CN118477594A - Device and method for producing 4-hydroxybutyl acrylate - Google Patents
Device and method for producing 4-hydroxybutyl acrylate Download PDFInfo
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- CN118477594A CN118477594A CN202410942085.9A CN202410942085A CN118477594A CN 118477594 A CN118477594 A CN 118477594A CN 202410942085 A CN202410942085 A CN 202410942085A CN 118477594 A CN118477594 A CN 118477594A
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- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title abstract description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 163
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 239000006227 byproduct Substances 0.000 claims abstract description 70
- 238000000926 separation method Methods 0.000 claims abstract description 64
- 239000000047 product Substances 0.000 claims abstract description 63
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 28
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 19
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 230000032050 esterification Effects 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- 101000618467 Hypocrea jecorina (strain ATCC 56765 / BCRC 32924 / NRRL 11460 / Rut C-30) Endo-1,4-beta-xylanase 2 Proteins 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- -1 hydroxybutyl Chemical group 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000066 reactive distillation Methods 0.000 claims description 8
- 238000004064 recycling Methods 0.000 claims description 8
- 238000012856 packing Methods 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000012847 fine chemical Substances 0.000 abstract 1
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- 239000003960 organic solvent Substances 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000003795 chemical substances by application Substances 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a device for producing 4-hydroxybutyl acrylate, which relates to the technical field of production of 4-hydroxybutyl acrylate and comprises a reaction rectifying tower, a product purifying tower, a byproduct separating tower, a primary side reactor, a secondary side reactor, a 1, 4-butanediol extractor and a 4-hydroxybutyl acrylate extractor. The invention also provides a method for producing the 4-hydroxy butyl acrylate, which adopts the reaction rectification and micro-reactor technology and the two-stage extraction separation to carry out high-efficiency rectification, thereby effectively realizing the high-efficiency energy-saving production of the high-end fine chemical 4-hydroxy butyl acrylate. The invention performs process strengthening by reaction rectification and micro-reaction technology aiming at a series of esterification reaction systems, effectively ensures the generation of target products, reduces the occurrence of side reactions and improves the selectivity of the products; the separation difficulty of the high-near-boiling point reactant system is solved by two-stage extraction, the separation energy consumption is reduced, the polymerization of the 4-hydroxybutyl acrylate is inhibited, and the product yield is improved.
Description
Technical Field
The invention relates to the technical field of production of 4-hydroxybutyl acrylate, in particular to a device and a method for producing 4-hydroxybutyl acrylate.
Background
The 4-hydroxybutyl acrylate (4-HBA), also known as 1, 4-butanediol monoacrylate (BDMA), is a high-activity difunctional monomer, is soluble in water and general organic solvents, and is widely used in the fields of coatings, resins, adhesives, fiber reinforced materials and the like. The 4-HBA has wide application in industrial paint such as automobile finish paint, repair paint, furniture paint and the like by virtue of a plurality of excellent properties such as low-temperature flexibility, scratch resistance, chemical resistance, weather resistance and the like.
The synthesis method of the 4-hydroxy butyl acrylate mainly comprises three methods of a direct esterification method, an ester exchange method and an acyl chloride method. In China, the industrialized production mainly takes Acrylic Acid (AA) and 1, 4-butanediol as raw materials, the raw materials are directly esterified, the reaction equation is shown in a formula (1), and the final product is obtained through the separation steps of esterification, extraction, rectification and the like. Since this reaction is a reversible reaction accompanied by a series of side reactions, as shown in the formula (2), the product 4-HBA is further esterified with the starting material AA to produce 1, 4-butanediol diacrylate (BDDA) as a by-product. The traditional production method adopts intermittent reaction and azeotropic agent dehydration technology, and aims to remove generated water from a reaction system in time so as to promote the esterification reaction to proceed in the forward direction, thereby improving the conversion rate of raw materials. After the byproduct water is removed from the reaction system, the entrainer, unreacted raw materials and main reaction byproducts (4-HBA and BDDA) are all extracted from the reaction kettle, and the boiling points of the 4-HBA and BDDA are high (290 ℃) and close to each other, so that the temperature difference is only about 9 ℃, the two products are difficult to separate by conventional vacuum rectification, the separation energy consumption is high, and the problems of polymerization and the like are easily caused.
The main reaction:
(1)
Side reaction:
Formula (2).
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a device and a method for producing 4-hydroxy butyl acrylate, which aim to reduce the separation difficulty of materials in a reaction kettle by inhibiting the generation of side reaction, and reduce the contact between a reaction product and raw material acrylic acid by adopting a normal pressure reaction and reduced pressure rectification method so as to inhibit the generation of the side reaction; meanwhile, aiming at the reaction products and partial unreacted materials, the high-efficiency separation among the raw materials 1, 4-butanediol, the product 4-hydroxybutyl acrylate and the byproduct 1, 4-butanediol diacrylate is realized by adopting two-stage extraction by utilizing the difference of the solubility of the reaction products and partial unreacted materials in the organic solvent and water. The invention can effectively inhibit side reaction, reduce side reaction between 4-hydroxy butyl acrylate and acrylic acid, improve the utilization rate of raw materials, and reduce energy consumption and working procedures of subsequent separation.
