CN110668917A - Synthesis device and synthesis method of 1, 3-butanediol - Google Patents
Synthesis device and synthesis method of 1, 3-butanediol Download PDFInfo
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- CN110668917A CN110668917A CN201911051513.4A CN201911051513A CN110668917A CN 110668917 A CN110668917 A CN 110668917A CN 201911051513 A CN201911051513 A CN 201911051513A CN 110668917 A CN110668917 A CN 110668917A
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 235000019437 butane-1,3-diol Nutrition 0.000 title claims abstract description 66
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 51
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims abstract description 44
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000006482 condensation reaction Methods 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000012043 crude product Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 125000000129 anionic group Chemical group 0.000 claims abstract description 3
- 238000010992 reflux Methods 0.000 claims description 56
- 238000000066 reactive distillation Methods 0.000 claims description 54
- 239000007791 liquid phase Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AXPZIVKEZRHGAS-UHFFFAOYSA-N 3-benzyl-5-[(2-nitrophenoxy)methyl]oxolan-2-one Chemical compound [O-][N+](=O)C1=CC=CC=C1OCC1OC(=O)C(CC=2C=CC=CC=2)C1 AXPZIVKEZRHGAS-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- C07C29/15—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 oxides of carbon exclusively
- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
-
- 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
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis device and a synthesis method of 1, 3-butanediol, wherein an acetaldehyde aqueous solution is subjected to condensation reaction in a reaction rectifying tower loaded with alkaline anionic resin, acetaldehyde fractionated from the top of the tower is returned to a raw material tank for recycling, and 3-hydroxybutyraldehyde fractionated from the bottom of the tower directly enters a tower reactor for hydrogenation reaction; carrying out hydrogenation reaction on 3-hydroxybutyraldehyde and hydrogen in a tower reactor, recycling the hydrogen at the tower top, and feeding the 1, 3-butanediol crude product obtained at the tower bottom into a vacuum refining system; the 1, 3-butanediol crude product enters a light component removal tower to remove light components, then enters a heavy component removal tower, and a 1, 3-butanediol product with the purity of more than 99.6 percent and no peculiar smell is obtained at the tower top. The invention has the characteristics of short flow, low energy consumption, less pollution and capability of realizing continuous production.
Description
Technical Field
The invention relates to the technical field of chemical reaction separation, in particular to a device and a method for synthesizing 1, 3-butanediol.
Background
1, 3-butanediol has good hygroscopicity and water solubility, no odor and low toxicity, so that the butanediol-containing water-soluble organic silicon dioxide is widely applied to cosmetics, medicines and high-grade building material products. However, the current domestic 1, 3-butanediol product almost completely depends on foreign import, and has no own industrialized device at home. With the popularization of the application range of the 1, 3-butanediol, the domestic research on the 1, 3-butanediol is increasing. At present, acetaldehyde is mostly used as a raw material in the research of a synthetic route of 1, 3-butanediol, and a specific route is that the acetaldehyde is condensed to generate 3-hydroxybutyraldehyde, and then the 3-hydroxybutyraldehyde is hydrogenated to generate the 1, 3-butanediol. The route is also the route for producing the 1, 3-butanediol at present abroad.
For example, the research of the liquid-phase aldol condensation reaction of acetaldehyde by the university of Tongji for many years, and a series of optimization researches are carried out on the reaction temperature, the PH value and the alkaline condition of the system.
At present, the patent also reports various methods for preparing hydroxyaldehydes and 1, 3-butanediol: canadian patent CN107849522A provides a non-naturally occurring microorganism having a 1,3-BDO pathway; chinese patent CN105585448A proposes that water is used as a solvent to optimize an acetaldehyde condensation reaction to obtain 3-hydroxybutyraldehyde, and then the 3-hydroxybutyraldehyde is injected into an autoclave to react to obtain 1, 3-butanediol; chinese patent CN206396080U provides a 1, 3-butanediol condensation reaction apparatus, which comprises a condensation reactor, a hydrogenation reactor and a first rectification tower. Patent 105037119A proposes a plate-type reactive distillation column for acetaldehyde condensation. Chinese patent CN109422624A shows that the yield and purity of 1, 3-butanediol prepared by the mainstream production process of 1, 3-butanediol are not ideal and have pungent smell, so that the production process of 1, 3-butanediol is optimized by adopting a fixed bed reactor and a supported nickel hydrogenation catalyst. Although the fixed bed reactor has less back mixing than the tank reactor, the back mixing still exists and the flow is complex. In addition, the acetaldehyde condensation section of the above patents has a large amount of salt generated and is difficult to handle.
