CN107519828B - Using the alkylation and device of micro passage reaction - Google Patents
Using the alkylation and device of micro passage reaction Download PDFInfo
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- CN107519828B CN107519828B CN201610449961.XA CN201610449961A CN107519828B CN 107519828 B CN107519828 B CN 107519828B CN 201610449961 A CN201610449961 A CN 201610449961A CN 107519828 B CN107519828 B CN 107519828B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00783—Laminate assemblies, i.e. the reactor comprising a stack of plates
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Abstract
The invention discloses a kind of alkylations using novel micro passage reaction, the reactor design is micro passage reaction, microchannel reaction zone is made of tubular type microchannel reaction zone and face the pathway reaction area two parts that decline, tubular type microchannel reaction zone is made 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 conduct heat folded plate constitute.Alkylation process of the present invention adds considerable amount of propane as cryogen and entrainer, realizes that vaporization takes heat, guarantee that reaction temperature is lower, and by reactor bottom there is the knockout drum of rotary filter press function to separate to product using iso-butane and C3 ~ C5 alkene as raw material.The present invention has the features such as can carrying out at low temperature, reaction raw materials are not necessarily to premixing, and bed pressure drop is small, and energy-saving effect is good, and product quality is high, it can be achieved that energy-efficient, safety, low-carbon and the continuous production of environmental protection.
Description
Technical field
The invention belongs to petrochemical industry, a kind of alkylation process using micro passage reaction is disclosed, and not
The liquid-phase system reaction unit to dissolve each other.
Background technique
Requirement of the every country to gasoline index is increasingly stringenter in the world at present, and the production technology of high-quality gasoline becomes
Current focal point, alkylation process are production high-quality gasoline blend component, the i.e. side of the routine of alkylate oil and maturation
Method.Alkylated reaction, that is, iso-butane generates under acid catalyst effect with C3-C5 alkene has the anti-of high octane gasoline component
It answers, reaction product has the characteristics that low-sulfur and aromatic-free or alkene.
Existing micro passage reaction is tubular type micro passage reaction, filler tool in micro passage reaction internal-response bed
There is tubular type microchannel structure, which makes it have great specific surface area, and the hundred times of reachable stirred tank specific surface area are very
To thousands of times.And micro passage reaction has fabulous heat transfer and mass transfer ability, and mass-transfer efficiency is the 10 of still reaction kettle to arrive
100 times or more, it can greatly improve the mixing efficiency of reactant, the moment that material may be implemented uniformly mixes and efficient biography
Heat can be rapidly reached stable state.It is compared with the traditional method, reduces reaction time and supplies consumption.Be conducive to strongly exothermic anti-
The steady control answered.But existing tubular type microchannel structure reactor is in certain reactions such as aforesaid alkylization reaction, reaction effect
Fruit needs further to be promoted, and structure of reactor need to advanced optimize.
1953804 A of CN discloses the alkylation and system of staged addition of olefin in microchannel.Have using microchannel
Some good heat transfers and mass transfer obtain higher temperature control.Make by microchannel reaction technology precise control of temperature oligomeric anti-
It should minimize, and the alkene introducing being classified reduces olefin partial concentration, increases the phase interface area of sour hydrocarbon dispersion, more
Add and accurately adjust temperature, compared with traditional handicraft, improves the octane number of alkylate, improve the quality of alkylates.
But above-mentioned patent paraffin material stream is largely fed, and will cause undesirable initial distribution, microchannel itself has
There is lesser radial diffusion coefficient, rely solely on microchannel and be extremely difficult to nature flow distribution, reaction efficiency is caused sharply to decline, holds
Easily cause local temperature excessively high, conversion zone can generate the temperature difference, so that alkyl rate is unbalanced.And it is filled with hydrogen in a device
Gas increases separating difficulty and operational danger.
Therefore, how micro passage reaction is promoted, invents a kind of novel microchannel and alkylation process to overcome
Drawbacks described above is those skilled in the art's technical issues that need to address.
Reaction system is that immiscible liquid-phase reaction system is more, most of more as the organic reaction of catalyst using liquid acid
Belong to such, such as using liquid acid as the esterification of catalyst.There is material and come into full contact in such reaction, and reaction outflow
The problems such as separation of object.
