CN105037151A - Preparation method of 3-alkoxy alkyl propionate - Google Patents
Preparation method of 3-alkoxy alkyl propionate Download PDFInfo
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- CN105037151A CN105037151A CN201510289293.4A CN201510289293A CN105037151A CN 105037151 A CN105037151 A CN 105037151A CN 201510289293 A CN201510289293 A CN 201510289293A CN 105037151 A CN105037151 A CN 105037151A
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- alkyl ester
- acid alkyl
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- rectifying tower
- alcohol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 47
- 125000005907 alkyl ester group Chemical group 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 18
- 238000007670 refining Methods 0.000 claims description 17
- 239000000470 constituent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 claims description 8
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 8
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 6
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 19
- 229960004756 ethanol Drugs 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- -1 alkali metal alkoxide Chemical class 0.000 description 5
- DKJCSMHIPYRALV-UHFFFAOYSA-N methoxymethyl propanoate Chemical compound CCC(=O)OCOC DKJCSMHIPYRALV-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MUOMSSHCYJTJQT-UHFFFAOYSA-N ethanol;prop-2-enoic acid Chemical compound CCO.OC(=O)C=C MUOMSSHCYJTJQT-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis and provides a preparation method of 3-alkoxy alkyl propionate. The method is characterized by using solid alkali as a catalyst and alkyl acrylate and lower alcohol as raw materials to carry out heterogeneous catalytic alkoxylation reaction, and comprises the steps that an alkoxylation reaction product enters a light component removal rectifying tower to be separated, and lower alcohol and an alkyl acrylate light component, which are recovered from the tower top, are cycled into the step of alkoxylation reaction; a heavy component mainly containing a product 3-alkoxy alkyl propionate is obtained in a tower reactor; the heavy component material in the light component removal rectifying tower reactor is separated by a refined rectifying tower, the product 3-alkoxy alkyl propionate is obtained at the tower top and a few high-boiling substances are obtained in the tower reactor. The preparation method has the beneficial effects that after being separated and recovered by the rectifying tower, the used raw materials and solid alkali serving as the catalyst can be directly put into reaction again without being reprocessed, thus greatly improving the utilization efficiency of the raw materials and the catalyst, reducing the production cost and avoiding environmental pollution.
Description
Technical field
The invention belongs to technical field of chemical synthesis, relate to a kind of preparation method of 3-alkoxypropan acid alkyl ester.
Background technology
3-methoxy methyl propionate and 3-ethoxyl ethyl propionate are the organic solvents of environmental protection, are widely used in the industries such as electronics, cleaning, coating, printing-ink, are also simultaneously the important intermediate in organic synthesis and pharmaceutical industries.
Patent CN101906038A discloses by 1, ammediol catalyzed oxidation prepares the method for 3-methoxy methyl propionate, this method is using carried noble metal gold or the metal oxide of palladium as catalyzer, need in reaction process to use oxygen, there is larger potential safety hazard, and the highest yield of 3-methoxy methyl propionate only 53%.
Document [Qin Bingchang, Deng. application chemical industry, 2007,36 (6): 596-598.] report methyl acrylate and methyl alcohol prepares 3-methoxy methyl propionate under the katalysis of sodium methylate, excessive 1.2 times at methyl alcohol, sodium methylate consumption is 1.3% of methyl acrylate quality, 3.5h is reacted at 50 DEG C, after the completion of reaction, with in Glacial acetic acid and sodium methylate, the yield of 3-methoxy methyl propionate can reach 97%.Document [Zhang Jibo, Deng. Jilin Institute of Chemical Technology journal, 2011,28 (3): 1-3.] first sodium hydroxide, methyl alcohol and anhydrous sodium sulphate are prepared sodium methylate at 65 DEG C, then methyl acrylate is joined in said mixture, after terminating Deng reaction, then use in sodium pyrosulfate and sodium methylate.At methyl alcohol excessive 1.5 times, sodium hydroxide concentration is react 6h at 10%, 55 DEG C, and the yield of 3-methoxy methyl propionate can reach more than 97%.Patent CN1258518C discloses a kind of preparation method of 3-methoxy methyl propionate, first methyl alcohol and quality are that the sodium methylate of methyl alcohol 5.3% ~ 14.3% or potassium methylate stir more than 10h in reactor by this method, then under excessive 2 ~ 3 times of conditions of methyl alcohol, 2 ~ 6h is reacted at 45 ~ 60 DEG C, after reaction terminates, by the vitriol oil and strong phosphoric acid catalyst neutralisation, the yield of methoxy methyl propionate is up to 91.4%.Patent CN101423475B discloses a kind of under the effect of basic metal or alkali metal alkoxide catalyst, and ethyl propenoate and ethanol synthesis obtain the method for 3-ethoxyl ethyl propionate.Be 0 ~ 80 DEG C in temperature of reaction, the mol ratio of ethanol and ethyl propenoate is 2 ~ 3: 1, and catalyst levels is 1.5% ~ 3% of ethyl propenoate quality, and the reaction times is under the condition of 1 ~ 16h, and the yield of 3-ethoxyl ethyl propionate is up to 89.9%.After the completion of reaction, the vitriol oil, acetic acid, hydrochloric acid, phosphoric acid, formic acid or nitric acid catalyst neutralisation is adopted.