Disclosure of Invention
The invention provides a device and a method for synthesizing 1, 3-butanediol, aiming at solving the technical problems.
The invention is realized according to the following technical scheme.
A1, 3-butanediol synthesis device comprises a condensation reaction system, a hydrogenation reaction system and a vacuum refining system which are sequentially connected through pipelines; the condensation reaction system adopts a reaction rectifying tower loaded with alkaline anion resin; the hydrogenation reaction system adopts a tower type hydrogenation reactor; the vacuum refining system comprises a light component removal tower and a heavy component removal tower.
Further, the top of the reactive distillation tower is connected with a condenser at the top of the reactive distillation tower through a pipeline, and the lower part of the reactive distillation tower is connected with a reboiler of the reactive distillation tower and a tower type hydrogenation reactor through a pipeline; the tower top condenser of the reactive distillation tower is connected with a reflux tank of the reactive distillation tower through a pipeline, and the reflux tank of the reactive distillation tower is connected with the reactive distillation tower through a pipeline;
the tower top of the tower type hydrogenation reactor is connected with the lower part of the tower type hydrogenation reactor through a pipeline, and the tower kettle of the tower type hydrogenation reactor is connected with the light component removal tower through a pipeline;
the top of the light component removal tower is connected with a condenser at the top of the light component removal tower through a pipeline, and the lower part of the light component removal tower is connected with a reboiler of the light component removal tower and a heavy component removal tower through pipelines; the condenser at the top of the light component removal tower is connected with a light component removal tower reflux tank through a pipeline, and the light component removal tower reflux tank is connected with the light component removal tower through a pipeline;
the top of the heavy component removal tower is connected with a tower top condenser of the heavy component removal tower through a pipeline, and the lower part of the heavy component removal tower is connected with a reboiler of the heavy component removal tower through a pipeline; the tower top condenser of the de-heavy tower is connected with a reflux tank of the de-heavy tower through a pipeline, and the reflux tank of the de-heavy tower is connected with the de-heavy tower through a pipeline;
and the tops of the light component removal tower and the heavy component removal tower are respectively connected with a light component removal tower vacuum-pumping pipeline and a heavy component removal tower vacuum-pumping pipeline.
Further, the operating temperature of the reactive distillation column is-5 ~ 50 ℃.
Further, the operation pressure of the tower hydrogenation reactor is 2.0 ~ 6.0.0 MpaA absolute pressure, and the operation temperature is 50 ~ 120 ℃.
Further, the operating pressure of the light ends removal column is 0.03 ~ 0.08.08 MpaA.
Further, the operating pressure of the de-heaving column is 0.0002 ~ 0.005.005 MpaA.
A method for synthesizing 1, 3-butanediol comprises the following steps:
s1, enabling an acetaldehyde aqueous solution to enter a reaction rectifying tower, and carrying out condensation reaction under the catalytic action of a basic anion resin catalyst loaded in the tower; condensing the light components at the top of the reactive distillation column which are not completely reacted into light components at the top of the reactive distillation column after the condensation of the reactive distillation column through a condenser at the top of the reactive distillation column, and then feeding the light components at the top of the reactive distillation column into a reflux tank of the reactive distillation column, wherein one part of the liquid phase in the reflux tank of the reactive distillation column is used as the reflux liquid phase of the reactive distillation column to reflux the reactive distillation column, and the other part is recycled acetaldehyde; the tower bottom of the reactive distillation tower is a tower bottom heavy component of the reactive distillation tower rich in 3-hydroxybutyraldehyde, one part of the heavy component is gasified by a reboiler of the reactive distillation tower and then is turned into the heavy component gasified by the reboiler to return to the tower, and the other part of the heavy component is used as a raw material of the 3-hydroxybutyraldehyde of the tower hydrogenation reactor and enters the tower hydrogenation reactor;
s2: carrying out hydrogenation reaction on 3-hydroxybutyraldehyde and total hydrogen in a tower type hydrogenation reactor, mixing circulating hydrogen at the tower top with supplemented fresh hydrogen, and then feeding the mixture into the tower type hydrogenation reactor, and obtaining a reaction product crude 1, 3-butanediol at the tower bottom; feeding the crude 1, 3-butanediol of the reaction product into a lightness-removing tower;