In order to achieve the above purpose, the invention is realized by the following technical scheme: a device for producing 4-hydroxybutyl acrylate comprises a reaction rectifying tower, a product purifying tower, a byproduct separating tower, a primary side reactor, a secondary side reactor, a 1, 4-butanediol extractor and a 4-hydroxybutyl acrylate extractor;
The outlets of the primary side reactor and the secondary side reactor are respectively connected with the side line of the reactive rectifying tower;
the tower bottom of the reaction rectifying tower is connected with the inlet of the tower bottom cooler of the reaction rectifying tower, the side outlet of the reaction rectifying tower is connected with the inlet of the secondary side reactor, and the outlet of the tower bottom cooler of the reaction rectifying tower is connected with the inlet of the 1, 4-butanediol extractor;
The light component outlet of the 1, 4-butanediol extractor is connected with the inlet of the 4-hydroxybutyl acrylate extractor, and the heavy component outlet of the 1, 4-butanediol extractor is connected with fresh 1, 4-butanediol feeding pipelines of the primary side reactor and the secondary side reactor;
The light component outlet of the 4-hydroxybutyl acrylate extractor is connected with the inlet of a byproduct separation tower preheater, the heavy component outlet of the 4-hydroxybutyl acrylate extractor is connected with the inlet of the product purification tower, and the byproduct separation tower preheater is connected with the inlet of a byproduct separation tower;
the top of the product purifying tower is connected with the inlet of the 4-hydroxybutyl acrylate extractor;
The gas phase outlet of the byproduct separation tower is connected with the inlet of a circulating extractant cooler, and the outlet of the circulating extractant cooler is connected with the inlet of the 1, 4-butanediol extractor;
And heat exchangers are arranged on the tower top and the tower bottom of the reaction rectifying tower and the product purifying tower.
Preferably, the common feed line of the primary side reactor and the secondary side reactor is provided with a primary micromixer and a secondary micromixer connected in series; the primary side reactor and the secondary side reactor are micron-sized micro-channel reactors, and oil baths are arranged outside the primary side reactor and the secondary side reactor and used for immersing the micron-sized micro-channel reactors.
Preferably, the reaction temperature of the primary side reactor and the secondary side reactor is 80-100 ℃, and the reaction pressure is normal pressure.
Preferably, the reaction rectifying tower is operated under reduced pressure, and the operating pressure is 0.001-0.02MPa; the operating pressure of the product purifying tower is 0.001-0.005MPa.
Preferably, the byproduct separation tower is a flash tower filled with random packing, and the operation pressure of the byproduct separation tower is consistent with that of a byproduct separation tower preheater, and is 0.01-0.06MPa.
The invention also provides a method for producing the 4-hydroxybutyl acrylate, which comprises the following steps:
s1, mixing fresh acrylic acid and an esterification catalyst containing a polymerization inhibitor in a first-stage micromixer, then entering a second-stage micromixer, fully mixing fresh 1, 4-butanediol with the acrylic acid and the esterification catalyst, and then respectively entering a first-stage side reactor and a second-stage side reactor after flow distribution; in a two-stage micron-sized micro-channel reactor, acrylic acid and excessive 1, 4-butanediol are subjected to esterification reaction to generate 4-hydroxybutyl acrylate and a small amount of byproduct 1, 4-butanediol diacrylate;
S2, separating a primary side reactor product and a secondary side reactor product in a reaction rectifying tower, wherein an aqueous solution is extracted from the top of the reaction rectifying tower, the aqueous solution comprises byproduct water and a small amount of unreacted and complete acrylic acid, 4-hydroxybutyl acrylate, unreacted and complete 1, 4-butanediol, an esterification catalyst and a small amount of byproduct 1, 4-butanediol diacrylate are extracted from the tower bottom of the reaction rectifying tower, a 1, 4-butanediol mixture after preliminary separation is extracted from the middle side line of the reaction rectifying tower, and the 1, 4-butanediol mixture enters the secondary side reactor;
S3, fully cooling a tower bottom extract of the reaction rectifying tower, entering a1, 4-butanediol extractor, adding a first extractant into the 1, 4-butanediol extractor, extracting and separating, extracting a first light component from the top of the 1, 4-butanediol extractor, extracting a first heavy component from the bottom of the 1, 4-butanediol extractor, wherein the first light component comprises a reaction product and a first extractant, the first heavy component comprises unreacted complete 1, 4-butanediol, and circulating the first heavy component into a side reactor through a fresh 1, 4-butanediol feeding pipeline for further reaction;
S4, the first light component enters a 4-hydroxybutyl acrylate extractor, a second extractant and a solid alkali neutralizer are added into the 4-hydroxybutyl acrylate extractor, a second light component is extracted from the top of the 4-hydroxybutyl acrylate extractor, and a second heavy component is extracted from the bottom of the 4-hydroxybutyl acrylate extractor, wherein the second light component comprises a reaction byproduct 1, 4-butanediol diacrylate and the first extractant, and the second heavy component comprises a reaction product 4-hydroxybutyl acrylate and the second extractant;
S5, the second light component is vaporized by the preheating part and enters a byproduct separation tower for flash separation, a gas phase outlet of the byproduct separation tower is used for extracting and circulating a first extractant, the first extractant is cooled and then circulated to a1, 4-butanediol extractor, and a liquid phase outlet of the byproduct separation tower is used for extracting byproducts of a reaction system;
s6, the second heavy component enters a product purification tower, and is subjected to rectification separation, a circulating second extractant is extracted from the top of the product purification tower and is circulated to a 4-hydroxybutyl acrylate extractor, and a 4-hydroxybutyl acrylate product is extracted from the tower bottom of the product purification tower.
