CN112457161A - Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde - Google Patents
Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde Download PDFInfo
- Publication number
- CN112457161A CN112457161A CN201910840683.4A CN201910840683A CN112457161A CN 112457161 A CN112457161 A CN 112457161A CN 201910840683 A CN201910840683 A CN 201910840683A CN 112457161 A CN112457161 A CN 112457161A
- Authority
- CN
- China
- Prior art keywords
- butanediol
- formaldehyde
- butynediol
- reactor
- tower
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 338
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 269
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 230000003014 reinforcing effect Effects 0.000 title description 3
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 238000002360 preparation method Methods 0.000 claims abstract description 66
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005728 strengthening Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 85
- 239000007789 gas Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 230000006835 compression Effects 0.000 claims description 12
- 238000007906 compression Methods 0.000 claims description 12
- 230000001276 controlling effect Effects 0.000 claims description 12
- 239000006200 vaporizer Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002309 gasification Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 3
- 230000002787 reinforcement Effects 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 18
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 10
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 20
- 239000012530 fluid Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000008098 formaldehyde solution Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000011949 solid catalyst 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
- 230000005587 bubbling Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002101 nanobubble Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 propylene alcohol Chemical compound 0.000 description 2
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 238000011085 pressure filtration Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention is suitable for the technical field of butanediol production, and provides a strengthening system and a strengthening process for preparing 1, 4-butanediol from acetylene and formaldehyde, wherein the strengthening system comprises a formaldehyde preparation device, a 1, 4-butynediol preparation device, a 1, 4-butanediol preparation device and a rectification device which are sequentially and correspondingly connected, and also comprises an intelligent control device; the 1, 4-butanediol preparation device comprises a 1, 4-butanediol reactor, wherein a micro-interface generator is arranged in the 1, 4-butanediol reactor and is used for crushing hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1 mm; the inlet end is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, and the outlet end is connected with a catalyst recoverer; the intelligent control device comprises a strategy setting unit, a parameter control unit and a model setting unit. Therefore, the invention can ensure that the reaction in the hydrogenation section is more sufficient, the yield of the 1, 4-butanediol is higher, the waste of catalyst raw materials is avoided, the production cost is reduced, and the intelligent operation is realized.
Description
Technical Field
The invention relates to the technical field of butanediol production, in particular to an enhancement system and a process for preparing 1, 4-butanediol from acetylene and formaldehyde.
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 prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide an enhanced system and process for preparing 1, 4-butanediol from acetylene and formaldehyde, which can enable the reaction in a hydrogenation section to be more sufficient, enable the yield of 1, 4-butanediol to be higher, avoid the waste of catalyst raw materials, reduce the production cost and realize intelligent operation.
In order to achieve the aim, the invention provides an enhancement system for preparing 1, 4-butanediol from acetylene and formaldehyde, which comprises a formaldehyde preparation device, a 1, 4-butynediol preparation device, a 1, 4-butanediol preparation device and a rectification device which are sequentially and correspondingly connected; the intelligent control device is further included.
The 1, 4-butanediol preparation device comprises a 1, 4-butanediol reactor, wherein a micro-interface generator is arranged at the bottom end inside the 1, 4-butanediol reactor and used for crushing reactant hydrogen to enable the diameter of micron-sized bubbles formed by crushing to be larger than or equal to 1 mu m and smaller than 1mm so as to be mixed with an intermediate product 1, 4-butynediol to form a gas-liquid emulsion.
The inlet end of the 1, 4-butanediol reactor is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, the hydrogen tank is connected with the micro-interface generator, and the feeding pump is connected with the 1, 4-butynediol preparation device; catalyst feeding structure includes the feeder hopper, the relative both sides in well lower part of feeder hopper are equipped with the backup pad, all be provided with the cylinder in the backup pad, the cylinder is connected the inside feeding baffle of feeder hopper.
The outlet end of the 1, 4-butanediol reactor is connected with a catalyst recoverer; the catalyst recoverer is connected with the rectifying device.
The intelligent control device is electrically connected with the reaction parameter controllers in the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectifying device; the intelligent control device comprises a strategy setting unit, a parameter control unit and a model setting unit; the strategy setting unit is used for setting the range of the reaction parameters and the learning strategy; the parameter control unit is used for controlling the reaction parameters of the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectification device according to a preset strategy and the range of the reaction parameters; the model setting unit is used for establishing a correlation model of the reaction parameters and the target object parameters.
According to the strengthening system for preparing 1, 4-butanediol from acetylene and formaldehyde, the catalyst recoverer comprises a thrust plate and a compression plate which are connected to two ends of a frame, a filtering structure is connected between the thrust plate and the compression plate, and the compression plate is connected with a compression structure; the filter structure comprises a plurality of filter plates, the middle parts of the filter plates are recessed inwards, and every two filter plates form a filter chamber.
According to the strengthening system for preparing 1, 4-butanediol by acetylene and formaldehyde, the formaldehyde preparation device comprises a formaldehyde reactor, a methanol vaporizer, a formaldehyde absorption tower and a circulating fan; the 1, 4-butynediol preparation device comprises a water washing tower, a 1, 4-butynediol reactor and a concentrator; the rectification device comprises a concentration tower, a salt tower, a low-boiling tower and a high-boiling tower.
