WO2022205717A1 - 一种丙烯羰基化制丁醛的反应***及方法 - Google Patents
一种丙烯羰基化制丁醛的反应***及方法 Download PDFInfo
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- WO2022205717A1 WO2022205717A1 PCT/CN2021/109748 CN2021109748W WO2022205717A1 WO 2022205717 A1 WO2022205717 A1 WO 2022205717A1 CN 2021109748 W CN2021109748 W CN 2021109748W WO 2022205717 A1 WO2022205717 A1 WO 2022205717A1
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- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 66
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 20
- 230000006315 carbonylation Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 103
- 238000003860 storage Methods 0.000 claims description 41
- 239000007788 liquid Substances 0.000 claims description 37
- 239000012071 phase Substances 0.000 claims description 26
- 239000007791 liquid phase Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 15
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000009827 uniform distribution Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005805 hydroxylation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- GNPXKHTZVDUNOY-UHFFFAOYSA-N oxomethylidenerhodium Chemical compound O=C=[Rh] GNPXKHTZVDUNOY-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/12—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by gravity in a downward flow
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/004—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by means of a nozzle
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/082—Controlling processes
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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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
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- B01J2208/00902—Nozzle-type feeding elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00911—Sparger-type feeding elements
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/46—Ruthenium, rhodium, osmium or iridium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the invention relates to the field of propylene hydroxylation reaction preparation, in particular to a reaction system and method for preparing butyraldehyde by propylene carbonylation.
- Butoctanol is an important raw material for the synthesis of fine chemical products, and the preparation of n-butyraldehyde is the most important part in the process of preparing butanol.
- the generation of butyraldehyde mainly takes synthesis gas and propylene as raw materials, and takes carbonyl rhodium/triphenylphosphine complex as a catalyst, and the reaction generates mixed butyraldehyde, and after separating the catalyst, further rectification is performed to obtain a butyraldehyde mixture;
- the synthesis gas, propylene and catalyst cannot be fully mixed inside the oxo reactor, resulting in low reaction efficiency and high energy consumption during the reaction process. And because the reaction temperature is too high, the yield of n-butyraldehyde in the generated butyraldehyde mixture is low, the service life of the catalyst is short
- the first object of the present invention is to provide a reaction system for producing butyraldehyde by hydroxylation of propylene.
- a micro-interface generator is arranged inside the reactor to disperse and break the material into micro-bubbles, thereby increasing the gas phase and liquid phase.
- the interphase area between them makes the mass transfer space fully satisfied, increases the residence time of the gas in the liquid phase, reduces the energy consumption, and improves the reaction efficiency; on the other hand, it reduces the operating temperature and pressure inside the reactor, The safety and stability of the entire reaction system are improved.
- the second object of the present invention is to provide a reaction method for preparing butyraldehyde by adopting the above-mentioned reaction system for preparing butyraldehyde by hydroxylation of propylene. energy consumption, and achieve better reaction effect than the existing process.
- the invention provides a reaction system for producing butyraldehyde by carbonylation of propylene, comprising: a reactor, a propylene storage tank, a carbon monoxide storage tank, a hydrogen storage tank, a propylene pipeline and a synthesis gas pipeline; A catalyst inlet, a propylene inlet and a synthesis gas inlet are arranged in sequence at the bottom; a solvent inlet is arranged at the bottom of the reactor;
- the inside of the reactor is provided with two micro-interface generators from top to bottom, and the micro-interface generator located above is connected to the propylene inlet to break the propylene gas into micro-bubbles of micron level; the micro-interface generator located at the bottom is The micro-interface generator is connected to the syngas inlet for breaking the syngas into micro-bubbles of micron level; the outlets of the two micro-interface generators are opposite to each other, and gas distributors for uniform distribution of raw materials are connected to the outlets. ;
- the propylene inlet is connected to the propylene storage tank through the propylene pipeline; the carbon monoxide storage tank and the hydrogen storage tank are connected in parallel, and the carbon monoxide storage tank and the hydrogen storage tank are connected to each other through the synthesis gas pipeline.
- the synthesis gas inlet is connected; the propylene pipeline and the synthesis gas pipeline are both provided with a bubble generator for pre-dispersing and breaking the gas into bubbles.
- butyraldehyde mainly takes synthesis gas and propylene as raw materials, and uses carbonyl rhodium/triphenylphosphine complex as a catalyst to react to generate mixed butyraldehyde.