Above-mentioned employing alkali metal alkoxide catalyst prepares the method for 3-methoxy methyl propionate and 3-ethoxyl ethyl propionate, because catalyzer and reaction mixture mix, belong to homogeneous reaction, all need to use in acid and basic catalyst, not only cause catalyzer not reuse, improve production cost, and the sodium salt formed needs process further, and have waste water to produce, contaminate environment.
Summary of the invention
The object of the invention is to solve that 3-alkoxypropan acid alkyl ester yield in existing preparation method is not high or production cost is higher, the disagreeableness problem of environment, provides the novel method that a kind of alkoxylate prepares 3-alkoxypropan acid alkyl ester.
For solving the problem, the present invention adopts following technical proposals to realize
1. the invention provides a kind of preparation method of 3-alkoxypropan acid alkyl ester, the method is carried on the solid alkali that solid carrier obtains with alkali metal alcoholates be catalyzer, with alkyl acrylate and low-carbon alcohol for raw material, three mixes rear generation heterogeneous catalysis alkoxylation, then be separated and obtain 3-alkoxypropan acid alkyl ester product, specifically comprise the steps: 1) by fresh low-carbon alcohol stream stock, fresh propylene acid alkyl ester stream stock and solid base catalyst, join in alkoxylation device, heterogeneous catalysis alkoxylation occurs; The reaction feed liquid stream stock containing unreacted low-carbon alcohol, alkyl acrylate and product 3-alkoxypropan acid alkyl ester is obtained after reaction terminates;
2) alkoxylation feed liquid stream stock is separated in de-light rectifying tower, obtain unreacted low-carbon alcohol and alkyl acrylate light constituent material stream in recovered overhead, obtain mainly containing the heavy constituent material stream of product 3-alkoxypropan acid alkyl ester in tower reactor;
3) the main heavy constituent material stream containing product 3-alkoxypropan acid alkyl ester is separated in refining rectifying tower, and obtaining the 3-alkoxypropan acid alkyl ester product flow stock of massfraction more than 99.5% at tower top, is high boiling material in tower reactor.
Low-carbon alcohol stream stock refers to the stream stock that low-carbon alcohol liquid is formed, and represents same substance with low-carbon alcohol; Alkyl acrylate stream stock refers to the stream stock that alkyl acrylate is formed, and represents same substance with alkyl acrylate.
2. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, step 2) after alkoxylation feed liquid stream stock is separated in de-light rectifying tower, the unreacted low-carbon alcohol that tower top obtains and alkyl acrylate light constituent material stream, enter alkoxylation device after merging with fresh low-carbon alcohol stream stock, fresh propylene acid alkyl ester stream stock, be again cycled to used in alkoxylation step.
3. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, step 2) the required theoretical plate number of de-light rectifying tower (6) is 6 ~ 20 pieces, is preferably 9 ~ 14 pieces; Required reflux ratio 0.1 ~ 7, is preferably 0.4 ~ 1.2; Required vacuum tightness is 0.05 ~ 0.095MPa, is preferably 0.08 ~ 0.09MPa.
4. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, step 3) the required theoretical plate number of refining rectifying tower (9) is 6 ~ 20 pieces, preferably 9 ~ 14 pieces; Required reflux ratio 0.1 ~ 10, preferably 0.4 ~ 1.0; Required vacuum tightness is 0.07 ~ 0.1MPa, preferably 0.085 ~ 0.095MPa.
5. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, in alkoxylation, alkyl acrylate and low-carbon alcohol mol ratio are 1: 1 ~ 1: 2, and solid alkali consumption is the 0.5wt% ~ 2wt% of alkyl acrylate quality, and temperature of reaction is 0 ~ 80 DEG C; In fresh low-carbon alcohol stream stock, fresh propylene acid alkyl ester stream stock, water-content is all lower than 0.03%.
6. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, step 2) after dehydrogenation rectifying tower (6) is stable, each stream plume rate is alkoxylation feed liquid stream stock (5) is 480-500kg/h, light constituent material stream (7) is 105-110kg/h, and heavy constituent material stream (8) is 392-395kg/h.
7. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, step 3) after refining rectifying tower (9) is stable, each stream plume rate component materials stream stock (8) of attaching most importance to is 390-395kg/h, high boiling material (11) for 3.7-7.28kg/h, 3-methoxy methyl propionate product flow stock (10) be 385.69-390.00kg/h.
8. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, the procurement process of solid base catalyst is as follows: be dissolved in by alkali metal alcoholates in corresponding alcohol, solid carrier is joined in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2 ~ 12h; After backflow terminates, be cooled to room temperature, by toluene wash, the solid matter obtained vacuum-drying 5h at 60 ~ 80 DEG C obtained solid base catalyst; Described solid carrier is silicon oxide or siliceous molecular sieve, molecular sieve preferred MCM-41, SBA-15, ZSM-5.
The alcohol that correspondence refers to use sets according to alkali metal alcoholates, if alkali metal alcoholates is sodium methylate, corresponding alcohol is methyl alcohol; If alkali metal alcoholates is sodium ethylate or potassium ethylate, corresponding alcohol is ethanol; The like.
9. the preparation method of the above-mentioned 8 3-alkoxypropan acid alkyl esters provided, wherein, described alkali metal alcoholates is sodium methylate or sodium ethylate or potassium methylate or potassium ethylate; The quality of described alkali metal alcoholates is the 10-50% of solid carrier quality.
10. the preparation method of the above-mentioned 1 3-alkoxypropan acid alkyl ester provided, wherein, the alkyl alcohol of described low-carbon alcohol to be carbonatoms be 1-6, preferably adopts carbonatoms to be the alkyl alcohol of 1-4; Further, adopt the alkyl alcohol of carbon atom numerical digit 1-3, preferably adopt methyl alcohol or ethanol; Alkyl acrylate is methyl acrylate or ethyl propenoate.
Relative to the preparation method of traditional 3-alkoxypropan acid alkyl ester, object of the present invention is intended to by reaction and separation processes flow process minute design, improves the service efficiency of reactant and catalyzer, Loss reducing.According to restrictions such as reaction raw materials provided by the present invention, catalyzer, reaction conditionss, through corresponding steps, obtain target product, achieve the goal.
Beneficial effect of the present invention:
1. the present invention is by selecting solid base catalyst, and optimize reaction raw materials consumption and reaction conditions, reaction product is separated through 2 rectifying tower, and massfraction reaches more than 99.5%, and all higher than the purity that prior art obtains, whole reaction process is simple, easy handling.
2. the present invention use raw material, as the solid alkali of catalyzer after rectifying tower Separation and Recovery, do not need through reprocessing, directly can again put into recycle in reaction, avoid the use of acid neutralizing agent, considerably increase the utilising efficiency of raw material and catalyzer, reduce the loss of raw material and catalyzer, reduce production cost, do not cause environmental pollution.
3. the whole process of the present invention all can realize Automated condtrol, and reaction process is precisely controlled, reduces human cost, improves reaction efficiency, adapts to large-scale commercial production.
Accompanying drawing explanation
The heterogeneous catalysis alkoxylation process flow sheet of Fig. 1: 3-alkoxypropan acid alkyl ester
Wherein, 1-low-carbon alcohol stream stock; 2-alkyl acrylate stream stock; 3-solid base catalyst; 4-alkoxylation device; 5-alkoxylation feed liquid stream stock; 6-takes off light rectifying tower; 7-takes off the unreacted low-carbon alcohol of light rectifying tower recovered overhead and alkyl acrylate light constituent material stream; 8-takes off light tower bottom of rectifying tower mainly containing the heavy constituent material stream of product 3-alkoxypropan acid alkyl ester; 9-refines rectifying tower; The residual high boiling material of 10-still; 11-3-alkoxypropan acid alkyl ester product flow stock.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and the experimental technique of unreceipted actual conditions in the following example, usually according to the known approaches of this area.