According to the strengthening system for preparing the 1, 4-butanediol by using the acetylene and the formaldehyde, the top of the 1, 4-butanediol reactor is provided with the regulating valve for controlling the pressure of the 1, 4-butanediol reactor to be maintained at 0.2-3 MPa.
According to the strengthening system for preparing the 1, 4-butanediol by using the acetylene and the formaldehyde, the top of the concentration tower is also provided with a cooler for controlling the temperature of the top of the concentration tower, and a reflux pump for controlling the reflux quantity of the top of the concentration tower is also arranged on a reflux pipeline at the top of the concentration tower.
According to the strengthening system for preparing 1, 4-butanediol from acetylene and formaldehyde, the working pressure in the concentration tower is 60-90 KPa.
According to the strengthening system for preparing 1, 4-butanediol by acetylene and formaldehyde, the concentration mass concentration of the concentration tower to crude 1, 4-butanediol is more than or equal to 94%. .
According to the strengthening system for preparing 1, 4-butanediol from acetylene and formaldehyde, the vacuum pressure in the salt tower, the low-boiling tower and the high-boiling tower is less than or equal to 15 KPa.
According to the reinforcing system for preparing 1, 4-butanediol from acetylene and formaldehyde, the catalyst recoverer is connected with the intelligent control device.
According to the strengthening system for preparing 1, 4-butanediol by acetylene and formaldehyde, the invention also provides a process for preparing 1, 4-butanediol, which comprises the following steps:
step one
Introducing methanol into a methanol vaporizer for gasification, and then mixing the gasified methanol with fresh air to obtain mixed gas;
adding an iron-molybdenum catalyst into a formaldehyde reactor, and introducing the mixed gas into the formaldehyde reactor for reaction to obtain formaldehyde gas;
and introducing the formaldehyde gas into water to form a formaldehyde water solution with the volume concentration of 37-52%.
Step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the formaldehyde aqueous solution to obtain a crude 1, 4-butynediol feed liquid;
and (3) rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain the 1, 4-butynediol.
Step three
Introducing hydrogen gas in a hydrogen tank and the 1, 4-butynediol into a micro-interface generator; the micro-interface generator crushes the large hydrogen bubbles into micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and then the micron-sized bubbles and the 1, 4-butynediol are fully mixed to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor added with a Raney nickel catalyst for reaction to obtain crude 1, 4-butanediol with the mass concentration of 37-45%;
in the reaction process, the pressure of the 1, 4-butanediol reactor is 0.2-3 MPa.
Step four
Introducing the crude 1, 4-butanediol into a concentration tower, enabling the mass concentration of the crude 1, 4-butanediol to be more than or equal to 94% under the pressure of 60-90 KPa, and simultaneously separating by-products such as water and butanol contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure less than or equal to 15KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after the impurities are removed.
The invention aims to provide a strengthening system and a strengthening process for preparing 1, 4-butanediol from acetylene and formaldehyde, wherein a formaldehyde preparation device, a 1, 4-butynediol preparation device, a 1, 4-butanediol preparation device and a rectification device are arranged and correspondingly connected in sequence, wherein the outlet end of a 1, 4-butanediol reactor is connected with a catalyst recoverer, and a micro-interface generator is also arranged at the confluence position of a feeding pump and a hydrogen tank; the micro-interface generator can crush hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, and simultaneously, the micron-sized bubbles and 1, 4-butynediol are fully mixed to form a gas-liquid emulsion, so that the contact area of the hydrogen and the 1, 4-butynediol is increased, the hydrogen and the 1, 4-butynediol are mixed more uniformly and react more fully, and the amount of generated 1, 4-butanediol is more; the catalyst recoverer can collect the residual catalyst, so that waste is avoided, and the catalyst is prevented from influencing the normal production of a subsequent system; the invention is also provided with an intelligent control device to realize intelligent selection of optimal reaction conditions, so that the reaction is efficiently carried out, and time and labor waste caused by manual operation are avoided. In conclusion, the beneficial effects of the invention are as follows: the reaction in the hydrogenation section is more sufficient, the yield of the 1, 4-butanediol is higher, the waste of catalyst raw materials is avoided, the production cost is reduced, and the intelligent operation is realized.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic structural view of a catalyst feed structure according to the present invention;
FIG. 3 is a schematic diagram of a catalyst reclaimer configuration of the present invention;
in the figure, 1-formaldehyde preparation unit, 2-1, 4-butynediol preparation unit, 3-1, 4-butanediol preparation unit, 31-1, 4-butanediol reactor, 32-feed pump, 33-catalyst feed structure, 331-feed hopper, 332-feed baffle, 333-cylinder, 334-support plate; 34-hydrogen tank, 35-catalyst recoverer, 351-thrust plate, 352-compacting plate and 353-filter plate; 36-a micro-interface generator; 4-a rectifying device.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; 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 by those skilled in the art according to specific situations.