Preferably, the operation temperature of the 1, 4-butanediol extractor and the 4-hydroxybutyl acrylate extractor is 25-40 ℃, the first extractant is cyclohexane, and the second extractant is desalted water.
Preferably, the molar ratio of the acrylic acid to the 1, 4-butanediol total feed in the primary side reactor and the secondary side reactor is 1:1.5-1:3.
Preferably, the mass ratio of the first extractant feed amount to the 1, 4-butanediol feed amount in the tower kettle extract of the reaction rectifying tower is 5:1-8:1.
Preferably, the mass ratio of the feeding amount of the second extractant to the feeding amount of the 4-hydroxybutyl acrylate in the tower bottom extract of the reaction rectifying tower is 5:1-8:1.
The invention discloses a device and a method for producing 4-hydroxybutyl acrylate, which have the following beneficial effects:
1. The invention adopts reactive distillation and micro-reaction technology to strengthen the process, so that the selectivity of the product 4-hydroxy butyl acrylate is obviously improved, and meanwhile, the operation temperature of the tower bottom of the reactive distillation tower is controlled by setting the excessive 1, 4-butanediol of the raw material of the reactive distillation system, thereby reducing the polymerization of the reactive system and improving the product yield.
2. According to the invention, for the rectification separation of a high-near-boiling point and easy-polymerization system, a two-stage extraction separation technology is adopted, and suitable low-boiling point and low-cost extractants are screened, so that the separation difficulty and the separation energy consumption of a 4-hydroxybutyl acrylate production system are greatly reduced, and meanwhile, the recycling of the two extractants is realized through rectification separation and flash evaporation separation, the discharge amount of industrial three wastes is obviously reduced, and the economical efficiency and the environmental protection performance are obviously improved.
3. The production method of the 4-hydroxy butyl acrylate disclosed by the invention realizes continuous production of the 4-hydroxy butyl acrylate, so that the reaction and separation can realize high conversion rate and low energy consumption under the respective optimal working conditions, and meanwhile, the maximum economic benefit is obtained, the yield of the 4-hydroxy butyl acrylate is more than 94%, and the production energy consumption of the 4-hydroxy butyl acrylate product is reduced by more than 30%.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic view of an apparatus for producing hydroxybutyl 4-acrylate according to an embodiment of the present invention;
In the figure: r1-primary side reactor, R2-secondary side reactor, T1-reactive distillation column, E1-reactive distillation column top condenser, E2-reactive distillation column bottom reboiler, T2-product purification column, E3-product purification column top condenser, E4-product purification column bottom reboiler, E5-byproduct separation column preheater, E6-circulating extractant cooler, E7-reactive distillation column bottom cooler, T3-byproduct separation column, EX1-1, 4-butanediol extractor, EX 2-4-hydroxybutyl acrylate extractor, M1-primary micromixer, M2-secondary micromixer, V-oil bath;
1-fresh acrylic acid, 2-fresh 1, 4-butanediol, 3-first heavy component, 4-primary side reactor product, 5-secondary side reactor product, 6-1, 4-butanediol mixture, 7-aqueous solution, 8-reaction rectifying tower bottom extract, 9-first extractant, 10-first light component, 11-second extractant, 12-second light component, 13-cycle first extractant, 14-reaction system byproduct, 15-second heavy component, 16-cycle second extractant, 17-4-hydroxybutyl acrylate product, 18-esterification catalyst containing polymerization inhibitor, and 19-solid alkali neutralizer.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: the apparatus for producing hydroxybutyl 4-acrylate according to FIG. 1 comprises a reaction rectifying column T1, a product purifying column T2, a byproduct separating column T3, a primary side reactor R1, a secondary side reactor R2, a1, 4-butanediol extractor EX1 and a 4-hydroxybutyl acrylate extractor EX2.
