CN114505027A - 1, 4-butanediol micro-interface preparation system and method - Google Patents
1, 4-butanediol micro-interface preparation system and method Download PDFInfo
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- CN114505027A CN114505027A CN202210201593.2A CN202210201593A CN114505027A CN 114505027 A CN114505027 A CN 114505027A CN 202210201593 A CN202210201593 A CN 202210201593A CN 114505027 A CN114505027 A CN 114505027A
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000005886 esterification reaction Methods 0.000 claims abstract description 25
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims abstract description 21
- 230000032050 esterification Effects 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 8
- 238000003756 stirring Methods 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 26
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 5
- 239000011344 liquid material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 4
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- -1 propylene alcohol Chemical compound 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- 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
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- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/04—Pressure vessels, e.g. autoclaves
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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
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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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention provides a 1, 4-butanediol micro-interface preparation system which comprises a mixing tank, wherein the mixing tank is connected with a methanol feeding pipeline and a maleic anhydride feeding pipeline, the mixing tank is sequentially connected with a heat exchanger, a single esterification reactor, a double esterification reactor, a hydrogenation reactor, a flash tower, a methanol rectifying tower, a dimethyl maleate rectifying tower and a 1, 4-butanediol rectifying tower, a product outlet is formed in the 1, 4-butanediol rectifying tower, a gas-liquid linkage type micro-interface generator is arranged in the hydrogenation reactor, and the gas-liquid linkage type micro-interface generator is connected with a hydrogen inlet pipeline and a circulating pump. According to the invention, the gas-liquid linkage type micro-interface generator disperses and crushes hydrogen into hydrogen microbubbles, so that the mass transfer area of gas and liquid phases is increased, and the gas-liquid linkage type micro-interface generator has a circulating stirring function, so that hydrogen can better react with mixed liquid during hydrogenation reaction, and the hydrogenation reaction is more sufficient.
Description
Technical Field
The invention belongs to the technical field of butanediol production, and particularly relates to a 1, 4-butanediol micro-interface preparation system.
Background
1, 4-butanediol is one of methanol series product chains and is an important basic organic chemical and fine chemical raw material, a manufacturer generally does not use 1, 4-butanediol as a final product in the process of producing 1, 4-butanediol, but pays attention to the extension of a 1, 4-butanediol derivative, and the 1, 4-butanediol derivative is a fine chemical product with higher added value and is widely used as a solvent, a medicine, a cosmetic, a plasticizer, a curing agent, a pesticide, an herbicide, foamed artificial leather, fiber, engineering plastics and the like; because of the wide application and large consumption of 1, 4-butanediol, the production technology of 1, 4-butanediol needs to be improved continuously.
The production method of the 1, 4-butanediol mainly comprises the following steps: (1) a Reppe method (alkynal method) using formaldehyde and acetylene as raw materials; (2) butadiene acetoxylation with butadiene and acetic acid as raw materials; (3) a propylene oxide process using propylene oxide/propylene alcohol as a raw material; (4) davy method using n-butane/maleic anhydride as a raw material. Because butadiene and propylene oxide are in short supply in China, the 1, 4-butanediol produced by the two methods is not mature, the production method is selected according to resource advantages, and the Reppe method (acetylenic aldehyde method) is mainly used in China.
The production process flow of the Reppe method mainly comprises a formaldehyde working section, an ethynylation working section, a hydrogenation working section and a product rectification working section, wherein the formaldehyde working section mainly generates formaldehyde by raw materials of methanol and air under the action of a catalyst; the ethynylation section is mainly used for carrying out acetylenic aldehyde reaction on acetylene and formaldehyde aqueous solution under the action of a catalyst to generate refined 1, 4-butynediol; the hydrogenation section is mainly to generate crude 1, 4-butanediol by 1, 4-butynediol and hydrogen under certain pressure and the action of a catalyst; the product rectification working section is mainly used for rectifying the 1, 4-butanediol to obtain a high-purity 1, 4-butanediol product.