Referring to fig. 1, the invention provides an enhancement system for preparing 1, 4-butanediol from acetylene and formaldehyde, which comprises a formaldehyde preparation device 1, a 1, 4-butynediol preparation device 2, a 1, 4-butanediol preparation device 3 and a rectification device 4 which are sequentially and correspondingly connected, and also comprises an intelligent control device.
The formaldehyde preparation device 1 and the formaldehyde preparation device 1 mainly have the function of enabling methanol and air to generate formaldehyde under the action of an iron-molybdenum catalyst. The formaldehyde preparation device 1 comprises a formaldehyde reactor, a methanol vaporizer, a formaldehyde absorption tower and a circulating fan. During use, methanol is gasified into methanol gas in a methanol vaporizer, the methanol gas is mixed with fresh air brought in by a circulating fan, and then the methanol gas enters a formaldehyde reactor to react under the action of an iron-molybdenum catalyst to generate formaldehyde gas; the mixed gas of formaldehyde gas and air enters a formaldehyde absorption tower, gas-phase formaldehyde is absorbed by water, the residual air is discharged into a tail gas absorption system to be incinerated and discharged, the product is a formaldehyde aqueous solution with the volume concentration of 37-52%, and the formaldehyde aqueous solution is discharged from the bottom of the formaldehyde absorption tower.
1, 4- butynediol preparation device 2, 1, 4-butynediol preparation device 2 is mainly used for acetylene aldehyde reaction between acetylene and formaldehyde aqueous solution under the action of a copper bismuth catalyst to generate refined 1, 4-butynediol. The 1, 4-butynediol preparation device 2 comprises a water washing tower, a 1, 4-butynediol reactor and a concentrator. In the using process, acetylene gas is compressed to 0.3-0.5 MPa through a water washing tower and then is sent into a 1, 4-butynediol reactor to react with 37-52% of formaldehyde solution in a copper-bismuth overflow bed, and slurry obtained by reaction is filtered and separated through a concentrator to obtain crude 1, 4-butynediol feed liquid; then rectifying and recovering formaldehyde doped in the crude 1, 4-butynediol feed liquid, and then carrying out ion removal to obtain the 1, 4-butynediol.
Since the formaldehyde preparation device 1 and the 1, 4-butynediol preparation device 2 are mature devices in the prior art, even though the two devices are not specifically described in the present invention, a person skilled in the art can also implement the preparation work of formaldehyde and 1, 4-butynediol according to the prior art, and therefore, the present invention is not described in detail for the formaldehyde preparation device 1 and the 1, 4-butynediol preparation device 2.
1, 4- butanediol preparation device 3, 1, 4-butanediol preparation device 3 is used for generating crude 1, 4-butanediol by 1, 4-butynediol and hydrogen under the action of a Raney nickel catalyst under a certain pressure. The 1, 4-butanediol preparation device 3 comprises a 1, 4-butanediol reactor 31, wherein a micro-interface generator 36 is arranged at the bottom end inside the 1, 4-butanediol reactor 31, the inlet end of the 1, 4-butanediol reactor 31 is respectively connected with a feeding pump 32, a catalyst feeding structure 33 and a hydrogen tank 34, the hydrogen tank 34 is connected with the micro-interface generator 36, and the feeding pump 32 is connected with the 1, 4-butynediol preparation device 2; the outlet end of the 1, 4-butanediol reactor 31 is connected with a catalyst recoverer 35, and the catalyst recoverer 35 is connected with the rectifying device 4.
In the using process, adding a catalyst into the 1, 4-butanediol reactor 31 through the catalyst feeding structure 33, and conveying 1, 4-butynediol into the 1, 4-butanediol reactor 31 through the feeding pump 32; in the process of conveying hydrogen from the hydrogen tank 34 to the 1, 4-butanediol reactor 31, the hydrogen firstly passes through the micro-interface generator 36 at the bottom end, the micro-interface generator 36 converts the pressure energy of the hydrogen into bubble surface energy and transfers the bubble surface energy to the hydrogen, so that the hydrogen is crushed to form micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, the contact area of the hydrogen and the 1, 4-butynediol is increased, the thickness of a liquid film is reduced, and the contact resistance of the hydrogen and the 1, 4-butynediol is reduced; micron-sized bubbles on the hydrogen are discharged from the micro-interface generator 36, enter the 1, 4-butanediol reactor 31, meet the 1, 4-butynediol and the catalyst, and are fully mixed to form a gas-liquid emulsion under the action of a stirrer in the 1, 4-butanediol reactor 31, so that the reaction is more complete, and finally the crude 1, 4-butanediol with the mass concentration of 37-45% is obtained. In the present invention, the top of the 1, 4-butanediol reactor 31 is provided with an adjusting valve, and the pressure inside the 1, 4-butanediol reactor 31 is controlled to be maintained at 0.2 to 3 MPa.