Summary of the invention
For the deficiency of current alkylation process technology, the invention discloses a kind of alkylations using micro passage reaction
Technique, and it is used for immiscible liquid-phase system reaction unit.This method keeps the mixing of reactant and acid catalyst visibly homogeneous,
Side reaction can be reduced, the mass-transfer efficiency of reactant and catalyst is improved, and then improves the quality and yield of reaction product, it can
The purpose of energy saving is realized simultaneously.While cost is reduced, the influence to environment and product produced are also reduced
The unstability of performance, replaces the reaction kettle production operation in traditional inefficient gap, realize energy-efficient, safety, low-carbon and
The continuous production of environmental protection.
The present invention uses the alkylation process of 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-
Channel reactor includes shell and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically arranged inside housings, microchannel plate
Answer that area is at least arranged a tubular type microchannel reaction zone and a face declines pathway reaction area.The microchannel reaction zone is vertical
It is vertically arranged inside housings, refers to that reaction channel is vertical and be vertically arranged；Micro passage reaction bottoms material is exported and is separated
The following position in middle part is arranged in knockout drum in connection inside tank, bottoms material outlet；Setting in micro passage reaction bottom shell
Fixed swirl vane, make by material occur cyclonic action；Axial center is set in micro passage reaction bottom shell
Center outlet tube is set, material inlet is arranged in center outlet tube lower part, and center outlet tube top is arranged material and draws branch pipe, and material draws
The above position in middle part is arranged in knockout drum in the outlet of branch pipe out.
A kind of immiscible liquid-phase system reaction unit, including micro passage reaction and reacting rear material knockout drum are micro- logical
Road reactor includes shell and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically arranged inside housings, and microchannel plate is answered
Area is at least arranged a tubular type microchannel reaction zone and a face declines pathway reaction area；The outlet of micro passage reaction bottoms material
It is connected to knockout drum inside, the following position in middle part is arranged in knockout drum in bottoms material outlet；Micro passage reaction bottom shell
The fixed swirl vane of interior setting, make by material cyclonic action occurs；Axial centre in micro passage reaction bottom shell
Material inlet is arranged in position setting center outlet tube, center outlet tube lower part, and center outlet tube top is arranged material and draws branch pipe,
The above position in middle part is arranged in knockout drum in the outlet that material draws branch pipe.
Tubular type microchannel reaction zone and face the pathway reaction area that declines vertically are arranged in series in shell, preferably multiple
Tubular type microchannel reaction zone and face decline pathway reaction area alternately be arranged in series.Usually, preferably 2 ~ 10 tubular type microchannels
Reaction zone and 1 ~ 10 face decline pathway reaction area alternately be arranged in series.It is determined with specific reference to treating capacity and residence time micro- logical
The quantity of ballast covering.Described is arranged in series, refer to reaction mass pass sequentially through tubular type microchannel reaction zone and face decline it is logical
Road reaction zone.Decline spatial volume ratio that pathway reaction area occupies of tubular type microchannel reaction zone and face is 0.5:1~10:1, preferably
For 2:1~5:1.
Case top is arranged material and introduces structure, and it includes liquid inlet opening and gas gas material mouth, shell that material, which introduces structure,
Feed distributor is set on interior microchannel reaction zone, and reacting rear material collection structure is arranged in lower part of the housing.Liquid feedstock distribution
Device guarantees that liquid feedstock distribution reaches 30 ~ 200 points/m2, preferably 50 ~ 100 points/m2.In addition, level sensing is set as needed
Control device, temp detecting controller, pressure detection control device, material gasification situation detection device etc..
Reactor shell shape is preferably cylindrical body, 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 of two kinds of structure microchannel components.Pipe
The pathway reaction area that declines is made of tubular type microchannel component.Tubular type microchannel component is by the material with fiber densification hole shape structure
Material composition, can be the materials such as the organic polymers such as glass fibre, polyethylene or inorganic matter, and the duct of tubular type microchannel component is horizontal
Section can be various suitable shapes, such as polygon, irregular shape, and channel diameter (cross-sectional area is equivalent to justify) can be with
It is micron order or grade, duct average diameter is generally 0.05~10mm, preferably 0.1 ~ 5 mm.Tubular type microchannel component is main
(while may include the frame for increasing intensity, increasing the structures such as muscle) is made of fibrous material, fibrous material, which is made, has densification
The component of hole shape structure, the densification hole, that is, tubular type microchannel reaction zone tubular type microchannel, the i.e. duct of the densification hole
Average diameter (cross-sectional area is equivalent to justify) is 0.05~10mm.