s3, condensing the light components at the top of the light component removal tower into condensed light components at the top of the light component removal tower through a condenser at the top of the light component removal tower, and then feeding the condensed light components into a light component removal tower reflux tank, wherein one part of the liquid phase in the light component removal tower reflux tank is used as the light component removal tower reflux liquid phase reflux light component removal tower, and the other part is extracted as the light components; the tower kettle of the light component removal tower is a heavy component of the tower kettle of the light component removal tower rich in 1, 3-butanediol, one part of the heavy component removal tower is gasified by a reboiler of the light component removal tower to form the heavy component of the tower kettle of the light component removal tower gasified by the reboiler and returns to the tower, and the other part of the heavy component removal tower is used as a raw product of the 1, 3-butanediol with the light component removed from the raw material fed into the heavy component removal tower and enters the heavy component removal tower;
s4: a light component at the top of the heavy component removal tower is gas-phase 1, 3-butanediol, the gas-phase 1, 3-butanediol is condensed into a condensed heavy component removal tower through a condenser at the top of the heavy component removal tower and then enters a heavy component removal tower reflux tank, a part of a liquid phase in the heavy component removal tower reflux tank is returned to the heavy component removal tower as a heavy component removal tower reflux liquid phase, and a part of the liquid phase is extracted as a 1, 3-butanediol product; and the tower kettle of the heavy component removal tower is heavy components of the tower kettle of the heavy component removal tower, one part of the heavy components are gasified by a reboiler of the heavy component removal tower and then become the heavy components of the heavy component removal tower gasified by the reboiler to return to the tower, and the other part of the heavy components are taken out as heavy component streams.
Further, the operating temperature of the reactive distillation column is-5 ~ 50 ℃.
Further, the operation pressure of the tower hydrogenation reactor is 2.0 ~ 6.0.0 MpaA absolute pressure, and the operation temperature is 50 ~ 120 ℃.
Further, the operating pressure of the light component removal tower is 0.03 ~ 0.08.08 MpaA, and the operating pressure of the heavy component removal tower is 0.0002 ~ 0.005.005 MpaA.
The present invention obtains the following advantageous effects.
According to the invention, a high-quality 1, 3-butanediol product with the purity of more than 99.6% and no peculiar smell is obtained by adopting a reaction rectifying tower loaded with alkaline anion resin, a tower reactor and a vacuum refining system. The method has the characteristics of short flow, low energy consumption, less pollution and capability of realizing continuous production. Therefore, the method has great implementation value, social benefit, environmental benefit and economic benefit.
Drawings
FIG. 1 is a schematic diagram of the process for synthesizing and refining 1, 3-butanediol of the present invention.
Wherein, 1, acetaldehyde aqueous solution; 2. reacting light components at the top of the rectifying tower; 3. condensing the light components on the top of the reaction rectifying tower; 4. refluxing liquid phase in the reactive distillation tower; 5. recycling acetaldehyde; 6. heavy components in the tower kettle of the reactive distillation tower; 7. a heavy component vaporized by a reboiler; 8.3-hydroxybutyraldehyde; 9. circulating hydrogen; 10. fresh hydrogen gas; 11. total hydrogen; 12. crude 1, 3-butanediol; 13. light components at the top of the light component removal tower; 14. condensing light components at the top of the lightness-removing tower; 15. refluxing liquid phase in the light component removal tower; 16. light components; 17. heavy components in the tower kettle of the light component removal tower; 18. heavy components in a tower kettle of the light component removal tower gasified by a reboiler; 19. removing light components of the 1, 3-butanediol crude product; 20. removing light components at the top of the heavy tower; 21. the condensed components of the de-weighting tower; 22. refluxing the liquid phase in the de-heavy tower; 1, 3-butanediol product; 24. heavy components in a tower kettle of the de-heavy tower; 25. heavy components in a heavy component removal tower gasified by a reboiler; 26. a heavies stream; 27. a reactive distillation column; 28. a condenser at the top of the reaction rectifying tower; 29. a reflux tank of the reaction rectifying tower; 30. a reboiler at the tower bottom of the reactive distillation tower; 31. a tower hydrogenation reactor; 32. a light component removal tower; 33. a condenser at the top of the light component removal tower; 34. a light component removal tower reflux tank; 35. a light component removal tower reboiler; 36. a de-weighting tower; 37. a tower top condenser of the de-heavy tower; 38. a reflux tank of the de-weighting tower; 39. a de-heaving column reboiler; 40. vacuumizing a pipeline of the light component removal tower; 41. and (4) vacuumizing a pipeline of the de-weighting tower.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
As shown in fig. 1, a 1, 3-butanediol synthesis apparatus comprises a condensation reaction system, a hydrogenation reaction system and a vacuum refining system which are connected in sequence by pipelines; the condensation reaction system adopts a reaction rectifying tower 27 loaded with basic anion resin; the hydrogenation reaction system adopts a tower type hydrogenation reactor 31; the vacuum refining system includes a light ends removal column 32 and a heavy ends removal column 36.