- the mixture is subjected to isomer separation to obtain n-butyraldehyde; but in the prior art, in the oxo reaction of synthesis gas and propylene under the action of a catalyst, the synthesis gas, propylene and the catalyst cannot be fully mixed inside the oxo reactor, As a result, the reaction efficiency is low in the reaction process, the energy consumption is high, and the yield of n-butyraldehyde in the generated butyraldehyde mixture is low, which increases the production cost of the enterprise.
- the present invention provides a reaction system for producing butyraldehyde by carbonylation of propylene.
- the reaction system disperses and crushes propylene and synthesis gas by arranging two micro-interface generators inside the reactor, thereby improving the transmission efficiency. It can greatly improve the mass transfer rate and reduce the temperature and pressure required for the reaction; by making the two micro-interface generators face each other, the propylene micro-bubbles and the syngas micro-bubbles can play a hedging effect, so as to realize the uniformity of the micro-bubbles.
- the micro-bubbles are further distributed evenly; by setting the bubble generator, the raw gas is pre-broken, and the gas is broken into large gas before dispersing into micro-bubbles.
- the micro-interface generator breaks these large bubbles into micro-bubbles, which improves the generation efficiency of micro-bubbles.
- the micro-interface generator located at the upper part is connected to the propylene inlet
- the micro-interface generator located at the lower part is connected to the synthesis gas inlet
- the synthesis gas is relatively the gas source. It needs to be pre-synthesized, and the raw materials are all flammable and explosive gases, so in order to improve its safety, try to set the position of its air inlet as low as possible, and because it is easier to flow toward the top of the reactor after entering the reactor , so the micro-interface generator for crushing propylene is set in the upper part, and the micro-interface generator for crushing syngas is set in the lower part.
- Syngas passes through After the micro-interface generator is sufficiently broken and dispersed, it will pass through the gas distributor located on the upper part of the micro-interface generator with a higher probability to achieve a more uniform distribution.
- the gas distributor comprises a distributor main body and a plurality of nozzles; a plurality of the nozzles are obliquely arranged on the distributor main body to uniformly disperse the micro-bubbles generated by the micro-interface generator.
- the purpose of the inclined arrangement is also to make the bubbles more dispersed, and the dispersed tile area is larger and more dispersed, thereby further improving the reaction efficiency.
- the gas distributors are arranged at the position of the air outlet of each micro-interface generator, so as to ensure that all the micro-bubbles generated by the micro-interface generator enter into the main body of the distributor seamlessly and are sprayed out through the nozzle.
- the invention not only ensures the gas dispersion and crushing, but also improves the utilization rate of each micro-bubble through gas distribution, and avoids the disordered state of the micro-bubble, which is not conducive to the smooth progress of the reaction. .
- the setting position of the micro-interface generator and the connection arrangement with the gas distributor are obtained through a lot of practice.
- the bubble generator includes a gas-phase main circuit and a liquid-phase branch; the liquid-phase branch is connected to the reactor, and the solvent in the reactor enters the gas-phase main circuit through the liquid-phase branch.
- the gas phase mixes with the gas in the main gas phase to form bubbles.
- a catalyst inlet is provided on the side wall of the reactor, and a sprayer is arranged in the reactor, and the sprayer is located above the micro-interface generator; the sprayer is connected to the catalyst inlet. connected; the catalyst inlet is connected with a catalyst storage tank.
- the catalyst is sprayed by the sprayer, which improves the reaction effect and makes the catalyst distribution more uniform.
- two micro-interface generators are arranged in the reactor, which are respectively connected with the propylene inlet and the synthesis gas inlet.
- the reactor is first filled with a solvent, so that the two micro-interface generators are immersed in the solvent, Propylene is dispersed and broken into large propylene bubbles in the bubble generator, and enters the micro-interface generator through the propylene inlet, and is further dispersed and broken into micro-bubbles in the micro-interface generator.
- the syngas is dispersed in the bubble generator.
- the solvent provides a liquid medium for the dispersion and crushing of propylene and syngas;
- Propylene and syngas were respectively subjected to a micro-interface system, which improved the efficiency of dispersion and crushing. Opposing the outlets of the two micro-interface generators against each other can play a hedging effect to achieve uniform distribution of micro-bubbles.