The face pathway reaction area that declines is made of the face channel component that declines.Face decline channel component by vertical installation multiple groups plate
Composition, the structure of plate are flat, ring-plate or folded plate type.Between two plates face formula path clearance be micron order or grade, one
As be 0.1~10mm, preferably 0.5~2mm, the gap between two plates constitutes face and declines pathway reaction space.Using folded structure
When, the angle between two plates is between 5 ° ~ 180 °, between preferably 10 ° ~ 60 °.
The face pathway reaction area (board-like microchannel reaction zone) that declines is made of the face channel component that declines.Face declines channel component
It can be ring-plate, folded plate by the multiple groups board group of vertical installation at (the multiple groups plate fingerboard face of vertical installation is perpendicular to horizontal plane)
The specific structures such as formula, face formula path clearance is micron order or grade between two plates, generally 0.1~10mm, preferably 0.5~
2mm, the gap between two plates constitute face and decline pathway reaction space.When using folded structure, angle a between two plates 5 ° ~
Between 180 °, between preferably 10 ° ~ 60 °.
The face pathway reaction area that declines is made of the face channel component that declines, and the face channel component that declines is multiple groups plank frame, and two
Gap between plate constitutes face and declines channel；The tubular type microchannel of tubular type microchannel reaction zone is arranged perpendicular to horizontal plane, face formula
Decline channel and horizontal plane of the face of microchannel reaction zone is arranged.Face decline pathway reaction area face decline channel plane it is wide
Degree is generally 5 cm or more, preferably 10 cm or more, most preferably 15 cm or more.I.e. face decline channel for height 30 ~ 200cm,
Pancake " face formula " reaction channel of 5 cm or more of width, 0.1~10mm of thickness.
Preferably, wherein the face declines, channel component is set as with indirect heat exchange type structure.Face decline channel knot
A part of structure is reaction channel.Adjacent with reaction channel, setting heat transferring medium flows channel, i.e. structure is similar to conventional board-like
Heat exchanger type structure introduces the taking-up that cooling medium is conducive to reaction heat.It is also face formula channel that heat transferring medium, which flows channel, but
Microchannel structure for micron or millimeter is not limited between two plates, and the channel of reaction mass circulation is the face formula of design structure of the present invention
Microchannel structure.The decline structure of channel component of face is referred to plate heat exchanger formula structure, and parameter is preferably set by above-mentioned parameter
Meter.It is not limited to above-mentioned micron order or grade for being passed through face formula channel between two plates of cooling medium (i.e. cooling duct is unlimited
In microchannel structure), it can be designed and be determined by technical staff according to heat transferring medium and heat exchange amount.
Knockout drum is horizontal knockout drum, and overflow baffle is arranged inside horizontal knockout drum, and recycle acid outlet goes out with reaction product
Mouth is separately positioned on the tank body of overflow baffle two sides.The outlet of micro passage reaction bottoms material is located at recycle acid outlet place
Knockout drum region.
Micro passage reaction bottom shell at least partially inversed taper platform shape structure, swirl vane are arranged in inversed taper platform shape structure
On, fixed swirl vane is fixed on micro passage reaction bottom shell inner wall, and center outlet tube passes through fixed eddy flow leaf
Piece is fixed；Center outlet tube lower part material inlet is exported higher than micro passage reaction bottoms material.
Liquidometer is installed at the housing exterior walls between micro passage reaction distributor and reaction bed, detects sour hydrocarbon mixed liquor
Whether there is liquid layer in 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 gas
Resistance occurs.
Every section of microchannel bed height of micro passage reaction is 30 ~ 200cm, preferably 50 ~ 150cm.
It is 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) it is 10% ~ 60%, preferably 15% ~ 30%.
The alkylation process that the present invention uses is using micro passage reaction of the invention, is original with iso-butane and alkene
Material, propane are that cryogen and entrainer are alkylated reaction and obtain alkylate oil using liquid acid as catalyst.Alkene is C3 ~ C5
Alkene, preferably butylene.