It is understood that the micro-interface generator 36 of the present invention can also be used in other multi-phase reactions, such as multi-phase fluid formed by micro-scale particles, micro-nano-scale particles, micro-bubble fluid, micro-bubble micro-emulsion fluid, micro-flow, micro-dispersed fluid, two-phase micro-mixed fluid, micro-turbulent fluid, micro-bubble fluid, micro-nano-bubble micro-bubble fluid, micro-nano-scale bubble fluid, micro-bubble fluid, micro-nano-micro-emulsion fluid, micro-bubble fluid, micro-dispersed fluid, micro-turbulent fluid, micro-bubble fluid, micro-nano-bubble fluid, micro-nano-bubble fluid, micro-nano-micro-scale particles, etc. by using micro-mixing, micro-fluidization, ultra-micro-fluidization, micro-bubble fermentation, micro-bubble bubbling, or multiphase fluid (micro interface fluid for short) formed by micro-nano-scale particles, thereby effectively increasing the phase boundary mass transfer area between a gas phase and/or a liquid phase and/or a solid phase in the reaction process.
Referring to fig. 2, in the present invention, the catalyst feeding structure 33 includes an inverted cone shaped feed hopper 331 for storing the solid catalyst. Support plates 334 are arranged on two opposite sides of the middle lower part of the feed hopper 331, air cylinders 33 are arranged on the support plates 334, and the air cylinders 33 are connected with a feed baffle 332 extending into the feed hopper 331; certainly, the feeding hopper 331 is located above the supporting plate 334 and is provided with a long hole corresponding to the feeding baffle 332, so that the feeding baffle 332 can move smoothly in the long hole; when the system is operating, the air cylinder 33 can control the length of the two feed baffles 332 entering the feed hopper 331, thereby controlling the flow of catalyst.
Referring to fig. 3, the catalyst recoverer 35 includes a thrust plate 351 and a compression plate 352 connected to both ends of the frame, the filter structure is connected between the thrust plate 351 and the compression plate 352, and the compression plate 352 is connected to the compression structure. The filtering structure comprises a plurality of filtering plates 353, the middle parts of the filtering plates 353 are recessed inwards, a filtering chamber is formed between every two filtering plates 353, and the water guide groove can enable coarse 1, 4-butanediol to be quickly and uniformly injected into the filtering chamber; the filter plate 353 located between the pressing plate 352 and the thrust plate 351 is pressed by the pressing structure to ensure that the coarse 1, 4-butanediol with pressure is subjected to pressure filtration in the filter chamber, and meanwhile, the solid catalyst in the coarse 1, 4-butanediol is left outside the filter plate 353 to form a filter cake under the pressing force.
In the working process, an independent filter chamber is formed between every two filter plates 353, crude 1, 4-butanediol enters the filter chamber from the water guide groove under the action of the water pump, the solid catalyst is stored on one side of each filter plate 353, and the crude 1, 4-butanediol finally flows into the outlet and enters the rectifying device 4. When the surface of the filter layer on one side of the filter plate 353 reaches a certain solid thickness, backwashing can be carried out, the water inlet direction is changed into the water outlet direction, and the backwashing solid catalyst is discharged into the catalyst collecting system, so that the waste of the residual catalyst is avoided, and meanwhile, the catalyst is prevented from influencing the normal production of a subsequent system.
The rectifying device 4 and the rectifying device 4 are mainly used for rectifying the crude 1, 4-butanediol to obtain a high-purity 1, 4-butanediol product. The rectifying apparatus 4 includes a concentration column, a salt column, a low-boiling column and a high-boiling column. In the using process, crude 1, 4-butanediol enters a concentration tower from the middle part of the concentration tower, the crude 1, 4-butanediol with the mass concentration of 37-45% is dehydrated and concentrated to the concentration of more than or equal to 94% under the pressure of 60-90 KPa, most of water, butanol and other byproducts are primarily separated from the crude 1, 4-butanediol, after the 1, 4-butanediol with the concentration of more than or equal to 94% is led out by the concentration tower, the impurities are removed through a salt tower with the internal vacuum pressure of less than or equal to 15KPa, a low-boiling tower and a high-boiling tower in sequence, the salt tower mainly removes metal salts added in the hydrogenation process of the 1, 4-butanediol, generated heavy components, tar and trace water, the low-boiling tower and the high-boiling tower remove impurities with high and low boiling points relative to the 1, 4-butanediol, and the high-purity 1, 4-. In the invention, the top of the concentration tower is also provided with a cooler for controlling the temperature at the top of the concentration tower; a reflux pump is also arranged on the reflux pipeline at the top of the concentration tower and used for controlling the reflux quantity at the top of the tower.
Since the rectifying device 4 is a mature device in the prior art, even though the device is not specifically described in the present invention, a person skilled in the art can also purify the crude 1, 4-butanediol according to the prior art, and therefore, the rectifying device 4 is not described in detail in the present invention.
The intelligent control device is electrically connected with the reaction parameter controllers in the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectifying device; the intelligent control device comprises a strategy setting unit, a parameter control unit and a model setting unit; the strategy setting unit is used for setting the range of the reaction parameters and the learning strategy; the parameter control unit is used for controlling the reaction parameters of the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectification device according to a preset strategy and the range of the reaction parameters; the model setting unit is used for establishing a correlation model of the reaction parameters and the target object parameters.