- a gas distributor is arranged at the outlet of the micro-interface generator, and the generated micro-bubbles are sprayed in different directions through the nozzles on the gas distributor, so that the running direction of the micro-bubbles is changed, and the micro-bubbles are distributed more uniformly.
- the present invention improves the application effect of the micro-interface generator itself by applying the bubble generator, the micro-interface generator and the gas distributor in combination.
- micro-interface generator used in the present invention has been embodied in the inventor's prior patents, such as application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U.
- application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U In the previous patent CN201610641119.6, the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator) were introduced in detail.
- the body is provided with an inlet communicating with the cavity, the opposite first and second ends of the cavity are open, wherein the cross-sectional area of the cavity is from the middle of the cavity to the first and second ends of the cavity.
- the second end is reduced; the secondary crushing piece is arranged at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is arranged in the cavity, and both ends of the secondary crushing piece and the cavity are open
- An annular channel is formed between the through holes of the micro-bubble generator.
- the micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe.” From the specific structure disclosed in the application document, we can know that its specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe. In the bubble generator, ultra-high-speed rotation and cutting of the gas make the gas bubbles break into micro-bubbles at the micron level, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micro-bubble generator in this patent belongs to the pneumatic micro-interface generation. device.
- the previous patent 201610641251.7 records that the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed port with the gas-liquid mixture outlet, indicating that the bubble breaker is both It needs to be mixed with gas and liquid.
- the primary bubble breaker mainly uses circulating liquid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is a gas-liquid breaker. The mixture is simultaneously fed into the elliptical rotating ball for rotation, so that the bubbles are broken during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage type micro-interface generator.
- both hydraulic micro-interface generators and gas-liquid linkage micro-interface generators belong to a specific form of micro-interface generators.
- the micro-interface generators used in the present invention are not limited to the above-mentioned forms.
- the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can take.
- the previous patent 201710766435.0 recorded that "the principle of the bubble breaker is to achieve high-speed jets to achieve gas collision", and also stated that it can be used in micro-interface enhanced reactors to verify the relationship between the bubble breaker and the micro-interface generator.
- the top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet.
- the liquid phase entering from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the accompanying drawings.
- the bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.
- micro-interface generator Since the micro-interface generator was just developed in the early stage of the previous patent application, it was named as micro-bubble generator (CN201610641119.6), bubble breaker (201710766435.0), etc., and later changed its name to micro-interface generator with continuous technological improvement.
- the micro-interface generator in the present invention is equivalent to the previous micro-bubble generator, bubble breaker, etc., but the names are different. To sum up, the micro-interface generator of the present invention belongs to the prior art.
- the top of the reactor is connected with a first condenser; the non-condensable gas outlet of the first condenser is connected with a combustion system, and the condensate outlet of the first condenser is connected with the reactor.
- the tail gas at the top of the reactor is condensed by the first condenser, and the high-boiling substances such as n-butyraldehyde/isobutyraldehyde are condensed into liquid and returned to the reactor, and the non-condensable nitrogen, hydrogen, propane, carbon monoxide, etc. enter the combustion system for combustion and removal.
- a solvent inlet is provided at the bottom of the reactor, and a solvent storage tank is connected to the solvent inlet.
- the solvent in the solvent storage tank flows into the reactor through the solvent inlet to provide a medium for the reaction.
- the solvent is n-butyraldehyde or isobutyraldehyde.
- a product outlet is provided on the reactor, and a demister is connected to the product outlet;
- the tower is connected with a n-butyraldehyde storage tank.
- the demister traps small droplets entrained in the gas stream from the reactor and returns it to the reactor.
- a second condenser is arranged between the demister and the gas-liquid separator; the product after being defoamed by the demister is condensed by the second condenser and flows into the gas-liquid separator .
- the second condenser condenses the gas-phase product and flows into the gas-liquid separator.
- the gas-liquid separator is further connected with a third condenser, and the third condenser is connected with the micro-interface generator located above in the reactor; A portion of the product flows directly into the isomer separation column, and a portion is condensed by the third condenser and then flows back into the reactor.
- a circulating pump is arranged at the outlet of the gas-liquid separator, the liquid phase stream at the bottom of the gas-liquid separator enters the circulating pump to increase the pressure, and a part of the material at the outlet of the circulating pump flows into the isomer separation tower as a crude product, and the other part passes through.
- the third condenser is cooled down to about 80°C and returned to the micro-interface generator in the reactor to continue to participate in the reaction.