Alkylation process of the present invention reduces sour consumption, improves the selectivity and yield of reaction process, while alkylate oil
Octane number gets a promotion.Reaction pressure (gauge pressure) maintains 0MPa ~ 1.0MPa, preferably 0MPa ~ 0.5MPa.Reaction mass is anti-
Answering the residence time in device is 1 ~ 200min, preferably 30 ~ 90min.
The molar ratio (alkane alkene molar ratio) of alkylation process of the present invention, iso-butane and alkene is 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 refer to including
The liquid catalyst of various acid and ionic liquid.
Alkylation process of the present invention, iso-butane and propane molar ratio are 1:1 ~ 100:1, preferably 10:1 ~ 30:1.The present invention
The bed pressure drop of micro passage reaction, microchannel alkylation reactor is smaller, is conducive to the heat absorption vaporization of propane, reduces reaction
Hot spot.
The acid catalyst of alkylation process of the present invention, Reaction Separation can be recycled, and greatly reduce the loss of acid.Anti-
During answering, supplementing acid catalyst at any time ensures concentration range.After reaction using nitrogen, inert gas or carbon dioxide into
Luggage sets flushing.
For alkylation process of the present invention by using suitable micro passage reaction, reactor bed pressure drop is smaller, is conducive to
Mass transfer and heat transfer make to react more balanced, reactants and products may be implemented and efficiently separate, side reaction is few.The present invention has behaviour
Make mild condition, react easily controllable, the features such as feed distribution is good, and product quality is high effectively prevents single micro- logical of structure
The unbalanced problem of road reaction mass transfer heat transfer, while solving the problems such as equipment size is huge, and space utilization rate is low, it can be achieved that high
Imitate energy conservation, safety, low-carbon and environmental protection continuous production.Test result shows that tubular type microchannel component and face decline channel structure
Part alternately combines setting, there is more efficient reaction mass to contact mixed effect immiscible alkylation reaction system, has
Conducive to reaction efficiency is improved, side reaction is reduced, catalyst attrition amount is effectively reduced.
Present invention process uses the alkylation process of micro passage reaction, without providing extra power for catalyst and production
Raw material premix are closed, and bed pressure drop is smaller, are conducive to the heat absorption vaporization of alkane, are reduced the hot spot of reaction, solve reaction mass cream
Separation problem is difficult to caused by change.Considerable amount of propane is added in reaction raw materials as cryogen and entrainer, reduces reaction temperature
Degree, reduces side reaction.Rotary filter press is realized by horizontal tank, realizes efficiently separating for sour hydrocarbon, reduces equipment corrosion.It follows
The purity of epithio acid improves, and the alkylate oil octane number for reacting 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 reaction process of various immiscible liquid-phase systems,
Have many advantages, such as that material contact is abundant, reaction temperature is easily controllable, reaction effluent is easily isolated.
Detailed description of the invention
Fig. 1 is the micro passage reaction and knockout drum structural schematic diagram that the present invention uses.Wherein: 1 is knockout drum, and 2 were
Bed is crossed, 3 be distribution grid, and 4 be microchannel bed, and 5 be microchannel module, and 6 be acid spreader, and 7 be hydrocarbon distributor, and 8 be nitrogen
Inlet tube, 9 be sour inlet tube, and 10 be hydrocarbon inlet tube, and 11 be top bed, and 12 be level meters, and 13 be sampling pipe, and 14 enter for cryogen
Mouthful, 15 be thermocouple sheath, and 16 be gas phase outlet port, and 17 be hydrocarbon outlet port, and 18 be sour outlet port.
Fig. 2 is alkylation reaction technique flow diagram of the present invention.
Fig. 3 is micro passage reaction and knockout drum binding site structural schematic diagram of the invention.Wherein: 19 draw for material
Branch pipe, 20 be fixed swirl vane, and 21 be center outlet tube, and 22 export for micro passage reaction bottoms material, and 23 be micro- logical
Road reactor.
Fig. 4 is tubular type microchannel reaction zone sectional view.24 be fibrous material, and 25 be supporting rib, and 26 be constraint frame.