The reaction in the hydrogenation section is to generate crude 1, 4-butanediol from 1, 4-butynediol and hydrogen, as the reaction proceeds, slurry is formed by residual unreacted 1, 4-butynediol and generated crude 1, 4-butanediol in the reaction vessel, hydrogen needs to be mixed in the slurry to react with residual 1, 4-butynediol, and the hydrogen is easy to form bubbles after entering the slurry and is not uniformly mixed with the slurry, so that the reaction is insufficient, and the yield of 1, 4-butanediol is reduced.
In the prior art, in order to improve the mixing effect of hydrogen and butynediol and enable the reaction to be more sufficient so as to improve the yield of 1, 4-butanediol, a two-stage hydrogenation method is mainly adopted in a hydrogenation working section: a slurry bed reactor with stirring is adopted for the first-stage hydrogenation, the reaction temperature is 50-60 ℃, and the reaction pressure is 1.5-3.0 MPa; the second-stage hydrogenation adopts a fixed bed high-pressure 1, 4-butanediol reactor, the reaction temperature is 110-165 ℃, and the reaction pressure is 7-30 MPa. The two-stage hydrogenation method generally adopts a stirring or bubbling mode, and the traditional stirring paddle or bubbling tower reactor can only generate turbulent eddies with the size of centimeters or millimeters, so that most of energy can only be converted into heat energy even if the power of a stirring motor is increased, but not into surface energy required by small bubble generation, and the hydrogen and butynediol are not uniformly mixed; meanwhile, in order to further promote the reaction to fully progress, the dosage of the catalyst is increased in the hydrogenation process.
However, the hydrogenation section of the prior art still has the following problems:
1. in order to promote the reaction in the hydrogenation section, manufacturers increase the amount of catalyst, and increase the production cost.
2. Because the amount of the catalyst in the hydrogenation section is increased, the incomplete reaction of the catalyst often occurs, the waste of the residual catalyst is caused, and the normal production of a subsequent system is influenced after the residual catalyst enters the subsequent system.
3. In the process of mixing hydrogen and slurry, a stirring dead angle still exists, and the problems of uneven stirring of hydrogen, catalyst and slurry still exist, so that the reaction in a hydrogenation working section is insufficient, and the yield of 1, 4-butanediol is influenced.
4. The agitation does not or does not completely break the bubbles of the hydrogen gas, and the hydrogen gas cannot be uniformly mixed with the slurry.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a 1, 4-butanediol micro-interface preparation system, hydrogen is dispersed and crushed into hydrogen micro-bubbles through a gas-liquid linkage micro-interface generator, the gas-liquid two-phase mass transfer area is increased, and the gas-liquid linkage micro-interface generator has a circulating stirring function, so that hydrogen can better react with mixed liquid during hydrogenation reaction, and the hydrogenation reaction is more sufficient.
The second purpose of the invention is to provide a 1, 4-butanediol micro-interface preparation method, which saves the cost and improves the reaction efficiency.
In order to achieve the technical purpose, the invention provides the following technical scheme:
the invention provides a 1, 4-butanediol micro-interface preparation system which comprises a mixing tank for mixing methanol and maleic anhydride, wherein the mixing tank is connected with a methanol feeding pipeline and a maleic anhydride feeding pipeline, the mixing tank is sequentially connected with a heat exchanger for heating mixed raw materials, a single esterification reactor, a double esterification reactor, a hydrogenation reactor, a flash tower, a methanol rectifying tower, a dimethyl maleate rectifying tower and a 1, 4-butanediol rectifying tower, and the 1, 4-butanediol rectifying tower is provided with a product outlet;
the inside of hydrogenation ware is provided with gas-liquid linkage formula micro-interface generator, gas-liquid linkage formula micro-interface generator is connected with hydrogen admission line and circulating pump.
According to the invention, the gas-liquid linkage type micro-interface generator is arranged to disperse and crush hydrogen into hydrogen microbubbles, and the hydrogen microbubbles react with dimethyl maleate to increase the phase boundary mass transfer area and improve the reaction efficiency. The gas-liquid linkage type micro-interface generator is divided into a hydraulic type micro-interface generator and a pneumatic type micro-interface generator, a circulating pump is connected outside the hydraulic type micro-interface generator, liquid materials are pumped and pressurized by the circulating pump and then returned to the hydraulic type micro-interface generator, and the liquid materials are compressed and retracted into the pneumatic type micro-interface generator through a communicating pipeline by the hydraulic type micro-interface generator, so that the problem that the pneumatic type micro-interface generator is blocked by dimethyl maleate in an air hole can be effectively solved, and meanwhile, the reaction efficiency is also improved.
