CN113416133A - Method for continuously producing (methyl) acrylic polyol ester - Google Patents
Method for continuously producing (methyl) acrylic polyol ester Download PDFInfo
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- CN113416133A CN113416133A CN202110616277.7A CN202110616277A CN113416133A CN 113416133 A CN113416133 A CN 113416133A CN 202110616277 A CN202110616277 A CN 202110616277A CN 113416133 A CN113416133 A CN 113416133A
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- acrylic acid
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- 229920005862 polyol Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 52
- -1 acrylic polyol ester Chemical class 0.000 title claims abstract description 50
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- 239000000945 filler Substances 0.000 claims abstract description 15
- 239000011973 solid acid Substances 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 63
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000001276 controlling effect Effects 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 238000010924 continuous production Methods 0.000 claims description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 238000000066 reactive distillation Methods 0.000 claims description 11
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229950000688 phenothiazine Drugs 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 238000003860 storage Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000004821 distillation Methods 0.000 description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000009833 condensation Methods 0.000 description 9
- 230000005494 condensation Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000032050 esterification Effects 0.000 description 8
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- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously producing (methyl) acrylic polyol ester, aiming at providing a method for continuously producing (methyl) acrylic polyol ester, which has the advantages of high esterification reaction rate, high raw material conversion rate, high target product selectivity and high product purity; the method comprises the steps of filling a rectification column with a solid acid catalyst and a filler in a mixing manner for catalytic reaction by using non-traditional reactive rectification equipment, continuously performing reactive rectification under a reduced pressure condition, discharging from the top of a tower, recovering a low-boiling-point reaction raw material or obtaining a high-purity (methyl) acrylic polyol ester product, and discharging from the bottom of the tower, and performing reduced pressure rectification to obtain the high-purity (methyl) acrylic polyol ester product or raw material; belongs to the technical field of fine chemical engineering.
Description
Technical Field
The invention belongs to the field of continuous production of (methyl) acrylic polyol ester, and particularly relates to a method for continuously producing (methyl) acrylic polyol ester and a (methyl) acrylic polyol ester product continuously obtained by the method.
Background
Polyol (meth) acrylate is an important chemical raw material. Because the molecule contains a series of active functional groups such as C-C, -OH, carboxyl derivatives, long side ester-based chain monomers and the like, the polymer monomer can be used as a polymerization monomer to be homopolymerized and copolymerized into a plurality of polymers, the structure of the polymer determines that the prepared high polymer has the characteristics of excellent weather resistance, ultraviolet light resistance, water resistance, heat resistance and the like, and the polymer is mainly applied to the fields of polymerization modification, adhesives, printing ink, coatings and the like.
At present, the methods for preparing (methyl) acrylic polyol ester at home and abroad mainly comprise a direct esterification method, an ester exchange method and the like. The direct esterification method is divided into a solvent esterification method and a melt esterification method, the solvent esterification method is a synthetic method which is characterized in that an organic solvent is added into a reaction system to be used as a water-carrying agent, so that an azeotrope is formed between the organic solvent and water generated in the reaction process, the water is continuously carried out of the reaction system, and the reaction is promoted to be carried out towards the direction of a product, and a catalyst and a polymerization inhibitor are often added into the reaction system. Compared with other methods, the method can reduce the dosage of the catalyst and the polymerization inhibitor on the premise of shortening the reaction time and obtaining higher yield and purer products, and the melt esterification method is better from the aspects of yield, product purity and economy. The transesterification method is to generate the higher polyol (meth) acrylate by transesterification of the lower polyol (meth) acrylate and the higher polyol, wherein the product methanol after transesterification and the lower polyol (meth) acrylate form a low boiling azeotrope, although the azeotrope can bring the methanol out of the reaction system to promote the forward reaction, the subsequent methanol is difficult to separate from the azeotrope, and the lower polyol (meth) acrylate with the stoichiometric ratio being many times is needed in the reaction process.
CN101891613A discloses a preparation method of hydroxyethyl methacrylate: putting a flask provided with a stirrer, a thermometer and a reflux condenser tube into a water bath kettle, adding ferric trioxide as a catalyst, hydroquinone as a polymerization inhibitor and methacrylic acid, heating in water bath to 80-85 ℃, replacing air in the reaction bottle with nitrogen, introducing ethylene oxide after ferric trioxide is completely dissolved in methacrylic acid, introducing air for 4 hours, continuing to react for 1 hour after the air introduction is finished, transferring the reactant into a gram-type distillation flask, adding a proper amount of hydroquinone, carrying out reduced pressure distillation, and collecting 82-85 ℃ fraction as a finished product.