- the present invention also provides a kind of reaction method adopting the above-mentioned reaction system of propylene carbonylation to prepare butyraldehyde, comprising the following steps:
- the propylene and synthesis gas are dispersed and broken through the micro-interface respectively, they are mixed with the catalyst to carry out the hydroxyl synthesis reaction, and then the crude product is obtained after defoaming and condensation gas-liquid separation.
- the crude product is separated from n-butyraldehyde and isobutyraldehyde. After distillation and purification, n-butyraldehyde was obtained.
- the reaction temperature for the synthesis of the hydroxyl group is 85-90° C., and the pressure is 1.1-1.8 MPa; preferably, the catalyst is a rhodium catalyst.
- the propylene and the synthesis gas are dispersed and crushed respectively by arranging a micro-interface generator inside the reactor, so that before the propylene and the synthesis gas are subjected to the carbonylation reaction, they are crushed into micro-particles with a diameter greater than or equal to 1 ⁇ m and less than 1 mm.
- the bubbles increase the mass transfer area of the phase boundary, improve the solubility of propylene and synthesis gas in the solvent, reduce the reaction pressure and improve the reaction efficiency.
- the n-butanol product obtained by the reaction method of the invention has good quality and high yield.
- the preparation method itself has low reaction temperature, greatly reduced pressure and significantly reduced cost.
- the reaction system of the present invention disperses and crushes propylene and synthesis gas respectively by arranging two micro-interface generators inside the reactor, which improves the mass transfer effect, greatly improves the mass transfer rate, reduces the temperature required for the reaction and pressure;
- the propylene micro-bubbles and the syngas micro-bubbles can play a hedging effect, so as to realize the uniform distribution of the micro-bubbles;
- the raw material gas is pre-broken. Before dispersing the gas into micro-bubbles, the gas is broken into large bubbles, and the micro-interface generator breaks these large bubbles into micro-bubbles, which improves the micro-bubble. Generation efficiency.
- Fig. 1 is the structural representation of the reaction system of the propylene carbonylation to prepare butyraldehyde provided in the embodiment of the present invention
- FIG. 2 is a schematic structural diagram of a shower provided by an embodiment of the present invention.
- FIG. 3 is a schematic structural diagram of a bubble generator provided by an embodiment of the present invention.
- the terms “installed”, “connected” and “connected” should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
- installed should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
- this embodiment provides a reaction system for producing butyraldehyde by carbonylation of propylene, including: a reactor 10, a propylene storage tank 150, a carbon monoxide storage tank 130, a hydrogen storage tank 140, and a propylene pipeline 200 And the synthesis gas pipeline 210; the side wall of the reactor 10 is sequentially provided with a propylene inlet 102 and a synthesis gas inlet 101 from top to bottom.
- the propylene inlet 102 is connected to the propylene storage tank 150 through the propylene pipeline 200; the carbon monoxide storage tank 130 is connected to the hydrogen storage tank 140 in parallel and both are connected to the synthesis gas inlet 101 through the synthesis gas pipeline 210; the propylene pipeline 200 is connected to the synthesis gas pipeline 210 Both are provided with bubble generators 190 for pre-dispersing and breaking the gas into bubbles.
- the bubble generator 190 includes a gas phase main circuit 1901 and a liquid phase branch circuit 1902; the liquid phase branch circuit 1902 is connected to the reactor 10, and the solvent in the reactor 10 enters the gas phase main circuit 1901 through the liquid phase branch circuit 1902 It mixes with the gas in the gas phase main path 1901 to form bubbles.
- propylene enters the gas phase main circuit 1901 of the bubble generator 190 through the propylene pipeline 200, and the solvent in the reactor 10 enters the gas phase main circuit 1901 through the liquid phase branch circuit 1902, and mixes with the propylene in the gas phase main circuit 1901 to form propylene bubbles.
- the propylene bubbles and the remaining solvent flow back to the reactor 10 from the propylene inlet 102; at the same time, the synthesis gas enters the gas phase main circuit 1901 of the bubble generator 190 through the synthesis gas pipeline 210, and the solvent in the reactor 10 passes through the liquid phase branch circuit 1902 Entering the gas phase main circuit 1901, it is mixed with the synthesis gas in the gas phase main circuit 1901 to form synthesis gas bubbles, and the propylene bubbles and the remaining solvent flow back to the reactor 10 from the propylene inlet 102.