The top of the reaction rectifying tower 27 is connected with a reaction rectifying tower top condenser 28 through a pipeline, and the lower part of the reaction rectifying tower 27 is connected with a reaction rectifying tower reboiler 30 and a tower type hydrogenation reactor 31 through pipelines; the reaction rectifying tower top condenser 28 is connected with a reaction rectifying tower reflux tank 29 through a pipeline, and the reaction rectifying tower reflux tank 29 is connected with the reaction rectifying tower 27 through a pipeline;
the top of the tower hydrogenation reactor 31 is connected with the lower part of the tower hydrogenation reactor 31 through a pipeline, and the bottom of the tower hydrogenation reactor 31 is connected with the light component removal tower 32 through a pipeline;
the top of the light component removal tower 32 is connected with a condenser 33 at the top of the light component removal tower through a pipeline, and the lower part of the light component removal tower 32 is connected with a reboiler 35 and a heavy component removal tower 36 through pipelines; the top condenser 33 of the light component removal tower is connected with a light component removal tower reflux tank 34 through a pipeline, and the light component removal tower reflux tank 34 is connected with the light component removal tower 32 through a pipeline;
the top of the de-heavy column 36 is connected with a de-heavy column overhead condenser 37 through a pipeline, and the lower part of the de-heavy column 36 is connected with a de-heavy column reboiler 39 through a pipeline; the heavy component removal tower top condenser 37 is connected with a heavy component removal tower reflux tank 38 through a pipeline, and the heavy component removal tower reflux tank 38 is connected with the heavy component removal tower 36 through a pipeline;
the tops of the light component removal tower 32 and the heavy component removal tower 36 are respectively connected with a light component removal tower vacuum-pumping pipeline 40 and a heavy component removal tower vacuum-pumping pipeline 41.
The operating temperature of the reactive distillation column 27 was-5 ~ 50 ℃.
The operating pressure of the tower hydrogenation reactor 31 is 2.0 ~ 6.0.0 MpaA absolute pressure, and the operating temperature is 50 ~ 120 ℃.
The operating pressure of the light ends removal column 32 was 0.03 ~ 0.08.08 MpaA.
The operating pressure of the de-heavies column 36 is 0.0002 ~ 0.005.005 MpaA.
A method for synthesizing 1, 3-butanediol comprises the following steps:
s1, feeding an acetaldehyde aqueous solution 1 into a reaction rectifying tower 27, and carrying out condensation reaction under the catalytic action of an alkaline anionic resin catalyst loaded in the tower; the light component 2 at the top of the reactive distillation tower which is not completely reacted is condensed into the light component 3 at the top of the reactive distillation tower which is condensed by a condenser 28 at the top of the reactive distillation tower, and then the light component enters a reflux tank 29 of the reactive distillation tower, part of the liquid phase in the reflux tank 29 of the reactive distillation tower is used as the reflux liquid phase 4 of the reactive distillation tower and flows back to the reactive distillation tower 27, and part of the liquid phase is recycled as the circulating acetaldehyde 5; the tower bottom of the reactive distillation tower 27 is a tower bottom heavy component 6 rich in 3-hydroxy butyraldehyde, one part of the heavy component is gasified by a reboiler 30 of the reactive distillation tower and then is converted into a heavy component 7 gasified by the reboiler, and the heavy component is returned to the tower, and the other part of the heavy component is used as a raw material 3-hydroxy butyraldehyde 8 of a tower hydrogenation reactor 31 and enters the tower hydrogenation reactor 31;
s2: carrying out hydrogenation reaction on 3-hydroxybutyraldehyde 8 and total hydrogen 11 in a tower type hydrogenation reactor 31, mixing circulating hydrogen 9 at the tower top with supplemented fresh hydrogen 10, and then feeding the mixture into the tower type hydrogenation reactor 31, and obtaining a reaction product crude 1, 3-butanediol 12 at the tower bottom; the crude 1, 3-butanediol 12 of the reaction product enters a lightness-removing tower 32;