Preferably, the gas-liquid linkage type micro-interface generator comprises a pneumatic type micro-interface generator and a hydraulic type micro-interface generator, the pneumatic type micro-interface generator is arranged at the bottom of the hydrogenation reactor, and the hydraulic type micro-interface generator is arranged right above the pneumatic type micro-interface generator.
Preferably, a communication pipeline is arranged between the pneumatic micro-interface generator and the hydraulic micro-interface generator.
Preferably, the pneumatic micro-interface generator is connected with a hydrogen gas inlet pipeline, and the hydraulic micro-interface generator is connected with a circulating pump.
Preferably, the top of the flash tower is connected with a hydrogen recovery channel, and the hydrogen recovery channel is connected with the hydrogen inlet pipeline.
Preferably, a catalyst bed layer is arranged in the double esterification reactor.
Preferably, the double esterification reactor is connected with a methanol feed pipeline.
Preferably, a feed pump for sucking methanol into the mixing tank is provided on the methanol feed pipe.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of application nos. CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and 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 adopt.
In addition, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the relevance between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase.
Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names. In summary, the micro-interface generator of the present invention belongs to the prior art.
In addition, the invention also provides a micro-interface preparation method of 1, 4-butanediol, which comprises the following steps:
the esterification reaction of methanol and cis-anhydride generates dimethyl maleate, then the dimethyl maleate is subjected to hydrogenation reaction, and finally the product is rectified and purified to obtain the 1, 4-butanediol.
Preferably, the hydrogenation reaction is carried out at the temperature of 160-220 ℃ and the pressure of 3-5 MPa.
Compared with the prior art, the invention has the advantages that:
1. by arranging the gas-liquid linkage type micro-interface generator, hydrogen is dispersed and crushed into hydrogen micro-bubbles, so that the phase boundary mass transfer area is increased, and the reaction efficiency is improved;
2. the gas-liquid linkage type micro-interface generator fully mixes the hydrogen with the liquid material, so that the reaction efficiency is improved;
3. the temperature and pressure are reduced during the hydrogenation reaction, and the energy consumption in the production process is saved.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic diagram of a system for the micro-interfacial preparation of 1, 4-butanediol;
wherein:
10-a mixing tank; 11-a feed pump;
a 12-maleic anhydride feed line; 13-methanol feed line;
20-a heat exchanger; 30-a mono-esterification reactor;
a 40-double esterification reactor; a 41-methanol feed line;
42-a first condenser; 43-catalyst bed;
50-a hydrogenation reactor; 51-gas-liquid linkage type micro-interface generator;
511-a hydraulic micro-interface generator; 512-pneumatic micro-interface generator;
513-a communication duct; 52-a circulation pump;
53-hydrogen inlet line; 60-a flash column;
a 70-methanol rectification column; 71-a second condenser;
72-a first reboiler; 80-dimethyl maleate rectifying tower;
81-a third condenser; 82-a second reboiler;
a 90-1, 4-butanediol rectifying tower; 91-a fourth condenser;
92-a third reboiler; 93-product outlet.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are a part of the embodiments of the present invention, rather than all of the embodiments, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1
Referring to fig. 1, the schematic structural diagram of the 1, 4-butanediol micro-interface preparation system provided by the present invention includes a mixing tank 10, a heat exchanger 20, a single esterification reactor 30, a double esterification reactor 40, a hydrogenation reactor 50, a flash tower 60, a methanol rectifying tower 70, a dimethyl maleate rectifying tower 80, and a 1, 4-butanediol rectifying tower 90.