The outlets of the primary side reactor R1 and the secondary side reactor R2 are respectively connected with the side line of the reactive rectifying tower T1. The tower kettle of the reaction rectifying tower T1 is connected with the inlet of a tower kettle cooler E7 of the reaction rectifying tower, the side outlet of the reaction rectifying tower T1 is connected with the inlet of a secondary side reactor R2, and the outlet of the tower kettle cooler E7 of the reaction rectifying tower is connected with the inlet of a 1, 4-butanediol extractor EX 1. The light component outlet of the 1, 4-butanediol extractor EX1 is connected with the inlet of the 4-hydroxybutyl acrylate extractor EX2, and the heavy component outlet of the 1, 4-butanediol extractor EX1 is connected with fresh 1, 4-butanediol feed lines of the primary side reactor R1 and the secondary side reactor R2. The light component outlet of the 4-hydroxybutyl acrylate extractor EX2 is connected with the inlet of the byproduct separating tower preheater E5, the heavy component outlet of the 4-hydroxybutyl acrylate extractor EX2 is connected with the inlet of the product purifying tower T2, and the byproduct separating tower preheater E5 is connected with the inlet of the byproduct separating tower T3. The top of the product purifying column T2 is connected with the inlet of the 4-hydroxybutyl acrylate extractor EX 2. The gas phase outlet of the byproduct separation tower T3 is connected with the inlet of a circulating extractant cooler E6, and the outlet of the circulating extractant cooler E6 is connected with the inlet of a 1, 4-butanediol extractor EX 1.
Further, the common feed line of the primary side reactor R1 and the secondary side reactor R2 is provided with a primary micromixer M1 and a secondary micromixer M2 connected in series. The primary side reactor R1 and the secondary side reactor R2 are micron-sized micro-channel reactors, and oil baths V are arranged outside the primary side reactor R1 and the secondary side reactor R2 and used for immersing the micron-sized micro-channel reactors. The reaction rectifying tower T1 is operated under reduced pressure, and the operating pressure can be 0.001-0.02MPa. The operating pressure of the product purification column T2 may be from 0.001 to 0.005MPa. The reaction temperature of the primary side reactor R1 and the secondary side reactor R2 can be 80-100 ℃, and the reaction pressure is normal pressure. The byproduct separation tower T3 is a flash tower filled with random packing, and the operating pressure of the byproduct separation tower T3 and the operating pressure of the byproduct separation tower preheater E5 are consistent and can be 0.01-0.06MPa.
Further, a reactive rectifying tower top condenser E1 is arranged at the top of the reactive rectifying tower T1, and a reactive rectifying tower kettle reboiler E2 is arranged at the bottom of the reactive rectifying tower. The top of the product purifying tower T2 is provided with a product purifying tower top condenser E3, and the tower bottom is provided with a product purifying tower bottom reboiler E4.
Example 2: a process for producing hydroxybutyl 4-acrylate using the apparatus of example 1, comprising the steps of:
s1, 1441.40kg/h of fresh acrylic acid 1 and esterification catalyst 18 containing polymerization inhibitor are mixed in a primary micromixer M1, then enter a secondary micromixer M2, the temperature is 35 ℃,1785.64kg/h of fresh 1, 4-butanediol 2 enters the secondary micromixer M2, and after being fully mixed with acrylic acid and esterification catalyst, the mixture is distributed by a regulating valve, and then the mixture is mixed with the mixture in a ratio of 1:1 respectively enter a primary side reactor R1 and a secondary side reactor R2; in a two-stage micron-sized micro-channel reactor, acrylic acid and excessive 1, 4-butanediol are subjected to esterification reaction to generate 4-hydroxybutyl acrylate and a small amount of byproduct 1, 4-butanediol diacrylate;
wherein, the heat conduction oil is introduced into an oil bath V outside the primary side reactor R1 to control the reaction temperature, the reaction temperature of the primary side reactor R1 is 80 ℃, and the operation pressure of the primary side reactor R1 is normal pressure; introducing heat conduction oil into an oil bath V outside the secondary side reactor R2 to control the reaction temperature, wherein the reaction temperature of the secondary side reactor R2 is 85 ℃, and the operating pressure of the secondary side reactor R2 is normal pressure; the operating pressure of the reaction rectifying tower T1 is 0.001MPa, and the inside of the reaction rectifying tower T1 is filled with random packing with the height of 16 m.