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 schematic diagram (i.e. in the channel of reaction mass circulation
Interior setting microchannel separates panel, and the channel for making reaction mass circulate constitutes face and declines channel).
Specific embodiment
Microchannel reaction zone in micro passage reaction is vertical to be vertically arranged, and a tubular type is at least arranged in microchannel reaction zone
Microchannel reaction zone and a face decline pathway reaction area (or referred to as board-like microchannel reaction zone).The microchannel plate is answered
Area 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 channel, face formula channel is referred to
It is arranged with horizontal plane.
A kind of alkylation process and equipment using micro passage reaction provided by the invention, according to Fig. 1, shown in Fig. 3
Micro passage reaction and knockout drum structural schematic diagram, micro passage reaction include liquid inlet opening, gas access, charging distribution
The structures such as device, microchannel reaction zone, settling section (decanting zone).After raw material enters reactor, it can be realized by feed distributor equal
Even distribution, distributor guarantee that liquid feedstock distribution reaches 30 ~ 200 points/m2, preferably 50 ~ 100 points/m2.It is set below distributor
Microchannel reaction zone is set, microchannel reaction zone belongs to vertical microchannel, consists of two parts, and upper end belongs to tubular type microchannel, by
Material composition with fiber densification hole shape structure, lower end belong to face and decline channel, be made of the folded plate of vertical installation, two plates
Between angle between 10 ° ~ 60 °.Redistribution is played, is mixed, reaction and other effects.
Knockout drum is combined with reactor group, as shown in figure 3, reaction effluent is occurred by fixed swirl vane 20
Cyclonic separation, light component are discharged by 21 and 19 from top, and heavy constituent is discharged by 22 from lower part, realize the separation of weight component.
Referring to Fig. 2, Fig. 2 is the alkylation process provided in an embodiment of the present invention using micro passage reaction.
In micro passage reaction, microchannel reaction zone is set below distributor, microchannel reaction zone belongs to vertical microchannel,
It is made of two kinds of structure microchannel components.Tubular type microchannel reaction zone is made of tubular type microchannel component.Tubular type microchannel component
It is made of the material with fiber densification hole shape structure, can be the organic polymers such as glass fibre, polyethylene or inorganic matter
Equal materials, microchannel structure needed for the hole between material constitutes reaction, the opening cross-sectional face of tubular type microchannel component can be with
It is various suitable shapes, such as polygon, irregular shape.In order to increase intensity, can be arranged in the component of tubular type microchannel
Supporting rib etc. increases the component of intensity or using structures such as multilayer constraint frames.It is shown in Figure 4 that (schematic diagram, fibrous material fill
Completely constrain frame interior space), 24 be fibrous material；25 be supporting rib；26 (set for constraint frame according to reactor shell structure
Set 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. has corrosion-resistant, it is ensured that service life.Using the material construction microchannel structure tool of fiber densification hole shape structure
There are low cost, material good mixing effect, and the tubular type for advantageously forming under reactiveness appropriate alkylated reaction is micro-
Channel design (mechanism may be under the influence of logistics souring and different material different from fibrous material adsorption,
Acid and the immiscible reaction environment of hydrocarbon in form tubular type microchannel structure), reaction raw materials contacted with catalyst it is more abundant,
Further promote the progress of reaction.Fibrous material can be processed into the fiber cloth of suitable shape, be loaded on constraint frame.
The face pathway reaction area (board-like microchannel reaction zone) that declines is made of the face channel component that declines.Face declines channel component
It can be ring-plate, folded plate by the multiple groups board group of vertical installation at (the multiple groups plate fingerboard face of vertical installation is perpendicular to horizontal plane)
The specific structures such as formula, face formula path clearance is micron order or grade between two plates, generally 0.1~10mm, preferably 0.5~
2mm, the gap between two plates constitute face and decline pathway reaction space.When using folded structure, angle a between two plates 5 ° ~
Between 180 °, between preferably 10 ° ~ 60 °.It is shown in Figure 5.Preferably, face decline channel component be set as have change indirectly
Hot type structure, i.e. structure are similar to conventional board-like heat exchanger type structure, but reaction channel is that face declines channel design, introduces cooling
Medium is conducive to the taking-up of reaction heat.The decline structure of channel component of face is referred to plate heat exchanger formula structure, and parameter is by upper
State parameter preferred design.Above-mentioned micron order or grade are not limited to (i.e. for being passed through face formula channel between two plates of cooling medium
Cooling duct is not limited to microchannel structure), it can be designed and be determined by technical staff according to heat transferring medium and heat exchange amount.