Embodiment:
Alkoxylation body in following examples amasss 3m
3; De-light rectifying tower and refining rectifying tower diameter are 500mm.
Embodiment 1:
10kg sodium methylate is dissolved in 200kg methyl alcohol, 20kgMCM-41 is joined in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2h; After backflow terminates, be cooled to room temperature, after 200kg toluene wash 3 times, the solid matter obtained vacuum-drying 5h at 80 DEG C is obtained the solid base catalyst (sodium methylate content is the mass ratio of sodium methylate and carrier MCM-41) of sodium methylate content 50%.
At 3m
3alkoxylation device in, add fresh propylene acid methyl esters 1200kg, fresh methanol 893kg, 50% sodium methoxide catalyst 6kg of MCM-41 load, 2h is reacted at 30 DEG C, after reaction terminates, filtering catalyst, reaction product is through gas chromatographic analysis, methyl acrylate, methyl alcohol, 3-methoxy methyl propionate become to be respectively 0.11%, 20.68%, 78.91% and 0.3% with the quality group of high boiling material, the transformation efficiency of methyl acrylate is 99.81%, and the yield of methoxy methyl propionate is 99.29%.The alkoxylation liquid obtained is continuously separated through dehydrogenation rectifying tower and refining rectifying tower successively with the flow rate of 500kg/h, refining rectifying tower obtains product methoxy methyl propionate from refining rectifying tower overhead product after reaching and stablizing, and massfraction reaches 99.90%.
Rectifying tower operating parameters: de-light theoretical number of plates of rectifying tower is 12, reflux ratio 0.45, vacuum tightness 0.08MPa, feed entrance point the 6th block of column plate; Refining theoretical number of plates of rectifying tower is 9, reflux ratio 0.41, vacuum tightness 0.09MPa, feed entrance point the 7th block of column plate.
Rectifying tower reaches each stream plume rate after stablizing in table 1.
Table 1
Embodiment 2:
10kg potassium methylate is dissolved in 100kg methyl alcohol, 100kgSBA-15 is joined in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2h; After backflow terminates, be cooled to room temperature, after 100kg toluene wash 3 times, the solid matter obtained vacuum-drying 5h at 80 DEG C is obtained the solid base catalyst (potassium methylate content is the mass ratio of potassium methylate and carrier S BA-15) of potassium methylate content 10%.
At 3m
3alkoxylation device in, add fresh propylene acid methyl esters 1780kg, fresh methanol 268.1kg, and the mixture 429.2kg of acrylic acid methyl esters and methyl alcohol, wherein methyl acrylate 20kg, methyl alcohol 401.9kg, the consumption of total methyl acrylate, methyl alcohol is 1800kg and 676kg respectively.10% potassium methylate catalyzer 27kg of SBA-15 load, 0.2h is reacted at 80 DEG C, after reaction terminates, filter out catalyzer, reaction product is through gas chromatographic analysis, methyl acrylate, methyl alcohol, 3-methoxy methyl propionate become to be respectively 0.51%, 20.08%, 78.91% and 0.5% with the quality group of high boiling material, and the transformation efficiency of methyl acrylate is 99.13%, and the yield of methoxy methyl propionate is 98.27%.The alkoxylation liquid obtained is continuously separated through dehydrogenation rectifying tower and refining rectifying tower successively with the flow rate of 500kg/h, and rectifying tower obtains product methoxy methyl propionate from treating tower overhead product after reaching and stablizing, and massfraction reaches 99.75%.
Rectifying tower operating parameters: de-light theoretical number of plates of rectifying tower is 10, reflux ratio 1.0, vacuum tightness 0.085MPa, feed entrance point the 5th block of column plate; Refining theoretical number of plates of rectifying tower is 8, reflux ratio 0.6, vacuum tightness 0.09MPa, feed entrance point the 6th block of column plate.
Rectifying tower reaches each stream plume rate after stablizing in table 2.