S2, respectively feeding a primary side reactor product 4 and a secondary side reactor product 5 from the heights of 12m and 4m into a reaction rectifying tower T1 for separation, wherein 365.16kg/h of aqueous solution 7 is extracted from the top of the reaction rectifying tower T1, and the aqueous solution 7 comprises byproduct water and a small amount of unreacted acrylic acid, wherein the mass content of the water is 98.26%; 5017.83kg/h of 4-hydroxybutyl acrylate, unreacted complete 1, 4-butanediol, an esterification catalyst and a small amount of byproduct 1, 4-butanediol diacrylate are extracted from the tower bottom of the reaction rectifying tower T1, wherein the mass content of the 4-hydroxybutyl acrylate is 60.79%; the 1, 4-butanediol mixture 6 after preliminary separation is extracted from the 8m high side line of the reaction rectifying tower T1, wherein the mass contents of 1, 4-butanediol, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and water are 79.32%, 17.95%, 2.32% and 0.41% respectively; the 1, 4-butanediol mixture 6 was fed into the secondary side reactor R2 at a flow rate of 1384.54 kg/h.
S3, the extract 8 at the bottom of the reaction rectifying tower is fully cooled by a cooler E7 at the bottom of the reaction rectifying tower and enters a 1, 4-butanediol extractor EX1, the operation temperature of the 1, 4-butanediol extractor EX1 is 25 ℃, a first extractant 9 which is 61.77kg/h of cyclohexane is added into the 1, 4-butanediol extractor EX1, 15513.23kg/h of a first light component 10 is extracted and separated from the top of the 1, 4-butanediol extractor EX1, and 2155.95kg/h of a first heavy component 3 is extracted from the bottom of the 1, 4-butanediol extractor EX 1; wherein the first light component 10 comprises a reaction product and a first extractant, and the mass contents of cyclohexane, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and 1, 4-butanediol are 81.37%, 17.69%, 0.72% and 0.22%, respectively; the first heavy fraction 3 comprises unreacted complete 1, 4-butanediol, wherein the mass contents of 1, 4-butanediol, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and cyclohexane are 84.37%, 14.60%, 0.90% and 0.12%, respectively, and the first heavy fraction 3 is recycled to the side reactor for further reaction via a fresh 1, 4-butanediol feed line at a flow rate of 2155.95 kg/h.
S4, the first light component 10 enters a 4-hydroxybutyl acrylate extractor EX2, the operation temperature of the 4-hydroxybutyl acrylate extractor EX2 is 30 ℃, a second extractant 11 and a solid alkali neutralizer 19 are added into the 4-hydroxybutyl acrylate extractor EX2, the second extractant 11 is desalted water of 2.73kg/h, a second light component 12 of 12665.83kg/h is extracted from the top of the 4-hydroxybutyl acrylate extractor EX2, and a second heavy component 15 of 18201.54kg/h is extracted from the bottom; wherein the second light component 12 comprises a reaction byproduct 1, 4-butanediol diacrylate and a first extractant, and the mass contents of cyclohexane, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and water are respectively 99.64%, 0.14%, 0.21% and 0.02%; the second component 15 comprises the reaction product hydroxybutyl 4-acrylate and a second extractant, wherein the mass content of water, hydroxybutyl 4-acrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol and cyclohexane is 84.34%, 14.98%, 0.47%, 0.18% and 0.02%, respectively.
S5, preheating a second light component 12 to 30 ℃ through a byproduct separation tower preheater E5, introducing the partially vaporized second light component into a byproduct separation tower T3 from a position with the height of 2.4m for flash separation, wherein the operating pressure of the byproduct separation tower T3 is 0.05Mpa, recycling a first extractant 13 from a gas phase outlet of the byproduct separation tower T3, recycling the recycled first extractant to a1, 4-butanediol extractor EX1 at a flow rate of 12589.58kg/h after cooling, recycling a reaction system byproduct 14 with the weight content of 76.25kg/h from a liquid phase outlet of the byproduct separation tower T3, and respectively enabling the mass contents of cyclohexane, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and water in the reaction system byproduct 14 to be 75.55%, 10.80%, 10.24% and 3.41%.
S6, a second recombinant 15 enters a product purification tower T2 from a position with the height of 1.2m, the operating pressure of the product purification tower T2 is 0.005MPa, 4.2m high random packing is filled in the product purification tower T2, the second extractant 16 is extracted and circulated from the top of the product purification tower T2 and recycled to the 4-hydroxybutyl acrylate extractor EX2 at the flow rate of 15351.41kg/h, 2850.13kg/h of 4-hydroxybutyl acrylate product 17, and the mass contents of 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol and cyclohexane in the hydroxybutyl acrylate product 17 of the product purification tower T2 are 95.69%, 2.99%, 1.17% and 0.15% respectively.
The conversion rate of the acrylic acid after the reaction of the embodiment reaches 99.56 percent, and the yield of the 4-hydroxybutyl acrylate reaches 94.87 percent.