- a water pump is provided at the inlet of the liquid phase branch 1902 to extract the solvent to the liquid phase branch 1902 .
- Two micro-interface generators 105 are arranged inside the reactor 10 from top to bottom, and the micro-interface generator 105 located above is connected to the propylene inlet 102 to break the propylene gas into micro-bubbles of micron level; the micro-interface generator located below 105 is connected to the syngas inlet 101 for breaking the syngas into micro-bubbles of micron level; the outlets of the two micro-interface generators 105 are opposite to each other, and gas distributors 106 for uniform distribution of raw materials are connected to the outlets.
- the gas distributor 106 includes a distributor body 1061 and a plurality of nozzles 1062 ; the plurality of nozzles 1062 are obliquely arranged on the distributor body 1061 to uniformly disperse the micro-bubbles generated by the micro-interface generator 105 .
- a catalyst inlet 103 is arranged on the side wall of the reactor 10, and a sprayer 104 is also arranged in the reactor 10.
- the sprayer 104 is located above the micro-interface generator 105; the sprayer 104 is connected with the catalyst inlet 103; the catalyst inlet A catalyst storage tank 160 is connected to 103 .
- the catalyst is sprayed by the sprayer 104, which can make the catalyst distribution more uniform.
- the catalyst used in this embodiment is a rhodium catalyst.
- a first condenser 180 is connected to the top of the reactor 10 ;
- the tail gas at the top of the reactor 10 is condensed by the first condenser 180, and the high-boiling substances such as n-butyraldehyde/isobutyraldehyde are condensed into liquid and returned to the reactor 10, and the non-condensable nitrogen, hydrogen, propane, carbon monoxide, etc. enter the combustion system 170 for combustion remove.
- a solvent inlet 107 is provided at the bottom of the reactor 10 , and a solvent storage tank 120 is connected to the solvent inlet 107 .
- the solvent in the solvent storage tank 120 flows into the reactor 10 through the solvent inlet 107 to provide a medium for the reaction.
- the selected solvent is n-butyraldehyde or isobutyraldehyde.
- the reactor 10 is provided with a product outlet 108, and the product outlet 108 is connected with a demister 20; , the rectifying tower 90 is connected with a n-butyraldehyde storage tank 110.
- the demister 20 captures small droplets entrained in the gas stream from the reactor 10 and returns to the reactor 10 .
- the top of the isomer separation tower 70 is provided with a fourth condenser 80 . Since the difference between the boiling points of n-butanol and isobutanol is small, a plurality of trays are arranged in the isomer separation tower 70 to increase reflux.
- a second condenser 30 is arranged between the demister 20 and the gas-liquid separator 40;
- the second condenser 30 condenses the gas-phase product and flows into the gas-liquid separator 40 .
- the gas-liquid separator 40 is also connected with a third condenser 60, and the third condenser 60 is connected with the micro-interface generator 105 located above in the reactor 10; a part of the product separated by the gas-liquid separator 40 directly flows into the isothermal In the structure separation tower 70, a part is condensed by the third condenser 60 and then flows back to the reactor 10.
- a circulating pump 50 is provided at the outlet of the gas-liquid separator 40, the liquid phase stream at the bottom of the gas-liquid separator 40 enters the circulating pump 50 to increase the pressure, and a part of the material at the outlet of the circulating pump 50 flows into the isomer separation tower as a crude product.
- the other part is cooled down to about 80° C. by the third condenser 60 and returned to the micro-interface generator 105 in the reactor 10 to continue to participate in the reaction.
- the outlet of the rectifying tower 90 is provided with a reboiler 100, and the reboiler 100 divides the flow out of the rectifying tower 90 into a gas-liquid two-phase stream, the gas phase stream flows back into the rectifying tower 90, and the liquid phase stream flows into the rectifying tower 90.
- n-butyraldehyde storage tank 110 n-butyraldehyde storage tank 110.
- the specific reaction process of the reaction system of this embodiment is as follows: Before the reaction, the reactor 10 is filled with a solvent, and the two micro-interface generators 105 are immersed in the solvent. During the reaction, propylene enters the bubble generator 190 through the propylene pipeline 200, is dispersed and broken into large propylene bubbles with the participation of the solvent, and enters the micro-interface generator 105 through the propylene inlet 102, and further in the micro-interface generator 105.