s3, condensing the light component 13 at the top of the lightness-removing column into a condensed light component 14 at the top of the lightness-removing column through a condenser 33 at the top of the lightness-removing column, and then feeding the condensed light component 14 into a reflux tank 34 of the lightness-removing column, wherein one part of the liquid phase in the reflux tank 34 of the lightness-removing column is taken as a reflux liquid phase 15 of the lightness-removing column to reflux the lightness-removing column 32, and the other part is taken as a light component 16; the bottom of the light component removal tower 32 is a heavy component 17 of the bottom of the light component removal tower rich in 1, 3-butanediol, one part of the heavy component removal tower is gasified by a reboiler 35 of the light component removal tower to form a heavy component 18 of the bottom of the light component removal tower gasified by the reboiler and returns to the tower, and the other part of the heavy component removal tower is used as a raw product 19 of the 1, 3-butanediol with the light component removed by the feeding of the heavy component removal tower 36 and enters the heavy component removal tower 36;
s4: a heavy component removal tower top 20 at the tower top of the heavy component removal tower 36 is gas-phase 1, 3-butanediol, the gas-phase 1, 3-butanediol is condensed into a condensed heavy component removal tower 21 through a heavy component removal tower top condenser 37 and then enters a heavy component removal tower reflux tank 38, a part of liquid phase in the heavy component removal tower reflux tank 38 is returned to the heavy component removal tower 36 as a heavy component removal tower reflux liquid phase 22, and a part of liquid phase is extracted as a 1, 3-butanediol product 23; the tower bottom of the heavy component removal tower 36 is the heavy component 24 of the tower bottom of the heavy component removal tower, one part of the heavy component removal tower is gasified by a heavy component removal tower reboiler 39 and then becomes the heavy component 25 of the heavy component removal tower gasified by the reboiler to return to the tower, and the other part of the heavy component removal tower is taken out as a heavy component stream 26.
The operating temperature of the reactive distillation column 27 was-5 ~ 50 ℃.
The operating pressure of the tower hydrogenation reactor 31 is 2.0 ~ 6.0.0 MpaA absolute pressure, and the operating temperature is 50 ~ 120 ℃.
The operating pressure of the light ends removal column 32 was 0.03 ~ 0.08.08 MpaA.
The operating pressure of the de-heavies column 36 is 0.0002 ~ 0.005.005 MpaA.
The synthesis device comprises a condensation reaction system, a hydrogenation reaction system and a vacuum refining system. Adopting a packing type reaction rectifying tower to realize the condensation of acetaldehyde to generate 3-hydroxybutyraldehyde; hydrogenating 3-hydroxybutyraldehyde in a tower reactor to obtain a 1, 3-butanediol crude product; and (3) feeding the 1, 3-butanediol crude product into a vacuum refining system to obtain a high-quality 1, 3-butanediol product.
The condensation reaction system adopts a reaction rectifying tower loaded with alkaline anion resin to realize the condensation reaction of acetaldehyde to generate 3-hydroxybutyraldehyde, and the acetaldehyde distilled from the tower top can be recycled; and the alkaline anion resin is used as a catalyst, so that the wastewater discharge of the device is reduced.
The hydrogenation reaction system adopts a tower reactor to realize the hydrogenation reaction of the 3-hydroxybutyraldehyde, the tower reactor can reduce the back mixing to the minimum, and the yield and the conversion rate of the reaction are improved.
The refining system is a vacuum system, namely the vacuum system is adopted to refine the 1, 3-butanediol crude product, the temperature is reduced, the decomposition of heat-sensitive substances is prevented, and the purity of the 1, 3-butanediol is improved.