Example 3: a process for producing hydroxybutyl 4-acrylate using the apparatus of example 1, comprising the steps of:
s1, 1441.40kg/h of fresh acrylic acid 1 and esterification catalyst 18 containing polymerization inhibitor are mixed in a primary micromixer M1, then enter a secondary micromixer M2, 30 ℃,1794.29kg/h of fresh 1, 4-butanediol 2 enters the secondary micromixer M2, and after being fully mixed with acrylic acid and esterification catalyst, the mixture is distributed by a regulating valve, and then the mixture is mixed with the mixture in a ratio of 1:1 respectively enter a primary side reactor R1 and a secondary side reactor R2; in a two-stage micron-sized micro-channel reactor, acrylic acid and excessive 1, 4-butanediol are subjected to esterification reaction to generate 4-hydroxybutyl acrylate and a small amount of byproduct 1, 4-butanediol diacrylate;
Wherein, the heat conduction oil is introduced into an oil bath V outside the primary side reactor R1 to control the reaction temperature, the reaction temperature of the primary side reactor R1 is 90 ℃, and the operation pressure of the primary side reactor R1 is normal pressure; introducing heat conduction oil into an oil bath V outside the secondary side reactor R2 to control the reaction temperature, wherein the reaction temperature of the secondary side reactor R2 is 85 ℃, and the operating pressure of the secondary side reactor R2 is normal pressure; the operating pressure of the reaction rectifying tower T1 is 0.001MPa, and the inside of the reaction rectifying tower T1 is filled with random packing with the height of 16 m.
S2, respectively feeding a primary side reactor product 4 and a secondary side reactor product 5 from the heights of 12m and 4m into a reaction rectifying tower T1 for separation, wherein 383.17kg/h of aqueous solution 7 is extracted from the top of the reaction rectifying tower T1, and the aqueous solution 7 comprises byproduct water and a small amount of unreacted acrylic acid, wherein the mass content of the water is 93.96%; 6658.23kg/h of 4-hydroxybutyl acrylate, unreacted complete 1, 4-butanediol, an esterification catalyst and a small amount of byproduct 1, 4-butanediol diacrylate are extracted from the tower bottom of the reaction rectifying tower T1, wherein the mass content of the 4-hydroxybutyl acrylate is 5.83%; the 1, 4-butanediol mixture 6 after preliminary separation is extracted from the 8m high side line of the reaction rectifying tower T1, wherein the mass contents of 1, 4-butanediol, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and water are respectively 80.43%, 10.87%, 6.37% and 2.33%; the 1, 4-butanediol mixture 6 was fed into the secondary side reactor R2 at a flow rate of 1940.18 kg/h.
S3, the extract 8 at the bottom of the reaction rectifying tower is fully cooled by a cooler E7 at the bottom of the reaction rectifying tower and enters a 1, 4-butanediol extractor EX1, the operation temperature of the 1, 4-butanediol extractor EX1 is 30 ℃, a first extractant 9 which is 92.91kg/h of cyclohexane is added into the 1, 4-butanediol extractor EX1, 30967.54kg/h of a first light component 10 is extracted and separated from the top of the 1, 4-butanediol extractor EX1, and 3805.71kg/h of a first heavy component 3 is extracted from the bottom of the 1, 4-butanediol extractor EX 1; wherein the first light component 10 comprises a reaction product and a first extractant, and the mass contents of cyclohexane, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and 1, 4-butanediol are respectively 90.74%, 8.92%, 0.31% and 0.03%; the first heavy fraction 3 comprises unreacted complete 1, 4-butanediol, wherein the mass contents of 1, 4-butanediol, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and cyclohexane are 94.94%, 4.49%, 0.51% and 0.06%, respectively, and the first heavy fraction 3 is recycled to the side reactor for further reaction via a fresh 1, 4-butanediol feed line at a flow rate of 3805.71 kg/h.
S4, the first light component 10 enters a 4-hydroxybutyl acrylate extractor EX2, the operation temperature of the 4-hydroxybutyl acrylate extractor EX2 is 35 ℃, a second extractant 11 and a solid alkali neutralizer 19 are added into the 4-hydroxybutyl acrylate extractor EX2, the second extractant 11 is desalted water of 2.73kg/h, a second light component 12 of 28192.57kg/h is extracted from the top of the 4-hydroxybutyl acrylate extractor EX2, and a second heavy component 15 of 23801.21kg/h is extracted from the bottom; wherein the second light component 12 comprises a reaction byproduct 1, 4-butanediol diacrylate and a first extractant, and the mass contents of cyclohexane, 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate and water are respectively 99.66%, 0.04%, 0.29% and 0.01%; the second component 15 comprises the reaction product hydroxybutyl 4-acrylate and a second extractant, wherein the mass content of water, hydroxybutyl 4-acrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol and cyclohexane is 88.33%, 11.56%, 0.06%, 0.04% and 0.01%, respectively.