Using micro passage reaction of the invention, using iso-butane and alkene as alkylated reaction raw material, catalyst uses liquid
Body acid catalyst, reaction raw materials are entered in the distributor of reaction unit after surge tank by liquid inlet opening, acid catalysis
Agent is entered in the distributor of reaction unit by liquid inlet opening, considerable amount of propane is added in the feed, as raw material
Cryogen and entrainer, realize that the vaporization of raw material takes heat, guarantee that reaction temperature is lower, material quantity and acid catalysis dosage are by flow tune
The given control of section, after the first distribution of liquid distribution trough, according to certain liquid hourly space velocity (LHSV), with drip state uniform flow, into
Enter reaction bed.Reaction raw materials can be uniformly entered to after the reaction zone of microchannel, and the tubular type in microchannel upper end is micro- logical first
Road is reacted, and the great specific surface area provided by tubular type microchannel is conducive to alkylated reaction, while will not generate channel
Phenomenon.Then, fluid is mixed by the face of the microchannel lower end channel that declines, is redistributed, and reacted.Raw material is micro-
Mix splendid in channel, temperature accurately controls in reaction process, and raw material proportioning accurately controls, and the yield of product significantly improves.
Material is after microchannel reaction zone reacts, and into settling section, reaction mass is layered through sedimentation, because of propane and different
The boiling point of butane is different, and with pressure change, propane takes heat gradually to vaporize in the middle part of settling section, to sedimentation pars infrasegmentalis propane vapour
To change, part iso-butane also realizes vaporization, and reaction mass is through sedimentation layering, into the horizontal knockout drum with rotary filter press function,
Lower layer's acid catalyst is extracted out by circulating pump and is recycled, and top tank air is discharged through compressor, and middle layer product is gone out to enter coalescence by pumping
Separator, the product after separation send to centrifugal station or storage tank, and a small amount of acid returns to reactor.
Liquid catalyst used in alkylated reaction can be can be arbitrarily alkylated instead with catalyzing iso-butane alkane and alkene
The liquid acid catalyst answered, specially HF, H2SO4, phosphoric acid, boric acid, it is a kind of in the liquid catalysts such as acetic acid or ionic liquid or
It is several.
The terms such as " vertical ", " vertical " in the application indicate comprising vertical and close to vertical, deliberately avoid the present invention and
Certain inclination angle (such as with horizontal plane at 80~an angle of 90 degrees etc.) is set, should belong in the application protection scope.
The protection scope for illustrating reaction effect of the invention below with reference to example, but being not intended to limit the present invention.
Embodiment 1 ~ 3
Reactor and alkylated reaction process shown in Fig. 2 using structure as shown in Figure 1, the bed of microchannel reaction zone
Pressure drop is 0.1 ~ 1.0MPa, preferably 0 ~ 0.5MPa.Using iso-butane and butylene as raw material, using sulfuric acid as catalyst, made with propane
Reaction is alkylated for cryogen.
Sulfuric acid charging and the sour hydrocarbon volume ratio that iso-butane and butene mixture are fed are 0.1:1 ~ 5:1, preferably 0.5:1 ~
3:1.Alkane alkene molar ratio is 1:1 ~ 50:1, preferably 5:1 ~ 20:1.Iso-butane and propane molar ratio are 1:1 ~ 100:1, preferably
10:1 ~ 30:1, reaction pressure maintain 0MPa ~ 1.0MPa, preferably 0MPa ~ 0.5MPa.Side reaction is inhibited, acid is reduced
Consumption, improves the selectivity and yield of reaction process, while alkylate oil octane number gets a promotion.Reaction mass is in reactor
Residence time be 1 ~ 200min, preferably 30 ~ 90min.