For example, the pressure of the 1, 4-butanediol reactor is 0.2-3MPa, the internal pressure of the concentration tower is 60-90 KPa, and the internal vacuum pressure of the salt tower, the low-boiling tower and the high-boiling tower is less than or equal to 15 KPaA. The strategy setting unit sets the ranges of the three parameters to be 0.2, 0.55, 0.9, 1.25, 1.6, 1.95, 2.3, 2.65 and 3MPa of the 1, 4-butanediol reactor pressure, the internal pressure of the concentration tower to be 60, 63, 70, 75, 78, 80, 83, 85 and 90KPa, the internal vacuum pressure of the salt tower, the low-boiling tower and the high-boiling tower to be 15, 14.5, 14, 13.6, 13.2, 13, 12.8, 12.4 and 12KPaA, of course, the three parameters are not limited in the actual operation process, and the range of each parameter is not limited to the characteristic values; the parameter control unit takes a value from the range of each parameter, combines a plurality of taken parameter values into a reaction condition, and simultaneously carries out reaction according to the reaction condition until the characteristic values of all the parameters are traversed, and each reaction condition records a reaction result; the model setting unit selects the best reaction result from all the reaction results, and finds the reaction condition corresponding to the reaction result, i.e. finds the characteristic value of each reaction parameter, and controls or adjusts the characteristic value through the controller (e.g. temperature controller, pressure controller, flow controller, etc.) of each reaction parameter.
In the invention, the catalyst recoverer can be controlled by the intelligent control device to realize intelligent operation. The back flushing time of the crude 1, 4-butanediol can also be controlled by an automatic intelligent control device.
By using the strengthening system, the invention also provides a process for preparing 1, 4-butanediol from acetylene and formaldehyde, which comprises the following steps:
step one
Introducing methanol into a methanol vaporizer for gasification, and then mixing the gasified methanol with fresh air to obtain mixed gas;
adding an iron-molybdenum catalyst into a formaldehyde reactor, and introducing the mixed gas into the formaldehyde reactor for reaction to obtain formaldehyde gas;
introducing formaldehyde gas into water to form a formaldehyde water solution with the volume concentration of 37-52%.
Step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the aqueous formaldehyde solution prepared in the first step to obtain a crude 1, 4-butynediol feed liquid;
rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain the 1, 4-butynediol.
Step three
Introducing the hydrogen in the hydrogen tank 34 and the 1, 4-butynediol prepared in the second step into a micro-interface generator 36; after the micro-interface generator 36 crushes the hydrogen big bubbles into micron-sized bubbles, the micron-sized bubbles are fully and uniformly mixed with the 1, 4-butynediol to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor 31 into which a Raney nickel catalyst is added for reaction, and continuously stirring in the reaction process; obtaining crude 1, 4-butanediol with the mass concentration of 37-45%;
in the reaction process, the pressure of the 1, 4-butanediol reactor 31 is 0.2-3 MPa.
Step four
Introducing the crude 1, 4-butanediol prepared in the third step into a concentration tower, concentrating the concentration of the crude 1, 4-butanediol to be more than or equal to 94% under the pressure of 60-90 KPa, and separating out most of water, butanol and other byproducts contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure less than or equal to 15KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol.
In order to verify the system and process of the process for the preparation of 1, 4-butanediol from acetylene and formaldehyde according to the invention, the invention is provided with the following examples.
Example 1
Step one
Introducing methanol into a methanol vaporizer for gasification, and simultaneously adding an iron-molybdenum catalyst into a formaldehyde reactor; mixing the gasified methanol with fresh air, and introducing the mixture into a formaldehyde reactor for reaction to obtain formaldehyde gas;
formaldehyde gas was passed into water to form a 38% by volume aqueous formaldehyde solution.
Step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the aqueous formaldehyde solution prepared in the first step to obtain a crude 1, 4-butynediol feed liquid;
rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain the 1, 4-butynediol.
Step three
Introducing the hydrogen in the hydrogen tank 34 and the 1, 4-butynediol prepared in the second step into a micro-interface generator 36; after the micro-interface generator 36 crushes the hydrogen big bubbles into micron-sized bubbles, the micron-sized bubbles are fully and uniformly mixed with the 1, 4-butynediol to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor 31 into which a Raney nickel catalyst is added for reaction, and continuously stirring in the reaction process; obtaining crude 1, 4-butanediol with the mass concentration of 38%;
in the reaction process, the pressure of the 1, 4-butanediol reactor 31 was 0.2 MPa.
Step four
Introducing the crude 1, 4-butanediol obtained in the third step into a concentration tower, concentrating the concentration of the crude 1, 4-butanediol to 95% under the pressure of 65KPa, and separating most of water and butanol and other byproducts contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure of 15KPa, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.