CN100349852C discloses a method for preparing (meth) acrylic acid higher aliphatic polyol ester, which comprises directly esterifying (meth) acrylic acid and higher aliphatic polyol (higher than dodecyl polyol) as raw materials in the presence of at least one polymerization inhibitor and entrainer under the action of acidic catalyst to synthesize (meth) acrylic acid higher aliphatic polyol ester. After the esterification reaction is finished, the reaction product is subjected to post-treatment, and then the residual entrainer and water are removed through reduced pressure distillation, so that the product purity is more than 98%, the acidity is less than 0.03%, and the chroma is less than 100 (APHA). The method provided by the invention has the advantages of simple operation, high yield and good product quality, and can realize industrial production, a large amount of entrainer can be consumed in the industrial production process, toluene and the like are frequently used as the entrainer in industry, the subsequent separation is difficult, and the product is impure.
CN107056613A discloses a method for preparing acrylic acid low-carbon polyol ester by coal pyrolysis gas, which comprises the following steps: cooling the high-temperature coal pyrolysis gas by an oil-gas separation heat exchange device; removing dust solids in the coal pyrolysis gas after oil-gas separation; removing sulfur and oxygen impurities in the dried tail gas; further purifying the deoxidized and desulfurized coal pyrolysis gas, removing hydrogen and methane gas in the coal pyrolysis gas to obtain purified CO gas, removing moisture in the tail gas after dust removal, and pressurizing the dried purified CO gas to reaction pressure; the pressurized CO gas is used as a carbonylation raw material and reacts with acetylene and low-carbon polyol in a reactor through a catalyst to generate acrylic low-carbon polyol ester. By the method, a large amount of carbon monoxide gas in the coal pyrolysis gas is utilized, and the acrylic acid low-carbon polyol ester product is obtained. The method for producing the acrylic acid low-carbon polyol ester product has too complex working procedures and difficult subsequent product separation and purification.
CN108586237A discloses a preparation method of neopentyl glycol dimethacrylate, which comprises the steps of reacting neopentyl glycol with methacrylic acid at 78-92 ℃ for 4-7 hours under the action of a catalyst p-toluenesulfonic acid and in the presence of a polymerization inhibitor and an azeotropic water-carrying agent to synthesize the neopentyl glycol dimethacrylate; the molar ratio of the methacrylic acid to the neopentyl glycol is 2.15:1, the amount of the azeotropic water-carrying agent n-hexane is 45% of the total mass of the reactants, the amount of the catalyst is 4% of the total mass of the reactants, and the amount of the polymerization inhibitor phenothiazine is 0.1% of the total mass of the reactants.
In the published papers and patents, regarding the preparation method of (meth) acrylic polyol ester, the (meth) acrylic acid and corresponding polyol are mostly adopted to intermittently react under the combined action of water-carrying agents, catalysts and polymerization inhibitors to generate the (meth) acrylic polyol ester, the method for producing the (meth) acrylic polyol ester consumes more catalysts and polymerization inhibitors, the water-carrying agents used in the method are generally toxic organic reagents such as toluene and the like, the subsequent separation is difficult, the obtained (meth) acrylic polyol ester is impure, and the like. At present, the methods for continuously producing the (meth) acrylic acid polyol ester are less, and because the continuous production of the (meth) acrylic acid polyol ester has unstable catalyst activity and unstable reaction process, the continuous production of the (meth) acrylic acid polyol ester is less reported.
Disclosure of Invention
The invention aims to provide a method for continuously producing (methyl) acrylic polyol ester, which has the advantages of high conversion rate of raw materials, high selectivity of target products, high reaction efficiency and high purity of obtained products.
The invention discloses a method for continuously producing (methyl) acrylic polyol ester, which comprises the following steps:
pretreatment: preheating the raw materials, adding a polymerization inhibitor into the raw materials for dissolving, uniformly stirring, uniformly mixing a solid acid catalyst and a filler, and filling a rectifying column;
reaction:
taking polyhydric alcohol and (methyl) acrylic acid as raw materials; or polyhydric alcohol and (methyl) acrylic acid lower alcohol ester are used as raw materials; or (meth) acrylic acid polyol monoester and (meth) acrylic acid are used as raw materials to produce corresponding (meth) acrylic acid polyol ester;
in the reaction process, non-traditional reaction rectification equipment is used, and the reaction rectification esterification reaction is carried out by regulating and controlling the conditions of feeding amount, reaction temperature, system pressure, air amount, reflux ratio and the like;
and (3) post-treatment: distilling the condensate at the top of the tower under reduced pressure to remove water or low-boiling-point products, wherein the residual distillate is the desired product or unreacted raw materials, if the residual distillate is the raw materials, returning to continue the reaction, and if the residual distillate is the product, collecting the residual distillate; and (4) carrying out reduced pressure rectification on the collected liquid in the tower bottom to separate the raw material or the product, if the collected liquid is the raw material, returning to continue the reaction, and if the collected liquid is the product, collecting the product.