The invention provides a device and a method for synthesizing 1, 3-butanediol on the basis of a plate-type reaction rectifying tower, a kettle-type reactor and a fixed bed reactor; optimizing the condensation reaction of acetaldehyde by adopting a reaction rectifying tower; a tower reactor is adopted to optimize the hydrogenation reaction of the 3-hydroxybutyraldehyde; and then refining the 1, 3-butanediol product by adopting vacuum rectification. The method has the advantages of simple whole process, realization of continuous operation, reduction of energy consumption, promotion of sustainable development, improvement of the quality of the 1, 3-butanediol product, enlargement of the application range and great economic, environmental and social benefits.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The 1, 3-butanediol synthesizing device is characterized in that: comprises a condensation reaction system, a hydrogenation reaction system and a vacuum refining system which are connected in sequence through pipelines; the condensation reaction system adopts a reaction rectifying tower (27) loaded with basic anion resin; the hydrogenation reaction system adopts a tower type hydrogenation reactor (31); the vacuum refining system includes a light ends removal column (32) and a heavy ends removal column (36).
2. The apparatus for synthesizing 1, 3-butanediol as claimed in claim 1, wherein:
the top of the reactive distillation column (27) is connected with a condenser (28) at the top of the reactive distillation column through a pipeline, and the lower part of the reactive distillation column (27) is connected with a reboiler (30) of the reactive distillation column and a tower hydrogenation reactor (31) through a pipeline; the reaction rectifying tower top condenser (28) is connected with a reaction rectifying tower reflux tank (29) through a pipeline, and the reaction rectifying tower reflux tank (29) is connected with the reaction rectifying tower (27) through a pipeline;
the top of the tower hydrogenation reactor (31) is connected with the lower part of the tower hydrogenation reactor (31) through a pipeline, and the tower kettle of the tower hydrogenation reactor (31) is connected with the light component removal tower (32) through a pipeline;
the top of the light component removal tower (32) is connected with a condenser (33) at the top of the light component removal tower through a pipeline, and the lower part of the light component removal tower (32) is connected with a reboiler (35) of the light component removal tower and a heavy component removal tower (36) through pipelines; the condenser (33) at the top of the light component removal tower is connected with a light component removal tower reflux tank (34) through a pipeline, and the light component removal tower reflux tank (34) is connected with a light component removal tower (32) through a pipeline;
the top of the de-heavy tower (36) is connected with a de-heavy tower overhead condenser (37) through a pipeline, and the lower part of the de-heavy tower (36) is connected with a de-heavy tower reboiler (39) through a pipeline; the overhead condenser (37) of the de-heavy tower is connected with a reflux tank (38) of the de-heavy tower through a pipeline, and the reflux tank (38) of the de-heavy tower is connected with the de-heavy tower (36) through a pipeline;
the top parts of the light component removing tower (32) and the heavy component removing tower (36) are respectively connected with a light component removing tower vacuum-pumping pipeline (40) and a heavy component removing tower vacuum-pumping pipeline (41).
3. A synthesis device of 1, 3-butanediol as defined in claim 1, characterized in that the operation temperature of said reactive distillation column (27) is-5 ~ 50 ℃.
4. The 1, 3-butanediol synthesizer according to claim 1, characterized in that the operating pressure of the tower hydrogenation reactor (31) is 2.0 ~ 6.0.0 Mpa absolute and the operating temperature is 50 ~ 120 ℃.
5. The apparatus for synthesizing 1, 3-butanediol as set forth in claim 1, wherein the operating pressure of the light ends removal column (32) is 0.03 ~ 0.08.08 MpaA.
6. The apparatus for synthesizing 1, 3-butanediol as defined in claim 1, wherein the operating pressure of the de-heavy column (36) is 0.0002 ~ 0.005.005 MpaA.
