, the face channel component that declines is arranged to indirect heat exchange type structure, i.e. structure is similar to conventional board-like heat exchanger type structure, but reaction channel is that face declines channel design, introduces the taking-up that cooling medium is advantageous to reaction heat.The decline structure of channel component of face is referred to plate type heat exchanger formula structure, and parameter presses above-mentioned parameter decision design.Above-mentioned micron order or grade are not limited to for face formula passage between being passed through two plates of cooling medium（I.e. cooling duct is not limited to MCA）, can be designed and determined by technical staff according to heat transferring medium and heat exchange amount.
Using the micro passage reaction of the present invention, using iso-butane and alkene as alkylated reaction raw material, catalyst uses liquid acid catalyst, entered after the buffered tank of reaction raw materials by liquid inlet opening among the distributor of reaction unit, acid catalyst is entered among the distributor of reaction unit by liquid inlet opening, considerable amount of propane is added in the feed, cryogen and entrainer as raw material, realize that the vaporization of raw material takes heat, ensure that reaction temperature is relatively low, material quantity and acid catalysis dosage are by the given control of Flow-rate adjustment, after the first distribution of liquid distribution trough, according to certain liquid hourly space velocity (LHSV), with drip state uniform flow, into reaction bed.Reaction raw materials can be uniformly entered to after the reaction zone of microchannel, reacted first in the tubular type microchannel of microchannel upper end, the great specific surface area provided by tubular type microchannel, be advantageous to alkylated reaction, while will not produce channeling.Then, mixed, redistributed, and reacted by the face of the microchannel lower end passage convection body that declines.Raw material mixes splendid in microchannel, and temperature accurately controls in course of reaction, and raw material proportioning accurately controls, and the yield of product significantly improves.
Material is after microchannel reaction zone reacts, into settling section, reaction mass is layered through sedimentation, because propane is different with the boiling point of iso-butane, with pressure change, propane takes hot gradually vaporization in the middle part of settling section, to sedimentation pars infrasegmentalis propane vaporization, part iso-butane also realizes vaporization, reaction mass is layered through sedimentation, into the horizontal knockout drum with rotary filter press function, lower floor's acid catalyst is circulated by circulating pumped, top tank air is discharged through compressor, middle level product enters coalescing separator by pumped, product after separation sends to centrifugal station or storage tank, a small amount of acid returns to reactor.
Liquid catalyst used in alkylated reaction can be the liquid acid catalyst that reaction can be arbitrarily alkylated with catalyzing iso-butane alkane and alkene, specially HF, H2SO4, it is phosphoric acid, boric acid, one or more of in the liquid catalyst such as acetic acid or ionic liquid.
The expression of the terms such as " vertical ", " vertical " in the application is included vertically and close to vertically, intentional avoidance is of the invention and sets certain inclination angle（Such as with the horizontal 80~an angle of 90 degrees etc.）, should belong within the application protection domain.
Illustrate the reaction effect of the present invention with reference to example, but therefore do not limit the scope of the invention.
Embodiment 1 ~ 3
Using the alkylated reaction flow shown in the reactor and Fig. 2 of structure as shown in Figure 1, the bed pressure drop of microchannel reaction zone is 0.1 ~ 1.0MPa, preferably 0 ~ 0.5MPa.Using iso-butane and butylene as raw material, using sulfuric acid as catalyst, reaction is alkylated using propane as cryogen.
It is 0.1 that sulfuric acid, which feeds the sour hydrocarbon volume ratio fed with iso-butane and butene mixture,:1~5:1, preferably 0.5:1~3:1.Alkane alkene mol ratio is 1:1~50:1, preferably 5:1~20:1.Iso-butane is 1 with propane mol ratio:1~100:1, preferably 10:1~30:1, reaction pressure maintains 0MPa ~ 1.0MPa, preferably 0MPa ~ 0.5MPa.Side reaction is inhibited, reduces sour consumption, improves the selectivity and yield of course of reaction, while alkylate oil octane number gets a promotion.Residence time of the reaction mass in reactor is 1 ~ 200min, preferably 30 ~ 90min.
Structure of reactor is：" tubular type microchannel-face decline passage-tubular type microchannel-face decline passage-tubular type microchannel " five segment structures, the volume of every section of microchannel conversion zone are identical.The pore size of tubular type microchannel component is 3mm, and gap of the angle that face declines between the plate of channel component two between 45 °, two plates is 1mm.Reactor determines as shown in Figure 3 with knockout drum binding site structure.
Specific reaction condition is shown in Table 1, and reaction result is shown in Table 2.
Comparative example 1 ~ 2
Comparative example 1 sets the horizontal mechanical stirred reactor of refrigeration tube bank using conventional inside, and comparative example 2 is using only tubular type microchannel component（Same embodiment）The micro passage reaction of composition, reaction condition is referring to table 1, and reaction result is referring to table 2.