Further, in the above method for continuously producing polyol (meth) acrylate, the (meth) acrylic acid is acrylic acid or methacrylic acid.
Further, in the above method for continuously producing polyol (meth) acrylate, the polyol is ethylene glycol, polyethylene glycol, propylene glycol, glycerol, pentaerythritol, or sorbitol.
Further, in the method for continuously producing the (methyl) acrylic acid polyol ester, the feeding amount of the polyol is 1-100 kg/h.
Further, in the method for continuously producing the (methyl) acrylic polyol ester, the polymerization inhibitor is hydroquinone, p-hydroxyanisole or phenothiazineOxazine, diethylhydroxylamine, trinitrobenzene, m-dinitrobenzene, m-nitrochlorobenzene, nitrobenzene, sodium nitrite, CuSO4/NaHSO4The dosage of the one or more of the combination is 0.05 to 2 percent of the mass of the raw materials.
Further, in the method for continuously producing the (methyl) acrylic polyol ester, the air amount is introduced into the tower kettle by 5-100L/h.
Further, in the above method for continuously producing a polyol (meth) acrylate, the solid acid catalyst is packed in a rectifying column, V (solid acid): and V (filler) is 1: 100-10: 1.
Further, in the method for continuously producing the (methyl) acrylic polyol ester, the non-traditional reaction rectification equipment supplies heat for the esterification reaction by virtue of the heating rectification column, the tower kettle is not heated, the pressure of the reaction rectification system is 5-100 KPa, and the temperature of the rectification column is 60-240 ℃.
Further, according to the method for continuously producing the (methyl) acrylic polyol ester, the reflux ratio of the top of the reaction rectifying equipment is 10: 1-10: 10.
Further, in the above-mentioned method for continuously producing a polyol (meth) acrylate, the number of carbon atoms is C4～C6The alcohol (meth) acrylate(s) being condensed at the top of the column and having a number of carbon atoms exceeding C7Collecting the (methyl) acrylic acid alcohol ester in the tower kettle.
Compared with the prior art, the method for continuously producing the (methyl) acrylic polyol ester has the following technical advantages:
(1) the reaction adopts solid acid as catalyst, the catalyst and filler are uniformly mixed and filled in a rectifying column, and the step of separating the catalyst required by the traditional catalyst post-treatment is avoided.
(2) The melting esterification method is adopted, and toxic water-carrying agents such as toluene and the like do not need to be added, so that high-purity products can be obtained easily in the subsequent process.
(3) The melting esterification reaction is carried out under the negative pressure state, and the low boiling point substances generated by the reaction are taken out of the system in time, so that the forward reaction is promoted, and the conversion rate of the raw materials is improved.
(4) By adding reaction materials in time, transferring condensed liquid at the top of the tower and collecting liquid at the bottom of the tower, continuous production is realized.
(5) According to the technical scheme provided by the invention, air is introduced in the reaction process, so that the contact time of the raw materials and the solid acid catalyst is effectively prolonged, the catalytic efficiency is improved, and the polymerization inhibition effect is enhanced by matching the air with the polymerization inhibitor.
(6) The technical scheme provided by the invention effectively controls the polymerization condition of unsaturated substances in the reaction rectification process by regulating and controlling the temperature of the rectification column of the reaction rectification equipment, and improves the reaction efficiency.
Drawings
FIG. 1 is a spectrum of measuring the content of hydroxybutyl 4- (meth) acrylate in example 1 of the present invention.
FIG. 2 is a spectrum of a mixture composition measurement at the start of the reaction in example 2 of the present invention.
FIG. 3 is a spectrum of the composition of the mixture after the reaction in example 2 of the present invention.
FIG. 4 is a spectrum of detecting the content of butylene glycol di (meth) acrylate in example 2 of the present invention.
FIG. 5 is a graph showing a measurement spectrum of neopentyl glycol di (meth) acrylate content in example 3 of the present invention.
FIG. 6 is a graph showing a measurement spectrum of the ethylene glycol di (meth) acrylate content in example 4 of the present invention.