Structure of reactor are as follows: " tubular type microchannel-face decline channel-tubular type microchannel-face decline channel-tubular type microchannel "
The volume of five segment structures, every section of microchannel conversion zone is identical.The pore size of tubular type microchannel component is 3mm, and face declines channel
Gap of the angle between 45 °, two plates between two plate of component is 1mm.Reactor and knockout drum binding site structure press Fig. 3 institute
Show determination.
Specific reaction condition is shown in Table 1, and reaction result is shown in Table 2.
Comparative example 1 ~ 2
Comparative example 1 uses the horizontal mechanical stirred reactor of conventional inside setting refrigeration tube bank, and comparative example 2, which uses, to be only had
The micro passage reaction that tubular type microchannel component (same to embodiment) is constituted, reaction condition is referring to table 1, and reaction result is referring to table 2.
1 embodiment of table and comparative example alkylated reaction essential condition
2 embodiment of table and comparative example alkylated reaction result
Claims (23)
1. a kind of alkylation using micro passage reaction, including following content: using iso-butane and alkene as raw material, with liquid
Body acid is catalyst, is alkylated reaction and obtains alkylate oil；It is characterized in that alkylated reaction is used as flowering structure is micro- logical
Road reactor: micro passage reaction includes shell and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically set in shell
Portion, microchannel reaction zone is at least arranged a tubular type microchannel reaction zone and a face declines pathway reaction area；Microchannel plate is answered
It is connected to inside the outlet of device bottoms material and knockout drum, the following position in middle part is arranged in knockout drum in bottoms material outlet；Microchannel
The fixed swirl vane of setting in reactor bottom shell, make by material cyclonic action occurs；Micro passage reaction bottom
Material inlet is arranged in axial center setting center outlet tube, center outlet tube lower part in shell, and center outlet tube top is set
Glove material draws branch pipe, and the above position in middle part is arranged in knockout drum in the outlet that material draws branch pipe.
2. alkylation according to claim 1, it is characterised in that: tubular type microchannel reaction zone and face formula microchannel plate
Area is answered vertically to be arranged in series in shell.
3. alkylation according to claim 1 or 2, it is characterised in that: multiple tubular type microchannels reaction zone and face formula
Microchannel reaction zone is alternately arranged in series.
4. alkylation according to claim 3, it is characterised in that: 2~10 tubular type microchannel reaction zones and 1~
10 faces decline pathway reaction area alternately be arranged in series.
5. alkylation according to claim 1, it is characterised in that: tubular type microchannel reaction zone and face formula microchannel plate
The spatial volume ratio for answering area to occupy is 0.5:1~10:1.
6. alkylation according to claim 1 or 5, it is characterised in that: tubular type microchannel reaction zone and face decline logical
The spatial volume ratio that road reaction zone occupies is 2:1~5:1.
7. alkylation according to claim 1, it is characterised in that: tubular type microchannel reaction zone is by tubular type microchannel structure
Part is constituted, and the opening cross-sectional face of tubular type microchannel component is suitable shape, and it is micro- that cross-sectional area, which is equivalent to round channel diameter,
Meter level or grade, the face pathway reaction area that declines are made of the face channel component that declines, and face declines channel component by vertical installation
Multiple groups board group is at being ring-plate, folded plate type specific structure, face formula path clearance is micron order or grade, two plates between two plates
Between gap constitute face and decline pathway reaction space.
8. alkylation according to claim 7, it is characterised in that: duct average diameter is 0.05~10mm.
9. alkylation according to claim 8, it is characterised in that: duct average diameter is 0.1 ~ 5mm.
10. alkylation according to claim 7, it is characterised in that: between two plates face formula path clearance be 0.1~
10mm。
11. alkylation according to claim 10, it is characterised in that: between two plates face formula path clearance be 0.5~
2mm。
12. alkylation according to claim 1, it is characterised in that: knockout drum is horizontal knockout drum, horizontal knockout drum
Inside setting overflow baffle.
13. alkylation according to claim 1, it is characterised in that: alkylation process using propane as cryogen, with
Liquid acid is catalyst.
14. alkylation according to claim 1, it is characterised in that: the reaction pressure of alkylated reaction is in terms of gauge pressure
0MPa ~ 1.0MPa is maintained, residence time of the reaction mass in reactor is 1 ~ 200min.