7. A method for synthesizing 1, 3-butanediol is characterized in that: the method comprises the following steps:
s1, feeding an acetaldehyde aqueous solution (1) into a reaction rectifying tower (27), and carrying out condensation reaction under the catalytic action of an alkaline anionic resin catalyst loaded in the tower; condensing the incompletely reacted light components (2) at the top of the reactive distillation tower into light components (3) at the top of the reactive distillation tower after the reactive distillation tower is condensed by a condenser (28) at the top of the reactive distillation tower, feeding the light components (3) into a reflux tank (29) of the reactive distillation tower, wherein one part of the liquid phase in the reflux tank (29) of the reactive distillation tower is used as the reflux liquid phase (4) of the reactive distillation tower to reflux the reactive distillation tower (27), and the other part of the liquid phase is recycled acetaldehyde (5); the tower bottom of the reactive distillation tower (27) is a tower bottom heavy component (6) rich in 3-hydroxybutyraldehyde, one part of the heavy component is gasified by a reboiler (30) of the reactive distillation tower and then is converted into a heavy component (7) gasified by the reboiler, and the heavy component returns to the tower, and the other part of the heavy component is used as a raw material 3-hydroxybutyraldehyde (8) of a tower type hydrogenation reactor (31) and enters the tower type hydrogenation reactor (31);
s2: carrying out hydrogenation reaction on 3-hydroxybutyraldehyde (8) and total hydrogen (11) in a tower type hydrogenation reactor (31), mixing circulating hydrogen (9) at the top of the tower with supplemented fresh hydrogen (10) and then feeding the mixture into the tower type hydrogenation reactor (31), and obtaining a reaction product crude 1, 3-butanediol (12) at the bottom of the tower; the crude 1, 3-butanediol (12) of the reaction product enters a lightness-removing tower (32);
s3, condensing the light component (13) at the top of the lightness-removing column into a condensed light component (14) at the top of the lightness-removing column through a condenser (33) at the top of the lightness-removing column, and then feeding the condensed light component (14) into a reflux tank (34) of the lightness-removing column, wherein one part of the liquid phase in the reflux tank (34) of the lightness-removing column is used as a reflux liquid phase (15) of the lightness-removing column to reflux the lightness-removing column (32), and the other part of the liquid phase is used as a light component (16) to; the bottom of the light component removal tower (32) is a heavy component (17) of the bottom of the light component removal tower rich in 1, 3-butanediol, one part of the heavy component removal tower is gasified by a reboiler (35) of the light component removal tower to form a heavy component (18) of the bottom of the light component removal tower gasified by the reboiler and returns to the tower, and the other part of the heavy component removal tower is used as a crude product (19) of 1, 3-butanediol with light components removed from the feed of the heavy component removal tower (36) and enters the heavy component removal tower (36);
s4: a heavy component (20) at the top of the heavy component removal tower (36) is gas-phase 1, 3-butanediol, the gas-phase 1, 3-butanediol is condensed into a condensed heavy component removal tower (21) by a heavy component removal tower top condenser (37), the condensed heavy component removal tower enters a heavy component removal tower reflux tank (38), one part of a liquid phase in the heavy component removal tower reflux tank (38) is returned to the heavy component removal tower (36) as a heavy component removal tower reflux liquid phase (22), and the other part of the liquid phase is extracted as a 1, 3-butanediol product (23); the tower bottom of the heavy component removal tower (36) is heavy component (24) at the tower bottom of the heavy component removal tower, one part of the heavy component removal tower is gasified by a heavy component removal tower reboiler (39) and then becomes heavy component removal tower (25) gasified by the reboiler to return to the tower, and the other part of the heavy component removal tower is taken out as heavy component stream (26).
8. A synthesis device of 1, 3-butanediol as defined in claim 7, characterized in that the operation temperature of the reactive distillation column (27) is-5 ~ 50 ℃.
9. A1, 3-butanediol synthesizing device according to claim 7, characterized in that the operating pressure of the tower hydrogenation reactor (31) is 2.0 ~ 6.0.0 Mpa absolute and the operating temperature is 50 ~ 120 ℃.
10. A synthesis plant of 1, 3-butanediol as defined in claim 7, characterized in that the operating pressure of the light ends removal column (32) is 0.03 ~ 0.08.08 Mpa A and the operating pressure of the heavy ends removal column (36) is 0.0002 ~ 0.005.005 Mpa A.
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| CN112390705A (en) * | 2019-08-14 | 2021-02-23 | 中国科学院青岛生物能源与过程研究所 | Purification method for deodorizing 1, 3-butanediol |
| CN113527063A (en) * | 2021-08-12 | 2021-10-22 | 南京朗碧源化工科技有限公司 | Energy-saving BDO rectification process by adopting alkynal method |
| CN114853571A (en) * | 2022-05-27 | 2022-08-05 | 辽宁石油化工大学 | Production process and system of 1, 4-butanediol |
| CN115028513A (en) * | 2022-05-30 | 2022-09-09 | 万华化学集团股份有限公司 | Method for producing 1, 3-butanediol |
| CN115304458A (en) * | 2022-07-08 | 2022-11-08 | 陕西延长石油（集团）有限责任公司 | System and process for separating and refining acetaldehyde prepared by ethanol dehydrogenation |
| CN115400706A (en) * | 2022-08-29 | 2022-11-29 | 山东海科新源材料科技股份有限公司 | Device and method for purifying and deodorizing cosmetics grade 1,3-butanediol |
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