Example 2
Step one
Introducing methanol into a methanol vaporizer for gasification, and simultaneously adding an iron-molybdenum catalyst into a formaldehyde reactor; mixing the gasified methanol with fresh air, and introducing the mixture into a formaldehyde reactor for reaction to obtain formaldehyde gas;
formaldehyde gas was passed into water to form a 43% by volume aqueous formaldehyde solution.
Step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the aqueous formaldehyde solution prepared in the first step to obtain a crude 1, 4-butynediol feed liquid;
rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain the 1, 4-butynediol.
Step three
Introducing the hydrogen in the hydrogen tank 34 and the 1, 4-butynediol prepared in the second step into a micro-interface generator 36; after the micro-interface generator 36 crushes the hydrogen big bubbles into micron-sized bubbles, the micron-sized bubbles are fully and uniformly mixed with the 1, 4-butynediol to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor 31 into which a Raney nickel catalyst is added for reaction, and continuously stirring in the reaction process; obtaining crude 1, 4-butanediol with the mass concentration of 40%;
in the reaction process, the pressure of the 1, 4-butanediol reactor 31 was 1.6 MPa.
Step four
Introducing the crude 1, 4-butanediol obtained in the third step into a concentration tower, concentrating the concentration of the crude 1, 4-butanediol to 95.3% under the pressure of 73KPa, and separating out most of water, butanol and other byproducts contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure of 14KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.
Example 3
Step one
Introducing methanol into a methanol vaporizer for gasification, and simultaneously adding an iron-molybdenum catalyst into a formaldehyde reactor; mixing the gasified methanol with fresh air, and introducing the mixture into a formaldehyde reactor for reaction to obtain formaldehyde gas;
introducing formaldehyde gas into water to form 50% formaldehyde water solution.
Step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the aqueous formaldehyde solution prepared in the first step to obtain a crude 1, 4-butynediol feed liquid;
rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain the 1, 4-butynediol.
Step three
Introducing the hydrogen in the hydrogen tank 34 and the 1, 4-butynediol prepared in the second step into a micro-interface generator 36; after the micro-interface generator 36 crushes the hydrogen big bubbles into micron-sized bubbles, the micron-sized bubbles are fully and uniformly mixed with the 1, 4-butynediol to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor 31 into which a Raney nickel catalyst is added for reaction, and continuously stirring in the reaction process; obtaining crude 1, 4-butanediol with the mass concentration of 42%;
in the reaction process, the pressure of the 1, 4-butanediol reactor 31 is 3 MPa.
Step four
Introducing the crude 1, 4-butanediol obtained in the third step into a concentration tower, concentrating the concentration of the crude 1, 4-butanediol to 96% under the pressure of 88KPa, and separating most of water, butanol and other byproducts contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure of 13KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.
The inventor also carries out other embodiments, which are not listed one by one, and the experimental data of other embodiments are shown in the table one.
TABLE Experimental data for several other examples
The 1, 4-butanediol produced in the above examples was produced in a large amount, and the reaction was relatively sufficient.
In summary, the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectification device are correspondingly connected in sequence, wherein the outlet end of the 1, 4-butanediol reactor is connected with the catalyst recoverer, and the confluence of the feed pump and the hydrogen tank is also provided with the micro-interface generator; the micro-interface generator can crush hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1mm, and simultaneously, the micron-sized bubbles and 1, 4-butynediol are fully mixed to form a gas-liquid emulsion, so that the contact area of the hydrogen and the 1, 4-butynediol is increased, the hydrogen and the 1, 4-butynediol are mixed more uniformly and react more fully, and the amount of generated 1, 4-butanediol is more; the catalyst recoverer can collect the residual catalyst, so that waste is avoided, and the catalyst is prevented from influencing the normal production of a subsequent system; the invention is also provided with an intelligent control device to realize intelligent selection of optimal reaction conditions, so that the reaction is efficiently carried out, and time and labor waste caused by manual operation are avoided. In conclusion, the beneficial effects of the invention are as follows: the reaction in the hydrogenation section is more sufficient, the yield of the 1, 4-butanediol is higher, the waste of catalyst raw materials is avoided, the production cost is reduced, and the intelligent operation is realized.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The strengthening system for preparing 1, 4-butanediol from acetylene and formaldehyde is characterized by comprising a formaldehyde preparation device, a 1, 4-butynediol preparation device, a 1, 4-butanediol preparation device and a rectification device which are correspondingly connected in sequence; the intelligent control device is also included;
the 1, 4-butanediol preparation device comprises a 1, 4-butanediol reactor, wherein a micro-interface generator is arranged at the bottom end inside the 1, 4-butanediol reactor and is used for crushing reactant hydrogen to ensure that the diameter of micron-sized bubbles formed by crushing is more than or equal to 1 mu m and less than 1mm so as to be mixed with an intermediate product 1, 4-butynediol to form a gas-liquid emulsion;
the inlet end of the 1, 4-butanediol reactor is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, the hydrogen tank is connected with the micro-interface generator, and the feeding pump is connected with the 1, 4-butynediol preparation device; the catalyst feeding structure comprises a feeding hopper, support plates are arranged on two opposite sides of the middle lower part of the feeding hopper, air cylinders are arranged on the support plates, and the air cylinders are connected with a feeding baffle inside the feeding hopper;
the outlet end of the 1, 4-butanediol reactor is connected with a catalyst recoverer, and the catalyst recoverer is connected with the rectifying device;
the intelligent control device is electrically connected with the reaction parameter controllers in the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectifying device; the intelligent control device comprises a strategy setting unit, a parameter control unit and a model setting unit; the strategy setting unit is used for setting the range of the reaction parameters and the learning strategy; the parameter control unit is used for controlling the reaction parameters of the formaldehyde preparation device, the 1, 4-butynediol preparation device, the 1, 4-butanediol preparation device and the rectification device according to a preset strategy and the range of the reaction parameters; the model setting unit is used for establishing a correlation model of the reaction parameters and the target object parameters.