S5, preheating a second light component 12 to 30 ℃ through a byproduct separation tower preheater E5, introducing the partially vaporized second light component into a byproduct separation tower T3 from a position with the height of 2.4m for flash separation, wherein the operating pressure of the byproduct separation tower T3 is 0.06Mpa, recycling a first extractant 13 from a gas phase outlet of the byproduct separation tower T3, recycling the recycled first extractant to a1, 4-butanediol extractor EX1 at a flow rate of 28022.11kg/h after cooling, recycling 170.46kg/h of a reaction system byproduct 14 from a liquid phase outlet of the byproduct separation tower T3, and respectively enabling the mass contents of cyclohexane, 1, 4-butanediol diacrylate, 4-hydroxybutyl acrylate and water in the reaction system byproduct 14 to be 53.54%, 41.79%, 3.14% and 1.53%.
S6, a second recombinant 15 enters a product purification tower T2 from a position with the height of 1.2m, the operating pressure of the product purification tower T2 is 0.003MPa, 4.2m high random packing is filled in the product purification tower T2, the second extractant 16 is extracted and circulated from the top of the product purification tower T2 and recycled to the 4-hydroxybutyl acrylate extractor EX2 at the flow rate of 21023.51kg/h, 2777.69kg/h of 4-hydroxybutyl acrylate product 17 is extracted from the tower bottom of the product purification tower T2, and the mass contents of 4-hydroxybutyl acrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol and cyclohexane in the product 17 are 99.05%, 0.50%, 0.39% and 0.06% respectively.
The conversion rate of the acrylic acid after the reaction of the embodiment reaches 99.89%, and the yield of the 4-hydroxybutyl acrylate reaches 95.42%.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing description merely illustrates the principles of the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The device for producing the 4-hydroxybutyl acrylate is characterized by comprising a reaction rectifying tower (T1), a product purifying tower (T2), a byproduct separating tower (T3), a primary side reactor (R1), a secondary side reactor (R2), a1, 4-butanediol extractor (EX 1) and a 4-hydroxybutyl acrylate extractor (EX 2);
the outlets of the primary side reactor (R1) and the secondary side reactor (R2) are respectively connected with the side line of the reactive rectifying tower (T1);
The tower bottom of the reaction rectifying tower (T1) is connected with the inlet of a tower bottom cooler (E7) of the reaction rectifying tower, the side outlet of the reaction rectifying tower (T1) is connected with the inlet of the secondary side reactor (R2), and the outlet of the tower bottom cooler (E7) of the reaction rectifying tower is connected with the inlet of the 1, 4-butanediol extractor (EX 1);
the light component outlet of the 1, 4-butanediol extractor (EX 1) is connected with the inlet of the 4-hydroxybutyl acrylate extractor (EX 2), and the heavy component outlet of the 1, 4-butanediol extractor (EX 1) is connected with fresh 1, 4-butanediol feed lines of the primary side reactor (R1) and the secondary side reactor (R2);
the light component outlet of the 4-hydroxybutyl acrylate extractor (EX 2) is connected with the inlet of a byproduct separation tower preheater (E5), the heavy component outlet of the 4-hydroxybutyl acrylate extractor (EX 2) is connected with the inlet of the product purification tower (T2), and the byproduct separation tower preheater (E5) is connected with the inlet of a byproduct separation tower (T3);
The top of the product purifying column (T2) is connected with the inlet of the 4-hydroxybutyl acrylate extractor (EX 2);
The gas phase outlet of the byproduct separation tower (T3) is connected with the inlet of a circulating extractant cooler (E6), and the outlet of the circulating extractant cooler (E6) is connected with the inlet of the 1, 4-butanediol extractor (EX 1);
The tower tops and the tower bottoms of the reaction rectifying tower (T1) and the product purifying tower (T2) are respectively provided with a heat exchanger.
2. The apparatus according to claim 1, characterized in that the common feed line of the primary side reactor (R1) and the secondary side reactor (R2) is provided with a primary micromixer (M1) and a secondary micromixer (M2) in series; the primary side reactor (R1) and the secondary side reactor (R2) are micron-sized micro-channel reactors, and oil baths (V) are arranged outside the primary side reactor (R1) and the secondary side reactor (R2) and are used for immersing the micron-sized micro-channel reactors.
3. The apparatus according to claim 1 or 2, wherein the reaction temperature of the primary side reactor (R1) and the secondary side reactor (R2) is 80 to 100 ℃, and the reaction pressure is normal pressure.
4. The apparatus according to claim 1 or 2, wherein the reactive distillation column (T1) is operated under reduced pressure, the operating pressure being 0.001-0.02MPa; the operating pressure of the product purifying column (T2) is 0.001-0.005MPa.
5. The apparatus according to claim 1 or 2, wherein the by-product separation column (T3) is a flash column filled with random packing, and the operating pressures of the by-product separation column (T3) and the by-product separation column preheater (E5) are in the range of 0.01 to 0.06MPa.