The embodiment of table 1 and comparative example alkylated reaction essential condition
The embodiment of table 2 and comparative example alkylated reaction result
Claims (13)
1. a kind of alkylation using micro passage reaction, including following content：Using iso-butane and alkene as raw material, using liquid acid as catalyst, it is alkylated reaction and obtains alkylate oil；It is characterized in that alkylated reaction uses following structure micro passage reaction：Micro passage reaction includes housing and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically set on enclosure interior, and microchannel reaction zone declines pathway reaction area at least provided with a tubular type microchannel reaction zone and a face；Micro passage reaction bottoms material is exported with being connected inside knockout drum, and bottoms material outlet is arranged on the following position in middle part in knockout drum；Fixed swirl vane is set in micro passage reaction bottom shell, and cyclonic action occurs for the material for making to pass through；Axial center setting center drain pipe in micro passage reaction bottom shell, center drain pipe bottom set material inlet, and center drain pipe top sets material to draw branch pipe, and the outlet that material draws branch pipe is arranged on middle part above position in knockout drum.
2. alkylation according to claim 1, it is characterised in that：Tubular type microchannel reaction zone and face the pathway reaction area that declines vertically are arranged in series in housing；It is preferred that multiple tubular type microchannels reaction zone and face decline, pathway reaction area is alternately arranged in series；It is preferred that 2~10 tubular type microchannel reaction zones and 1~10 face decline, pathway reaction area is alternately arranged in series.
3. alkylation according to claim 1 or 2, it is characterised in that：Tubular type microchannel reaction zone and face the spatial volume ratio that pathway reaction area occupies that declines are 0.5：1~10：1, preferably 2:1~5:1.
4. alkylation according to claim 1 or 2, it is characterised in that：Tubular type microchannel reaction zone is made up of tubular type microchannel component, and the opening cross-sectional face of tubular type microchannel component is suitable shape, and it is micron order or grade that cross-sectional area, which is equivalent to round channel diameter, and duct average diameter is preferably 0.05~10mm, preferably 0.1 ~ 5mm；The face pathway reaction area that declines is made up of the face channel component that declines, the face channel component that declines is made up of multigroup plate of vertical installation, for ring-plate, folded plate type concrete structure, formula path clearance in face is micron order or grade between two plates, preferably 0.1~10mm, most preferably 0.5~2mm, the gap between two plates form face and declined pathway reaction space.
5. alkylation according to claim 1, it is characterised in that：Knockout drum is horizontal knockout drum, and overflow baffle is set inside horizontal knockout drum.
6. alkylation according to claim 1, it is characterised in that：Alkylation process is using propane as cryogen, using liquid acid as catalyst.
7. alkylation according to claim 1, it is characterised in that：The reaction pressure of alkylated reaction maintains 0MPa ~ 1.0MPa, preferably 0MPa ~ 0.5MPa in terms of gauge pressure；Residence time of the reaction mass in reactor is 1 ~ 200min, preferably 30 ~ 90min.
8. alkylation according to claim 1, it is characterised in that：The iso-butane of alkylated reaction and the mol ratio of alkene are 1:1~50:1, preferably 5:1~20:1；Sour hydrocarbon volume ratio is 0.1:1~5:1, preferably 0.5:1~3:1, acid refers to the liquid catalyst including various acid and ionic liquid.
9. alkylation according to claim 6, it is characterised in that：The iso-butane of alkylated reaction is 1 with propane mol ratio:1~100:1, preferably 10:1~30:1.
10. alkylation according to claim 1, it is characterised in that：Micro passage reaction bottom shell at least partially inversed taper platform shape structure, swirl vane are arranged on inversed taper platform shape structure, and fixed swirl vane is fixed on micro passage reaction bottom shell inwall, and center drain pipe is fixed by fixed swirl vane；Center drain pipe bottom material inlet exports higher than micro passage reaction bottoms material.
11. alkylation according to claim 4, it is characterised in that：Tubular type microchannel component is mainly made up of fibrous material, and the component with fine and close hole shape structure is made in fibrous material, and the fine and close hole is the tubular type microchannel of tubular type microchannel reaction zone.
12. alkylation according to claim 4, it is characterised in that：The face channel component that declines is arranged to indirect heat exchange type structure.
A kind of 13. immiscible liquid-phase system reaction unit, it is characterised in that：Including micro passage reaction and reacting rear material knockout drum, micro passage reaction includes housing and microchannel reaction zone, microchannel reaction zone is vertical to be vertically set on enclosure interior, and microchannel reaction zone declines pathway reaction area at least provided with a tubular type microchannel reaction zone and a face；Micro passage reaction bottoms material is exported with being connected inside knockout drum, and bottoms material outlet is arranged on the following position in middle part in knockout drum；Fixed swirl vane is set in micro passage reaction bottom shell, and cyclonic action occurs for the material for making to pass through；Axial center setting center drain pipe in micro passage reaction bottom shell, center drain pipe bottom set material inlet, and center drain pipe top sets material to draw branch pipe, and the outlet that material draws branch pipe is arranged on middle part above position in knockout drum.
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