Methanol is conveyed to a mixing tank 10 through a feed pump 11 and a methanol feed pipeline 13, maleic anhydride is conveyed to the mixing tank 10 through a maleic anhydride feed pipeline 12, the methanol and the maleic anhydride are fully mixed in the mixing tank 10, then the mixed material is conveyed to a heat exchanger 20, low-pressure steam is conveyed to one end of the heat exchanger 20, and process water after heat exchange is discharged from the other end of the heat exchanger 20. The mixed feed heated to 75 ℃ is sent to the mono-esterification reactor 30.
The main material in the mono-esterification reactor 30 is monomethyl maleate, specifically about 85% of maleic anhydride is converted into monomethyl maleate, 12% of the monomethyl maleate is converted into dimethyl maleate, and the mono-esterification reactor 30 also contains unreacted maleic anhydride and methanol.
The mixture from the single esterification reactor 30 is completely transferred to the double esterification reactor 40, and a catalyst bed layer 43 is arranged inside the double esterification reactor 40, wherein the catalyst is DNW-I type ion exchange resin. The double esterification reactor 40 is connected to a methanol feed line 41, a first condenser 42, so that the reaction zone and the separation zone are carried out in the same reactor. At this point almost all of the maleic anhydride was converted to dimethyl maleate. The monomethyl maleate reacts with methanol in the catalyst bed 43, thus rectifying the dimethyl maleate.
Then the single esterification reactor 30 enters a hydrogenation reactor 50, and a gas-liquid linkage type micro-interface generator 51 is arranged in the hydrogenation reactor 50, wherein the gas-liquid linkage type micro-interface generator 51 comprises a hydraulic type micro-interface generator 511 and a pneumatic type micro-interface generator 512, and the hydraulic type micro-interface generator 511 is arranged right above the pneumatic type micro-interface generator 512 and is connected with the pneumatic type micro-interface generator through a communication pipeline 513. The exterior of the hydraulic micro-interface generator 511 is connected with a circulating pump 52, and the pneumatic micro-interface generator 512 is connected with a hydrogen inlet pipe 53. At this time, the maleic acid dimethyl ester reacts with hydrogen microbubbles and a catalyst Cu/MAC-41 to generate gamma-butyrolactone, 1, 4-butanediol and tetrahydrofuran. The reaction pressure is 3MPa, and the reaction temperature is 160 ℃. The hydrogen is separated from the material exiting the hydrogenation reactor 50 after entering the flash column 60 and returned to the hydrogenation reactor 50.
Then the material passes through a methanol rectifying tower 70, a second condenser 71 and a first reboiler 72 are arranged on the methanol rectifying tower 70 to separate out methanol, the methanol enters a dimethyl maleate rectifying tower 80, a third condenser 81 and a second reboiler 82 are arranged on the dimethyl maleate rectifying tower 80 to separate out dimethyl maleate,
then the material passes through a 1, 4-butanediol rectifying tower 90, a fourth condenser 91 and a third reboiler 92 are arranged on the 1, 4-butanediol rectifying tower 90, and the rectified 1, 4-butanediol rectifying tower 90 comes out from a product outlet 93 and is collected and stored.
The esterification reaction of methanol and cis-anhydride generates dimethyl maleate, then the dimethyl maleate is subjected to hydrogenation reaction, and finally the product is rectified and purified to obtain the 1, 4-butanediol.
The temperature of the hydrogenation reaction is 160 ℃, and the pressure is 3 MPa.
Example 2
The other operating steps are identical to those of example 1, except that: the hydrogenation reactor is internally provided with only a pneumatic micro-interface generator.
Example 3
The other operating steps are identical to those of example 1, except that: only a hydraulic micro-interface generator is arranged in the hydrogenation reactor.
Example 4
The other operating steps are identical to those of example 1, except that: there is no communication channel between the pneumatic micro-interface generator and the hydraulic micro-interface generator.
Comparative example 1
The other operating steps are identical to those of example 1, except that: the interior of the hydrogenation reactor is not provided with any micro-interface generator.
By comparing the above examples 1 to 4 with comparative example 1, the following data were obtained:
compared with the embodiments 2 to 4, the embodiment 1 has the advantages that the hydrogenation reactor is not provided with the gas-liquid linkage type micro-interface generator, but only provided with the single pneumatic type micro-interface generator and the hydraulic type micro-interface generator, so that the reaction efficiency of the 1, 4-butanediol is reduced, the temperature and the pressure of the hydrogenation reaction are improved, and the energy consumption of the reaction is increased.