6. A process for producing hydroxybutyl 4-acrylate, comprising the steps of:
S1, mixing fresh acrylic acid (1) with an esterification catalyst (18) containing a polymerization inhibitor in a primary micro-mixer (M1), then entering a secondary micro-mixer (M2), fully mixing the fresh 1, 4-butanediol (2) with the acrylic acid and the esterification catalyst, and then respectively entering a primary side reactor (R1) and a secondary side reactor (R2) after flow distribution; in a two-stage micron-sized micro-channel reactor, acrylic acid and excessive 1, 4-butanediol are subjected to esterification reaction to generate 4-hydroxybutyl acrylate and a small amount of byproduct 1, 4-butanediol diacrylate;
S2, a primary side reactor product (4) and a secondary side reactor product (5) are respectively fed into a reaction rectifying tower (T1) for separation, an aqueous solution (7) is produced from the top of the reaction rectifying tower (T1), the aqueous solution (7) comprises byproduct water and a small amount of unreacted and complete acrylic acid, 4-hydroxybutyl acrylate, unreacted and complete 1, 4-butanediol, an esterification catalyst and a small amount of byproduct 1, 4-butanediol diacrylate are produced from the tower bottom of the reaction rectifying tower (T1), a 1, 4-butanediol mixture (6) after preliminary separation is produced from the middle side line of the reaction rectifying tower (T1), and the 1, 4-butanediol mixture (6) is fed into a secondary side reactor (R2);
S3, fully cooling a tower bottom extract (8) of the reaction rectifying tower, entering a1, 4-butanediol extractor (EX 1), adding a first extractant (9) into the 1, 4-butanediol extractor (EX 1), extracting and separating, extracting a first light component (10) at the top of the 1, 4-butanediol extractor (EX 1), and extracting a first heavy component (3) at the bottom, wherein the first light component (10) comprises a reaction product and the first extractant, the first heavy component (3) comprises unreacted complete 1, 4-butanediol, and recycling the first heavy component (3) to a side reactor through a fresh 1, 4-butanediol feeding pipeline for further reaction;
S4, the first light component (10) enters a 4-hydroxybutyl acrylate extractor (EX 2), a second extractant (11) and a solid alkali neutralizer (19) are added into the 4-hydroxybutyl acrylate extractor (EX 2), a second light component (12) is extracted from the top of the 4-hydroxybutyl acrylate extractor (EX 2), a second heavy component (15) is extracted from the bottom of the 4-hydroxybutyl acrylate extractor (EX 2), wherein the second light component (12) comprises a reaction byproduct 1, 4-butanediol diacrylate and the first extractant, and the second heavy component (15) comprises a reaction product 4-hydroxybutyl acrylate and the second extractant;
S5, the second light component (12) enters a byproduct separation tower (T3) for flash evaporation separation after being partially vaporized by preheating, a gas phase outlet of the byproduct separation tower (T3) is used for extracting and circulating a first extractant (13), the first extractant is cooled and circulated to a1, 4-butanediol extractor (EX 1), and a liquid phase outlet of the byproduct separation tower (T3) is used for extracting a reaction system byproduct (14);
s6, the second heavy component (15) enters a product purifying tower (T2) and is subjected to rectification separation, a circulating second extractant (16) is extracted from the top of the product purifying tower (T2) and is circulated to a 4-hydroxybutyl acrylate extractor (EX 2), and a 4-hydroxybutyl acrylate product (17) is extracted from the tower bottom of the product purifying tower (T2).
7. The method according to claim 6, characterized in that the operating temperature of the 1, 4-butanediol extractor (EX 1), 4-hydroxybutyl acrylate extractor (EX 2) is 25-40 ℃, the first extractant (9) is cyclohexane and the second extractant (11) is desalted water.
8. The process according to claim 6 or 7, characterized in that the molar ratio of acrylic acid and 1, 4-butanediol total feed in the primary side reactor (R1) and secondary side reactor (R2) is 1:1.5-1:3.
9. The method according to claim 6 or 7, characterized in that the mass ratio of the feed amount of the first extractant (9) to the feed amount of 1, 4-butanediol in the reaction rectifying column bottom extract (8) is 5:1-8:1.
10. The method according to claim 6 or 7, characterized in that the mass ratio of the feed amount of the second extractant (11) to the feed amount of the hydroxybutyl 4-acrylate in the reaction rectifying column bottom extract (8) is 5:1-8:1.
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| CN105859530A (en) * | 2015-01-23 | 2016-08-17 | 上海优华系统集成技术有限公司 | Stabilizer tower and MTBE device catalytic distillation column combined cycle system |
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| CN109053450A (en) * | 2018-07-03 | 2018-12-21 | 青岛科技大学 | A kind of preparation method for the 4- hy-droxybutyl being separated by extraction |
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