FIG. 7 is a block diagram of a non-conventional reactive distillation apparatus employed in the present invention;
FIG. 8 is a block diagram of a non-conventional reactive distillation apparatus employed in the present invention;
FIG. 9 is a control block diagram of a non-conventional reactive distillation apparatus employed in the present invention.
Detailed Description
The following claims are presented in further detail in connection with specific examples of the invention, but are not to be construed as limiting the invention in any way.
Example 1
This example provides a continuous process for the production of hydroxybutyl 4- (meth) acrylate
The filler is V (perfluorosulfonic acid ion exchange resin): uniformly filling the V (theta ring filler) in a ratio of 1:10, taking (methyl) acrylic acid and 1, 4-butanediol as raw materials, weighing 1% of phenothiazine according to the mass of the raw materials, dissolving the phenothiazine in the raw materials, and preheating the (methyl) acrylic acid and the 1, 4-butanediol to 90 ℃. Regulating and controlling a rectifying column reaction section of reactive distillation equipment to be 90 ℃, the condensing temperature at the top of the rectifying column to be 13 ℃, the reflux ratio to be 10:5, the system pressure to be 80KPa, introducing air into a tower kettle for 20L/h, controlling an upper feeding hole of the 1, 4-butanediol for 5kg/h, feeding the 1, 4-butanediol into a lower feeding hole of the (methyl) acrylic acid for 10kg/h, and carrying out a feeding reaction, wherein the conversion rate of the 1, 4-butanediol is 98 percent by quantitatively analyzing materials before and after the reaction through gas chromatography.
Transferring the tower top condensate to a reduced pressure distillation device, wherein the tower top condensate is a mixed solution of water generated by the esterification reaction and unreacted (methyl) acrylic acid, controlling the pressure of a reduced pressure distillation system to be 4-5 KPa and the temperature to be 60-65 ℃, evaporating the water generated by the esterification reaction, and the residual kettle liquid is the (methyl) acrylic acid, and adding the (methyl) acrylic acid into a lower feed inlet storage tank to continuously participate in the reaction. Transferring the collected liquid in the tower kettle to a vacuum rectification device, wherein the collected liquid in the tower kettle is a mixed solution of 4- (methyl) hydroxybutyl acrylate and phenothiazine, controlling the pressure of a vacuum rectification system to be 2-3 KPa and the temperature to be 110-115 ℃ to obtain the 4- (methyl) hydroxybutyl acrylate, and as shown in figure 1, the content of the rectified 4- (methyl) hydroxybutyl acrylate reaches 99.01 percent according to a GC spectrogram.
Example 2
This example provides a continuous process for the production of butanediol di (meth) acrylate
The filler is V (Al)2O3/SO4 2-): uniformly filling the V (theta ring filler) in a ratio of 1:10, taking (methyl) acrylic acid and 4- (methyl) hydroxybutyl acrylate as raw materials, weighing 0.5% of polymerization inhibitor according to the mass of the raw materials, dissolving the polymerization inhibitor in the raw materials, and dissolving m (p-hydroxyanisole): m (hydroquinone) ═ 1:1, (meth) acrylic acid and 4-hydroxybutyl (meth) acrylate were preheated to 100 ℃. Regulating and controlling the reaction section of a rectifying column of the reactive distillation equipment to be 100 ℃, the condensing temperature at the top of the rectifying column to be 13 ℃, the reflux ratio to be 10:5, the system pressure to be 70KPa, introducing air into a tower kettle for 30L/h, controlling an upper feeding hole of the 4- (methyl) butyl acrylate to be 2kg/h, and feeding the (methyl) acrylic acid to be 1.5kg/h through a lower feeding holeThe conversion of 4-hydroxybutyl (meth) acrylate was 98% by quantitative analysis of the materials before and after the reaction by gas chromatography, and the ratio of the components in the mixture before and after the reaction was shown in fig. 2 and 3, and it was found from 26.29% of hydroxybutyl (meth) acrylate in the mixture from the beginning of the reaction to 1.44% of hydroxybutyl (meth) acrylate after the reaction, and it was found by quantitative analysis by internal standard method that the conversion of hydroxybutyl (meth) acrylate was about 98%, indicating that hydroxybutyl (meth) acrylate was substantially completely reacted under the above conditions.