- the reaction product After the reaction product is defoamed by the demister 20, it is condensed by the second condenser 30 and flows into the gas-liquid separator 40, and the gas phase after the gas-liquid separation flows back to the reactor 10, and a part of the liquid phase enters the isomer separation tower 70, The other part is cooled down to about 80° C. by the third condenser 60 and returned to the micro-interface generator 105 in the reactor 10 to continue to participate in the reaction.
- the isomer separation tower 70 separates the product, and the separated n-butyraldehyde is rectified in the rectification tower 90 and then flows into the n-butyraldehyde storage tank 110 .
- the reaction system of the present invention has low energy consumption, low cost, high safety, low required reaction temperature and pressure, few side reactions, and n-butyraldehyde.
- the yield is high, and it is worthy of widespread application.
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Abstract
Description
Claims (10)
- 一种丙烯羰基化制丁醛的反应***,其特征在于,包括:反应器、丙烯储罐、一氧化碳储罐、氢气储罐、丙烯管路和合成气管路;所述反应器侧壁由上到下依次设置有丙烯进口和合成气进口;所述反应器内部由上到下设置有两个微界面发生器,位于上方的所述微界面发生器与所述丙烯进口相连以将丙烯气体破碎成微米级别的微气泡;位于下方的所述微界面发生器与所述合成气进口相连以用于破碎合成气成微米级别的微气泡;两个所述微界面发生器的出口相对且出口处均连接有用于将原料均匀分布的气体分布器;所述丙烯进口通过所述丙烯管路与所述丙烯储罐连接;所述一氧化碳储罐与所述氢气储罐并联且所述一氧化碳储罐与所述氢气储罐均通过所述合成气管路与所述合成气进口相连;所述丙烯管路与所述合成气管路上均设置有用于将气体预分散破碎为气泡的气泡发生器。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述气体分布器包括分布器主体和多个喷嘴;多个所述喷嘴倾斜布置在所述分布器主体上以将所述微界面发生器产生的微气泡均匀分散。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述气泡发生器包括气相主路和液相支路;所述液相支路与所述反应器相连,所述反应器中的溶剂经所述液相支路进入所述气相主路与所述气相主路中的气体混合形成气泡。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述反应器侧壁上设置有催化剂进口,所述反应器内设置有喷淋器,所述喷淋器位于所述微界面发生器的上方;所述喷淋器与所述催化剂进口相连;所述催化剂进口连接有催化剂储罐。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述反应器顶部连接有第一冷凝器;所述第一冷凝器的不凝气出口连接有燃烧 ***,所述第一冷凝器的冷凝物出口与反应器相连。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述反应器底部设置有溶剂进口,所述溶剂进口连接有溶剂储罐。
- 根据权利要求1所述的丙烯羰基化制丁醛的反应***,其特征在于,所述反应器上设置有产物出口,所述产物出口连接有除沫器;所述除沫器依次连接有气液分离器、异构物分离塔和精馏塔,所述精馏塔连接有正丁醛储罐;优选的,所述除沫器与所述气液分离器间设置有第二冷凝器;经所述除沫器除沫后的产物经所述第二冷凝器冷凝流入所述气液分离器中。
- 根据权利要求7所述的丙烯羰基化制丁醛的反应***,其特征在于,所述气液分离器还连接有第三冷凝器,所述第三冷凝器与所述反应器中位于上方的所述微界面发生器相连;经所述气液分离器分离后的产物一部分直接流入所述异构物分离塔中,一部分经所述第三冷凝器冷凝后流回所述反应器中。
- 采用权利要求1-8任一项所述的丙烯羰基化制丁醛的反应***的反应方法,其特征在于,包括如下步骤:将丙烯和合成气分别经微界面分散破碎后,与催化剂混合,进行羟基合成反应,再经过除沫冷凝气液分离后得到粗产品,粗产品进行正丁醛和异丁醛的分离,经精馏纯化后得到正丁醛。
- 根据权利要求9所述的反应方法,其特征在于,所述羟基合成反应温度为85-90℃,压力为1.1-1.8MPa;优选的,所述催化剂为铑催化剂。
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CN113058517A (zh) * | 2021-03-23 | 2021-07-02 | 南京延长反应技术研究院有限公司 | 一种丁辛醇的微界面制备装置及方法 |
CN113041962A (zh) * | 2021-04-01 | 2021-06-29 | 南京延长反应技术研究院有限公司 | 一种丙烯羰基化制丁醛的反应***及方法 |
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