According to the invention, the gas-liquid linkage type micro-interface generator is arranged to disperse and crush hydrogen into hydrogen microbubbles, and the hydrogen microbubbles react with dimethyl maleate to increase the phase boundary mass transfer area and improve the reaction efficiency. The gas-liquid linkage type micro-interface generator is divided into a hydraulic type micro-interface generator and a pneumatic type micro-interface generator, a circulating pump is connected outside the hydraulic type micro-interface generator, liquid materials are pumped and pressurized by the circulating pump and then return to the hydraulic type micro-interface generator, and the hydraulic type micro-interface generator compresses the liquid materials into the pneumatic type micro-interface generator through a communicating pipeline, so that the problem that the pneumatic type micro-interface generator is blocked in air holes by dimethyl maleate can be effectively relieved, and meanwhile, the reaction efficiency is improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A1, 4-butanediol micro-interface preparation system is characterized by comprising a mixing tank for mixing methanol and maleic anhydride, wherein the mixing tank is connected with a methanol feeding pipeline and a maleic anhydride feeding pipeline, the mixing tank is sequentially connected with a heat exchanger for heating mixed raw materials, a single esterification reactor, a double esterification reactor, a hydrogenation reactor, a flash tower, a methanol rectifying tower, a dimethyl maleate rectifying tower and a 1, 4-butanediol rectifying tower, and the 1, 4-butanediol rectifying tower is provided with a product outlet;
the inside of hydrogenation ware is provided with gas-liquid linkage formula micro-interface generator, gas-liquid linkage formula micro-interface generator is connected with hydrogen admission line and circulating pump.
2. The micro-interface preparation system of claim 1, wherein the gas-liquid linkage micro-interface generator comprises a pneumatic micro-interface generator and a hydraulic micro-interface generator, the pneumatic micro-interface generator is disposed at the bottom of the hydrogenation reactor, and the hydraulic micro-interface generator is disposed directly above the pneumatic micro-interface generator.
3. The system of claim 2, wherein a communication channel is disposed between the pneumatic micro-interface generator and the hydraulic micro-interface generator.
4. The system of claim 2, wherein the pneumatic micro-interface generator is connected to the hydrogen inlet line and the hydraulic micro-interface generator is connected to the circulation pump.
5. The system of claim 1, wherein a hydrogen recovery channel is connected to the top of the flash column, and the hydrogen recovery channel is connected to the hydrogen inlet line.
6. The system of claim 1, wherein the double esterification reactor comprises a catalyst bed.
7. The system of claim 1, wherein the double esterification reactor is connected to a methanol feed line.
8. The system of claim 1, wherein the methanol feed line is provided with a feed pump for drawing methanol into the mixing tank.
9. A method of using a system for the micro-interfacial production of 1, 4-butanediol according to any of claims 1-8, comprising the steps of:
the esterification reaction of methanol and cis-anhydride generates dimethyl maleate, then the dimethyl maleate is subjected to hydrogenation reaction, and finally the product is rectified and purified to obtain the 1, 4-butanediol.
10. The method as claimed in claim 9, wherein the hydrogenation reaction is carried out at a temperature of 160-220 ℃ and a pressure of 3-5 MPa.
Priority Applications (2)
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| CN202210201593.2A CN114505027A (en) | 2022-03-03 | 2022-03-03 | 1, 4-butanediol micro-interface preparation system and method |
| PCT/CN2022/118442 WO2023165110A1 (en) | 2022-03-03 | 2022-09-13 | Micro-interface preparation system and method for 1,4-butanediol |
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| CN202210201593.2A CN114505027A (en) | 2022-03-03 | 2022-03-03 | 1, 4-butanediol micro-interface preparation system and method |
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| WO2023165110A1 (en) * | 2022-03-03 | 2023-09-07 | 南京延长反应技术研究院有限公司 | Micro-interface preparation system and method for 1,4-butanediol |
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| WO2023165110A1 (en) | 2023-09-07 |
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