Transferring the tower top condensate to a reduced pressure distillation device, wherein the tower top condensate is a mixed solution of water generated by the esterification reaction and unreacted (methyl) acrylic acid, controlling the pressure of a reduced pressure distillation system to be 4-5 KPa and the temperature to be 60-65 ℃, evaporating the water generated by the esterification reaction, and the residual kettle liquid is the (methyl) acrylic acid, and adding the (methyl) acrylic acid into a lower feed inlet storage tank to continuously participate in the reaction. Transferring the collected liquid in the tower kettle to a vacuum rectification device, wherein the collected liquid in the tower kettle is a mixed solution of 4- (methyl) hydroxybutyl acrylate, p-hydroxyanisole and hydroquinone, and controlling the pressure of a vacuum rectification system to be 2-3 KPa and the temperature to be 125-130 ℃ to obtain the butanediol di (methyl) acrylate with the purity of 98%, and as can be seen from figure 4, the content of the butanediol di (methyl) acrylate reaches 98%.
Example 3
This example provides a continuous process for the production of neopentyl glycol di (meth) acrylate
The filler is V (SO)4 2-/Fe2O): uniformly filling the V (theta ring filler) in a ratio of 1:10, taking (methyl) acrylic acid and neopentyl glycol as raw materials, weighing 0.5 percent of hydroquinone according to the mass of the raw materials, dissolving the hydroquinone in the raw materials, and preheating the (methyl) acrylic acid and the neopentyl glycol to 110 ℃. Regulating and controlling a rectifying column reaction section of reactive distillation equipment to be 110 ℃, the condensing temperature at the top of the rectifying column to be 15 ℃, the reflux ratio to be 10:8, the system pressure to be 80KPa, introducing air into a tower kettle for 30L/h, controlling a neopentyl glycol upper feeding port for 2kg/h, feeding materials into a (methyl) acrylic acid lower feeding port for 2kg/h for reaction, and quantitatively analyzing the materials before and after the reaction by gas chromatography to obtain the conversion rate of the neopentyl glycol to be 98.4%.
Transferring the tower top condensate to a reduced pressure distillation device, wherein the tower top condensate is a mixed solution of water generated by the esterification reaction and unreacted (methyl) acrylic acid, controlling the pressure of a reduced pressure distillation system to be 4-5 KPa and the temperature to be 60-65 ℃, evaporating the water generated by the esterification reaction, and the residual kettle liquid is the (methyl) acrylic acid, and adding the (methyl) acrylic acid into a lower feed inlet storage tank to continuously participate in the reaction. Transferring the tower kettle collected liquid to a vacuum rectification device, wherein the tower kettle collected liquid is a mixed solution of neopentyl glycol di (meth) acrylate and hydroquinone, and controlling the pressure of a vacuum rectification system to be 2-3 KPa and the temperature to be 130-135 ℃ to obtain the neopentyl glycol di (meth) acrylate with the purity of 98%, as can be seen from figure 5, the content of the neopentyl glycol di (meth) acrylate reaches 98%.
Example 4
This example provides a continuous process for the production of ethylene glycol di (meth) acrylate
The filler is V (mesoporous phenolic resin polymer-based solid acid catalyst): uniformly filling the V (theta ring filler) in a ratio of 1:10, taking methyl (meth) acrylate and ethylene glycol as raw materials, weighing 0.5% of p-hydroxyanisole according to the mass of the raw materials, dissolving the p-hydroxyanisole in the raw materials, and preheating the methyl (meth) acrylate and the ethylene glycol to 70 ℃. Regulating and controlling 75 ℃ of a rectifying column reaction section of reactive distillation equipment, 13 ℃ of condensation temperature at the top of a tower, 10:8 of reflux ratio, 80KPa of system pressure, 10L/h of air introduced into a tower kettle, 1kg/h of ethylene glycol upper feeding port, 5kg/h of feeding reaction at a (methyl) acrylic acid lower feeding port, and quantitatively analyzing materials before and after the reaction through gas chromatography, wherein the conversion rate of ethylene glycol is 98.8%.
Transferring the tower top condensate to a reduced pressure distillation device, wherein the tower top condensate is a mixed solution of methanol and methyl (meth) acrylate generated by transesterification, controlling the pressure of a reduced pressure distillation system to be 2-3 KPa and the temperature to be 50-55 ℃, distilling out the methanol generated by the transesterification, and adding the methyl (meth) acrylate into a lower feeding hole storage tank to continuously participate in the reaction, wherein the residual kettle liquid is the methyl (meth) acrylate. Transferring the tower kettle collecting liquid to a vacuum rectification device, wherein the tower kettle collecting liquid is a mixed solution of ethylene glycol di (meth) acrylate and p-hydroxyanisole, controlling the pressure of a vacuum rectification system to be 2-3 KPa, controlling the temperature to be 105-110 ℃, and obtaining the ethylene glycol di (meth) acrylate with the purity of 98%, as can be seen from figure 6, the content of the ethylene glycol di (meth) acrylate reaches 98%.