Table 2
Embodiment 3:
20kg potassium ethylate is dissolved in 700kg dehydrated alcohol, 100kgZSM-5 is joined in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2h; After backflow terminates, be cooled to room temperature, after 100kg toluene wash 3 times, the solid matter obtained vacuum-drying 5h at 80 DEG C obtained the solid base catalyst (potassium ethylate is containing the mass ratio for potassium ethylate and carrier ZSM-5) of potassium ethylate content 20%.
At 5m
3alkoxylation device in, add fresh propylene acetoacetic ester 2000kg, 20% potassium ethylate catalyzer 40kg of ZSM-5 load, 1288kg fresh ethanol being dripped at 0 DEG C enters in reactor, time for adding is 4h altogether, dropwise rear insulation reaction 2h, after reaction terminates, filter out catalyzer, reaction product is through gas phase chromatographic analysis, ethyl propenoate, ethanol, 3-ethoxyl ethyl propionate becomes to be respectively 0.41% with the quality group of high boiling material, 20.18%, 79.01% and 0.4%, the transformation efficiency of ethyl propenoate is 99.25%, the yield of 3-ethoxyl ethyl propionate is 98.53%.The alkoxylation liquid obtained is continuously separated through dehydrogenation rectifying tower and refining rectifying tower successively with the flow rate of 500kg/h, and rectifying tower obtains product 3-ethoxyl ethyl propionate from treating tower overhead product after reaching and stablizing, and massfraction reaches 99.62%.
Rectifying tower operating parameters: de-light theoretical number of plates of rectifying tower is 12, reflux ratio 1.2, vacuum tightness 0.085MPa, feed entrance point the 4th block of column plate; Refining theoretical number of plates of rectifying tower is 12, reflux ratio 0.8, vacuum tightness 0.085MPa, feed entrance point the 7th block of column plate.
Rectifying tower reaches each stream plume rate after stablizing in table 3.
Table 3
Embodiment 4:
20kg sodium ethylate is dissolved in 500kg dehydrated alcohol, by 50kgSiO
2join in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2h; After backflow terminates, be cooled to room temperature, after 100kg toluene wash 3 times, (sodium ethylate content is sodium ethylate and carrier S iO the solid matter obtained vacuum-drying 5h at 80 DEG C to be obtained the solid base catalyst of sodium ethylate content 40%
2mass ratio).
At 3m
3alkoxylation device in, add fresh propylene acetoacetic ester 1780kg, the mixture 248.1kg of Propylene recovery acetoacetic ester and ethanol, wherein vinylformic acid ethanol 20kg, ethanol 225.8kg (1: 3).SiO
2the sodium ethylate catalyzer 18kg of load, 1274.2kg fresh ethanol being dripped at 50 DEG C enters in reactor, time for adding is 2h altogether, dropwise rear insulation reaction 2h, after reaction terminates, filter out catalyzer, reaction product is through gas phase chromatographic analysis, ethyl propenoate, ethanol, 3-ethoxyl ethyl propionate become to be respectively 0.31%, 20.48%, 78.91% and 0.3% with the quality group of high boiling material, the transformation efficiency of ethyl propenoate is 99.43%, the transformation efficiency of ethyl propenoate is 99.45%, and the yield of ethoxyl ethyl propionate is 98.88%.The alkoxylation liquid obtained is continuously separated through dehydrogenation rectifying tower and refining rectifying tower successively with the flow rate of 500kg/h, and rectifying tower obtains product 3-ethoxyl ethyl propionate from treating tower overhead product after reaching and stablizing, and massfraction can reach 99.76%.
Rectifying tower operating parameters: de-light theoretical number of plates of rectifying tower is 14, reflux ratio 0.6, vacuum tightness 0.09MPa, feed entrance point the 4th block of column plate; Refining rectifying tower plates number is 10, reflux ratio 1.0, vacuum tightness 0.095MPa, feed entrance point the 6th block of column plate.Rectifying tower reaches each stream plume rate after stablizing in table 4.
Table 4
Can know; above-described embodiment is only in order to illustrate the illustrative embodiments that inventive principle adopts; but the present invention is not limited only to this; those skilled in the art are not departing under real situation of the present invention; can make various improvement and change, these improve and change and also belong to protection scope of the present invention.