2. The strengthening system for preparing 1, 4-butanediol by acetylene and formaldehyde according to claim 1, wherein the catalyst recoverer comprises a thrust plate and a compression plate which are connected to two ends of a frame, a filtering structure is connected between the thrust plate and the compression plate, and the compression plate is connected with the compression structure; the filter structure comprises a plurality of filter plates, the middle parts of the filter plates are recessed inwards, and every two filter plates form a filter chamber.
3. The system for enhancing the production of 1, 4-butanediol from acetylene and formaldehyde according to claim 2, wherein the formaldehyde production unit comprises a formaldehyde reactor, a methanol vaporizer, a formaldehyde absorption tower and a circulating fan; the 1, 4-butynediol preparation device comprises a water washing tower, a 1, 4-butynediol reactor and a concentrator; the rectification device comprises a concentration tower, a salt tower, a low-boiling tower and a high-boiling tower.
4. The system for strengthening the preparation of 1, 4-butanediol by acetylene and formaldehyde according to claim 3, wherein the top of the 1, 4-butanediol reactor is provided with a regulating valve for controlling the pressure of the 1, 4-butanediol reactor to be maintained at 0.2-3 MPa.
5. The system for enhancing the preparation of 1, 4-butanediol from acetylene and formaldehyde as claimed in claim 3, wherein the top of the concentration tower is further provided with a cooler for controlling the temperature of the top of the concentration tower, and the return line at the top of the concentration tower is further provided with a reflux pump for controlling the reflux amount at the top of the concentration tower.
6. The enhancement system for preparing 1, 4-butanediol from acetylene and formaldehyde according to claim 5, wherein the working pressure inside the concentration tower is 60-90 KPa.
7. The enhancement system for preparing 1, 4-butanediol from acetylene and formaldehyde as claimed in claim 6, wherein the concentration mass concentration of the concentration tower to crude 1, 4-butanediol is not less than 94%.
8. The enhancement system for preparing 1, 4-butanediol by acetylene and formaldehyde according to claim 3, wherein the vacuum pressure inside the salt tower, the low-boiling tower and the high-boiling tower is less than or equal to 15 KPaA.
9. The system for enhancing the preparation of 1, 4-butanediol from acetylene and formaldehyde according to claim 1, wherein the catalyst recoverer is connected to the intelligent control device.
10. A process for preparing 1, 4-butanediol using the reinforcement system of any one of claims 1-9, comprising the steps of:
step one
Introducing methanol into a methanol vaporizer for gasification, and then mixing the gasified methanol with fresh air to obtain mixed gas;
adding an iron-molybdenum catalyst into a formaldehyde reactor, and introducing the mixed gas into the formaldehyde reactor for reaction to obtain formaldehyde gas;
introducing the formaldehyde gas into water to form a formaldehyde water solution with the volume concentration of 37-52%;
step two
Adding a copper bismuth catalyst into a 1, 4-butynediol reactor, and then introducing acetylene gas and the formaldehyde aqueous solution to obtain a crude 1, 4-butynediol feed liquid;
rectifying the crude 1, 4-butynediol feed liquid to remove formaldehyde mixed therein, and then carrying out ion removal to obtain 1, 4-butynediol;
step three
Introducing hydrogen gas in a hydrogen tank and the 1, 4-butynediol into a micro-interface generator; the micro-interface generator crushes the large hydrogen bubbles into micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and then the micron-sized bubbles and the 1, 4-butynediol are fully mixed to form a gas-liquid emulsion;
introducing the gas-liquid emulsion into a 1, 4-butanediol reactor added with a Raney nickel catalyst for reaction to obtain crude 1, 4-butanediol with the mass concentration of 37-45%;
in the reaction process, the pressure of the 1, 4-butanediol reactor is 0.2-3 MPa;
step four
Introducing the crude 1, 4-butanediol into a concentration tower, enabling the mass concentration of the crude 1, 4-butanediol to be more than or equal to 94% under the pressure of 60-90 KPa, and simultaneously separating water and butanol contained in the crude 1, 4-butanediol;
and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure less than or equal to 15KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after the impurities are removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910840683.4A CN112457161A (en) | 2019-09-06 | 2019-09-06 | Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910840683.4A CN112457161A (en) | 2019-09-06 | 2019-09-06 | Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112457161A true CN112457161A (en) | 2021-03-09 |