From the above examples it can be seen that:
(1) selecting a proper solid acid catalyst and a filler to be uniformly mixed and filled in the rectifying column, so that the subsequent process of catalyst separation can be avoided;
(2) reaction and separation integration is realized by using reaction rectification equipment, and the investment of separation equipment is reduced;
(3) the reaction rectification system is decompressed, so that water or low-boiling-point products generated in the esterification or ester exchange reaction process can be transferred in time, and the conversion rate of raw materials is increased.
(4) The reaction raw materials of the storage tank are supplemented in time, the condensed liquid at the top of the tower and the collected liquid at the bottom of the tower are transferred, and the continuity of the whole reaction process can be realized.
In order to make the technical solutions provided in the present application better implemented by those skilled in the art, the following descriptions of the present application
Referring to fig. 7 to 9, the non-conventional reactive distillation apparatus used in the above embodiment includes a distillation column B as described in embodiment 1, and includes a hollow column 1 and a hollow column 1, both ends of the column 1 are open, and a heating module 2 for heating the column 1 is disposed on the column 1. The column body 1 is provided with a heating module 2 for heating the column body 1.
In this embodiment, the column 1 includes an upper rectifying column 11 and a lower rectifying column 12 which are connected with each other, a tubular reaction section 13 is arranged between the upper rectifying column 11 and the lower rectifying column 12, the outer wall of the tubular reaction section 13 is provided with a plurality of heat source input ports 22 and a heat source output port 23, heat conducting oil enters between the tubular reaction sections 13 through the heat source input ports 22 in the reaction, and the materials in the tubular reaction sections 13 are heated, and due to the arrangement of the plurality of heat source input ports 22, the materials are uniformly heated in the reaction process, and the influence of local aggregation on the reaction efficiency and the product yield is avoided.
In practical application, the two ends of the column body 1 are respectively connected with the tower head and the tower kettle, and the heating module 2 is arranged on the column body 1, so that the reaction efficiency of materials in the column body 1 can be improved, and excessive materials which are not completely reacted can be prevented from being gathered in the tower kettle.
Preferably, in order to ensure that the temperature of the heat conducting oil supply is not enough to ensure the temperature required by the reaction at a lower temperature, the heating module 2 further comprises a heating ring 21 arranged on the column body 1, wherein the heating ring 21 can be in a tubular shape, and hot steam or hot water is introduced into the heating ring 21 to heat the column body 1;
the heating module 2 may also be an annular sleeve structure through which hot steam or hot water is introduced, or an electric heating structure, and the like, which is not limited in this embodiment.
In this embodiment, the upper rectification column 11 and the lower rectification column 12 are both provided with a feeding nozzle a, and the outer parts of the upper rectification column 11, the upper rectification column 11 and the lower rectification column 12 are provided with a heat insulation layer (not shown in the figure) which is arranged outside the heating ring 21; the number of the heating rings 21 is 2, which are respectively arranged on the upper rectifying column 11 and the lower rectifying column 12;
the shell and tube reaction section 13 comprises a plurality of tubes arranged along the length direction of the column body 1, and theta ring packing is filled in the tubes.
The upper rectifying column is connected with a gas condensing unit 3, the lower rectifying column is connected with a tower kettle 4, the tower kettle 4 is connected with a first storage unit 5, the gas condensing unit 3 is connected with a second storage unit 6, and the upper rectifying column and the lower rectifying column are respectively fed through a feeding unit 7; a reboiler C is arranged on the tower kettle 4.
In practical application, the tower kettle 4 is heated by the reboiler C, the material is fed to the rectifying column B by the feeding unit 7, gas generated by reactive rectification is treated by the gas condensing unit 3 and then is output to the second storage unit 6, and liquid in the tower kettle 4 is output to the first storage unit 5, so that the rectifying device can realize continuous reaction;
heating rings are arranged on the upper rectifying column and the lower rectifying column, so that the reaction efficiency can be improved.
Specifically, the first storage unit 5 includes a first temporary storage tank 52 connected to the bottom of the tower tank 4 through a first transfer pipe 51; the second storage unit 6 comprises a plurality of second temporary storage tanks 62 connected with the gas condensation unit 3 through a second conveying pipe 61;
the input end and the output end of the first temporary storage tank 52 and the second temporary storage tank 62 are provided with valves E.