15. according to claim 1 or alkylation described in 14, it is characterised in that: the reaction pressure of alkylated reaction is with table
Pressure meter maintains 0MPa ~ 0.5MPa；Residence time of the reaction mass in reactor is 30 ~ 90min.
16. alkylation according to claim 1, it is characterised in that: the iso-butane of alkylated reaction and rubbing for alkene
You are than being 1:1 ~ 50:1, and sour hydrocarbon volume ratio is 0.1:1 ~ 5:1, and acid refers to the liquid catalyst including various acid and ionic liquid.
17. according to claim 1 or alkylation described in 16, it is characterised in that: the iso-butane and alkene of alkylated reaction
Molar ratio be 5:1 ~ 20:1；Sour hydrocarbon volume ratio is 0.5:1 ~ 3:1, and acid refers to the liquid catalyst including various acid and ionic liquid
Agent.
18. alkylation according to claim 1, it is characterised in that: the iso-butane and propane mole of alkylated reaction
Than for 1:1 ~ 100:1.
19. alkylation according to claim 18, it is characterised in that: the iso-butane and propane mole of alkylated reaction
Than for 10:1 ~ 30:1.
20. alkylation according to claim 1, it is characterised in that: micro passage reaction bottom shell is at least partly
For inversed taper platform shape structure, swirl vane is arranged on inversed taper platform shape structure, and fixed swirl vane is fixed on microchannel plate and answers
Device bottom shell inner wall, center outlet tube are fixed by fixed swirl vane；Center outlet tube lower part material inlet is higher than micro-
The outlet of channel reactor bottoms material.
21. alkylation according to claim 7, it is characterised in that: tubular type microchannel component is mainly by fibrous material
It constitutes, the component with fine and close hole shape structure, the densification hole, that is, tubular type microchannel reaction zone tubular type is made in fibrous material
Microchannel.
22. alkylation according to claim 7, it is characterised in that: face decline channel component be set as having it is indirect
Heat exchange type structure.
23. a kind of immiscible liquid-phase system reaction unit, it is characterised in that: including micro passage reaction and reacting rear material point
From tank, micro passage reaction includes shell and microchannel reaction zone, and microchannel reaction zone is vertical to be vertically arranged inside housings, micro-
Pathway reaction area is at least arranged a tubular type microchannel reaction zone and a face declines pathway reaction area；Micro passage reaction bottom
It is connected to inside material outlet and knockout drum, the following position in middle part is arranged in knockout drum in bottoms material outlet；Micro passage reaction
The fixed swirl vane of setting in bottom shell, make by material cyclonic action occurs；In micro passage reaction bottom shell
Material inlet is arranged in axial centre position setting center outlet tube, center outlet tube lower part, and material is arranged in center outlet tube top
Branch pipe is drawn, the above position in middle part is arranged in knockout drum in the outlet that material draws branch pipe.
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| CN109364825A (en) * | 2018-09-17 | 2019-02-22 | 清华大学 | A kind of method of micro- chemical system multistage feeding production alkylate oil |
| CN110802228B (en) * | 2019-10-24 | 2020-10-09 | 中国科学院力学研究所 | 3D printing micro-channel reactor for preparing natural gas from coal gas and printing process thereof |
| CN110947343A (en) * | 2019-12-25 | 2020-04-03 | 中冶焦耐(大连)工程技术有限公司 | Horizontal reaction separator integrating reaction and separation functions |
| CN113522192B (en) * | 2020-04-20 | 2022-10-21 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
| CN113522191B (en) * | 2020-04-20 | 2022-11-15 | 中国石油化工股份有限公司 | Apparatus and method for producing polyalphaolefins |
| CN111992174B (en) * | 2020-07-14 | 2022-06-03 | 中国石油天然气股份有限公司 | Alkylation reaction system and matched alkylation reaction process method thereof |
| CN115138302B (en) * | 2021-03-31 | 2023-05-26 | 中国石油天然气股份有限公司 | Liquid acid alkylation reaction process and reaction system |
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| US7304198B2 (en) * | 2004-05-14 | 2007-12-04 | Battelle Memorial Institute | Staged alkylation in microchannels |
| US8183425B2 (en) * | 2007-12-28 | 2012-05-22 | Chevron U.S.A. Inc. | Ionic liquid catalyst alkylation using split reactant streams |
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