Family
ID=74806899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910840683.4A Pending CN112457161A (en) | 2019-09-06 | 2019-09-06 | Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457161A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373118A (en) * | 2002-03-12 | 2002-10-09 | 扬子石油化工股份有限公司 | Intelligent control method for reaction temp in liquid-phase oxidizing reactor of p-xylene |
| CN1417176A (en) * | 2002-12-10 | 2003-05-14 | 扬子石油化工股份有限公司 | Intelligent control method for ethylene rectifying tower of ethylene equipment |
| CN106397129A (en) * | 2016-11-24 | 2017-02-15 | 查都（上海）科技有限公司 | System and process for continuously producing 2-butene-1,4-diol and co-producing 1,4-butanediol through hydrogenation of 1,4-butynediol |
| CN107778138A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method that Isosorbide-5-Nitrae butynediols two-stage hydrogenation prepares Isosorbide-5-Nitrae butanediol |
| CN109651110A (en) * | 2019-01-17 | 2019-04-19 | 新疆天智辰业化工有限公司 | A kind of production method of high-purity 1,4- butanediol |
| CN109678660A (en) * | 2019-02-15 | 2019-04-26 | 陕西陕化煤化工集团有限公司 | A kind of improvement technique producing 1,4-butanediol |
-
2019
- 2019-09-06 CN CN201910840683.4A patent/CN112457161A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373118A (en) * | 2002-03-12 | 2002-10-09 | 扬子石油化工股份有限公司 | Intelligent control method for reaction temp in liquid-phase oxidizing reactor of p-xylene |
| CN1417176A (en) * | 2002-12-10 | 2003-05-14 | 扬子石油化工股份有限公司 | Intelligent control method for ethylene rectifying tower of ethylene equipment |
| CN107778138A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | A kind of method that Isosorbide-5-Nitrae butynediols two-stage hydrogenation prepares Isosorbide-5-Nitrae butanediol |
| CN106397129A (en) * | 2016-11-24 | 2017-02-15 | 查都（上海）科技有限公司 | System and process for continuously producing 2-butene-1,4-diol and co-producing 1,4-butanediol through hydrogenation of 1,4-butynediol |
| CN109651110A (en) * | 2019-01-17 | 2019-04-19 | 新疆天智辰业化工有限公司 | A kind of production method of high-purity 1,4- butanediol |
| CN109678660A (en) * | 2019-02-15 | 2019-04-26 | 陕西陕化煤化工集团有限公司 | A kind of improvement technique producing 1,4-butanediol |
Non-Patent Citations (1)
| Title |
|---|
| 张志炳等: "多相反应体系的微界面强化简述", 《化工学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103159703B (en) | Method of continuously producing epichlorohydrin by directly epoxidizing chloropropene | |
| CN101735182B (en) | Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride | |
| WO2023165110A1 (en) | Micro-interface preparation system and method for 1,4-butanediol | |
| CN108821971A (en) | A kind of cyclopentyl acetate synthesis technology | |
| CN106278836A (en) | Intermediate concentration formaldehyde and the apparatus and method of methylal synthesis polymethoxy dimethyl ether | |
| CN111606790B (en) | System and method for continuously producing high-quality high-selectivity benzaldehyde and benzoic acid by using jet loop reactor | |
| CN113750941B (en) | Production equipment and production method of ethyl acetate | |
| CN212128025U (en) | Reinforcing system for preparing 1, 4-butanediol from acetylene and formaldehyde | |
| CN111217686A (en) | Preparation method of n-valeraldehyde and special Venturi ejector | |
| CN109438283A (en) | A kind of synthetic method and device of β-aminopropionitrile | |
| CN112457161A (en) | Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde | |
| CN103896977A (en) | Method for producing vinyl alkoxy silane and device thereof | |
| CN211487670U (en) | Device for preparing pivalic acid | |
| CN213388443U (en) | Reinforcing system for preparing 1, 4-butanediol from butadiene and acetic acid | |
| WO2023072047A1 (en) | Method for preparing succinic anhydride by means of hydrogenation of maleic anhydride and production system | |
| CN108273452B (en) | Grease epoxidation reactor | |
| CN112457156A (en) | Reinforcing system and process for preparing 1, 4-butanediol from butadiene and acetic acid | |
| CN202860529U (en) | Reaction device for producing cyclohexene by partial hydrogenation of benzene | |
| CN211394489U (en) | Starchy raw material liquefaction production equipment | |
| CN212818270U (en) | Extraction device for refining and purifying vinyl ethers | |
| CN108121387A (en) | A kind of automatic driving of exothermal reaction process and optimal control method | |
| CN113600109A (en) | Micro-interface reaction system and method for preparing acetic acid through methanol carbonylation | |
| CN111574346A (en) | External micro-interface strengthening system and method for preparing cyclohexanone by esterification method | |
| CN214974046U (en) | Loop reactor with high-efficient venturi sprayer | |
| CN218077800U (en) | Novel diethyl carbonate reaction device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210309 |