In this embodiment, the gas condensation unit 3 includes a tower head 31 connected to the upper rectification column and the second storage unit 6, respectively, and a first condensation component 32 extending into the tower head 31, the first condensation component 32 is connected to a low temperature circulating water bath 33, and the second delivery pipe 61 is connected to the tower head 31;
the tower head 31 comprises a leading-out part connected with the upper rectifying column and a condensing part connected with the leading-out part, the first condensing assembly 32 extends into the condensing part, the condensing part and the lower part of the leading-out part are further provided with a return pipe and other structures which are connected with the condensing part and the leading-out part, a product generated by reactive distillation is condensed through the first condensing assembly 32, a part of condensate flows back to the rectifying column B from the return pipe as a reflux liquid, the rest of the condensate is a product, namely, the condensate is output to the second temporary storage tank 62, and the second conveying pipe 61 is connected with the bottom of the condensing part.
Still be equipped with second condensation subassembly D on the first conveyer pipe 51, second condensation subassembly D with low temperature circulation water bath 33 is connected, further condenses the liquid that the reaction rectification obtained, guarantees product quality.
In this embodiment, the feeding unit 7 comprises a first feeding tank 72 connected to the feeding nozzle of the upper rectifying column through a first feeding pipe 71, and a second feeding tank 74 connected to the feeding nozzle of the lower rectifying column through a second feeding pipe 73, wherein the first feeding pipe 71 and the second feeding pipe 73 are both provided with a feeding pump 75 and a valve E;
the device also comprises an air compression feeding module 8, wherein the air compression feeding module 8 is connected with the first feeding tank 72, the second feeding tank 74, the first temporary storage tank 52, the second temporary storage tank 62 and the tower head 31 through an air supply pipe 81;
the air compression feeding module 8 is matched with the material conveying pump 75 to convey materials in the first feeding tank 72 and the second feeding tank 74, so that normal operation is ensured;
meanwhile, the output work of the materials in the first temporary storage tank 52, the second temporary storage tank 62 and the tower head 31 is also ensured, and the air feed pipe 81 is connected with the top of the condensation part of the tower head 31.
Specifically, the air pressure feeding module 8 comprises a vacuum pump 82 and a vacuum buffer tank 83 connected with the vacuum pump 82, and the air pipe 81 is connected with the vacuum buffer tank 83; the output end and the input end of the vacuum buffer tank 83 are also provided with valves E, and the vacuum buffer tank 83 is also provided with a pressure relief pipe which is also provided with a valve E.
Preferably, heat exchange assemblies F are arranged on the first material conveying pipe 71 and the second material conveying pipe 73, and the heat exchange assemblies F are connected with a high-temperature circulating water bath G, so that the temperature of the materials output by the first material feeding tank 72 and the second material feeding tank 74 is close to that of the materials output by the rectification column B, and the stability of the rectification system is ensured.
Preferably, the system further comprises a control module 9, wherein the control module 9 comprises a controller 91, a control main board 92 arranged in the controller 91, and a touch display screen 93 arranged on the controller 91;
the control module 9 further comprises a temperature sensor 94 arranged in the upper rectifying column, the lower rectifying column, the tower kettle 4, the reboiler C, the tower head 31, the first condensing assembly 32, the second condensing assembly D, the heat exchange assembly F, and a pressure sensor 95 arranged in the vacuum buffer tank 83;
a reflux ratio device 96 arranged at the output end is also arranged in the tower head 31, namely the reflux ratio device 96 is arranged at the output end of the condensation part, so that the separation effect in the rectification process is ensured;
the temperature sensor 94, the pressure sensor 95, the low-temperature circulating water bath 33, the high-temperature circulating water bath G, the heating ring, the reboiler C, the delivery pump 75, the vacuum pump 82, the reflux ratio device 96 and the touch display screen 93 are all electrically connected with the control mainboard 92;
the temperature sensor 94 is used for detecting the temperature data of the corresponding device, the pressure sensor 95 is used for detecting the pressure data in the vacuum buffer tank 83, the two data are transmitted to the control main board 92, the temperature information and the pressure information are displayed on the touch display screen 93 after being processed by the control main board 92, and the real-time monitoring of the temperature and the pressure parameters can be realized;
the controller 91 is also provided with a control button group 97 for controlling the operation of the low-temperature circulating water bath 33, the high-temperature circulating water bath G, the heating ring, the reboiler C, the material delivery pump 75, the vacuum pump 82 and the reflux ratio device 96;
in this embodiment, the liquid in the first temporary storage tank 83 can be manually taken out and analyzed, and then the operations of the low-temperature circulating water bath 33, the high-temperature circulating water bath G, the heating ring, the reboiler C, the feed pump 75, the vacuum pump 82 and the reflux ratio device 96 are controlled through the touch control screen and the control button group 97 according to the parameter information collected by the temperature sensor 94 and the pressure sensor 95 and the analysis result of the liquid in the first temporary storage tank 83, so that the real-time regulation and control of the temperature of each device of the device and the pressure of the vacuum buffer tank 83 can be realized.
A refrigerating component is arranged in the low-temperature circulating water bath 33, a heating component is arranged in the high-temperature circulating water bath G, circulating pumps are further arranged in the low-temperature circulating water bath 33 and the high-temperature circulating water bath G, and the refrigerating component, the heating component and the circulating pumps are electrically connected with the control main board 92.
The reboiler C is also provided with a feeding pipe for adding materials into the reboiler C, and the feeding pipe is also provided with a valve E; the valve E is a plug valve.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for continuously producing (methyl) acrylic acid polyol ester is characterized by comprising the following steps:
pretreatment: preheating the raw materials, adding a polymerization inhibitor into the raw materials for dissolving, uniformly stirring, uniformly mixing a solid acid catalyst and a filler, and filling a rectifying column;
reaction:
taking polyhydric alcohol and (methyl) acrylic acid as raw materials; or polyhydric alcohol and (methyl) acrylic acid lower alcohol ester are used as raw materials; or (meth) acrylic acid polyol monoester and (meth) acrylic acid are used as raw materials to produce corresponding (meth) acrylic acid polyol ester;
in the reaction process, non-traditional reaction rectification equipment is used, and the reaction rectification esterification reaction is carried out by regulating and controlling the feeding amount, the reaction temperature, the system pressure, the air amount, the reflux ratio and the conditions;
and (3) post-treatment: distilling the condensate at the top of the tower under reduced pressure to remove water or low-boiling-point products, wherein the residual distillate is the desired product or unreacted raw materials, if the residual distillate is the raw materials, returning to continue the reaction, and if the residual distillate is the product, collecting the residual distillate; and (4) carrying out reduced pressure rectification on the collected liquid in the tower bottom to separate the raw material or the product, if the collected liquid is the raw material, returning to continue the reaction, and if the collected liquid is the product, collecting the product.
2. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the (meth) acrylic acid is acrylic acid or methacrylic acid.
3. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the polyalcohol is ethylene glycol, polyethylene glycol, propylene glycol, glycerol, pentaerythritol and sorbitol.
4. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the feeding amount of the polyol is 1-100 kg/h.
5. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the polymerization inhibitor is hydroquinone, p-hydroxyanisole, phenothiazine, diethylhydroxylamine, trinitrobenzene, m-dinitrobenzene, m-nitrochlorobenzene, nitrobenzene, sodium nitrite and CuSO4/NaHSO4One or more of the combination of (A) and (B), the dosage of which is raw material0.05-2% of the mass.
6. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: and the air quantity introduced into the tower kettle is 5-100L/h.
7. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the solid acid catalyst is filled in a rectifying column, V (solid acid): and V (filler) is 1: 100-10: 1.
8. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the non-traditional reactive distillation equipment supplies heat to the esterification reaction by depending on a heating rectification column, a tower kettle is not heated, the pressure of a reactive distillation system is 5-100 KPa, and the temperature of the rectification column is 60-240 ℃.
9. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: the reflux ratio of the top of the reaction rectification equipment is 10: 1-10: 10.
10. The continuous production method of a polyol (meth) acrylate according to claim 1, characterized in that: having a carbon number of C4～C6The alcohol (meth) acrylate(s) being condensed at the top of the column and having a number of carbon atoms exceeding C7Collecting the (methyl) acrylic acid alcohol ester in the tower kettle.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717048A (en) * | 2020-05-24 | 2021-11-30 | 广东工业大学 | Preparation method of ethylene glycol dimethacrylate |
| CN114456070A (en) * | 2021-07-09 | 2022-05-10 | 广东新华粤石化集团股份公司 | Polymerization inhibition method in separation process of acrylic substance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113717048A (en) * | 2020-05-24 | 2021-11-30 | 广东工业大学 | Preparation method of ethylene glycol dimethacrylate |
| CN114456070A (en) * | 2021-07-09 | 2022-05-10 | 广东新华粤石化集团股份公司 | Polymerization inhibition method in separation process of acrylic substance |
| CN114456070B (en) * | 2021-07-09 | 2024-05-14 | 广东华锦达新材科技有限公司 | Polymerization inhibition method in acrylic acid substance separation process |
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