Claims (10)
1. the preparation method of a 3-alkoxypropan acid alkyl ester, it is characterized in that: the method is carried on the solid alkali that solid carrier obtains with alkali metal alcoholates be catalyzer, with alkyl acrylate and low-carbon alcohol for raw material, three mixes rear generation heterogeneous catalysis alkoxylation, then be separated and obtain 3-alkoxypropan acid alkyl ester product, specifically comprise the steps: 1) by fresh low-carbon alcohol stream stock (1), fresh propylene acid alkyl ester stream stock (2) and solid base catalyst (3), join in alkoxylation device (4), there is heterogeneous catalysis alkoxylation, reaction feed liquid stream stock (5) containing unreacted low-carbon alcohol, alkyl acrylate and product 3-alkoxypropan acid alkyl ester is obtained after reaction terminates,
2) alkoxylation feed liquid stream stock (5) is separated in de-light rectifying tower (6), obtain unreacted low-carbon alcohol and alkyl acrylate light constituent material stream (7) in recovered overhead, obtain mainly containing the heavy constituent material stream (8) of product 3-alkoxypropan acid alkyl ester in tower reactor;
3) the main heavy constituent material stream (8) containing product 3-alkoxypropan acid alkyl ester is separated in refining rectifying tower (9), obtaining 3-alkoxypropan acid alkyl ester product flow stock (11) of massfraction more than 99.5% at tower top, is high boiling material (10) in tower reactor.
2. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, it is characterized in that: step 2) after alkoxylation feed liquid stream stock (5) is separated in de-light rectifying tower (6), the unreacted low-carbon alcohol that tower top obtains and alkyl acrylate light constituent material stream (7), enter alkoxylation device (4) with fresh low-carbon alcohol stream stock (1), fresh propylene acid alkyl ester stream stock (2) after merging, be again cycled to used in alkoxylation step.
3. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, is characterized in that: step 2) the required theoretical plate number of de-light rectifying tower (6) is 6 ~ 20 pieces, is preferably 10 ~ 14 pieces; Required reflux ratio 0.1 ~ 7, is preferably 0.45 ~ 1.2; Required vacuum tightness is 0.05 ~ 0.095MPa, is preferably 0.08 ~ 0.09MPa.
4. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, is characterized in that: step 3) the required theoretical plate number of refining rectifying tower (9) is 6 ~ 20 pieces, preferably 8 ~ 12 pieces; Required reflux ratio 0.1 ~ 10, preferably 0.4 ~ 1.0; Required vacuum tightness is 0.07 ~ 0.1MPa, preferably 0.085 ~ 0.095MPa.
5. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, it is characterized in that: in alkoxylation, alkyl acrylate and low-carbon alcohol mol ratio are 1: 1 ~ 1: 2, solid alkali consumption is the 0.5wt% ~ 2wt% of alkyl acrylate quality, and temperature of reaction is 0 ~ 80 DEG C; In fresh low-carbon alcohol stream stock (1), fresh propylene acid alkyl ester stream stock (2), water-content is all lower than 0.03%.
6. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, it is characterized in that: step 2) after dehydrogenation rectifying tower (6) is stable, each stream plume rate is alkoxylation feed liquid stream stock (5) is 480-500kg/h, light constituent material stream (7) is 105-110kg/h, and heavy constituent material stream (8) is 392-395kg/h.
7. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, it is characterized in that: step 3) after refining rectifying tower (9) is stable, each stream plume rate component materials stream stock (8) of attaching most importance to is 390-395kg/h, high boiling material (11) for 3.7-7.28kg/h, 3-methoxy methyl propionate product flow stock (10) be 385.69-390.00kg/h.
8. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, it is characterized in that: the procurement process of solid base catalyst (3) is as follows: alkali metal alcoholates is dissolved in corresponding alcohol, solid carrier is joined in above-mentioned alcoholic solution, add the toluene with quality such as alcohol simultaneously, in a nitrogen atmosphere, stirring and refluxing 2 ~ 12h; After backflow terminates, be cooled to room temperature, by toluene wash, the solid matter obtained vacuum-drying 5h at 60 ~ 80 DEG C obtained solid base catalyst (3); Described solid carrier is silicon oxide or siliceous molecular sieve, molecular sieve preferred MCM-41, SBA-15, ZSM-5.
9. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 8, is characterized in that: described alkali metal alcoholates is sodium methylate or sodium ethylate or potassium methylate or potassium ethylate; The quality of described alkali metal alcoholates is the 10-50% of solid carrier quality.
10. the preparation method of 3-alkoxypropan acid alkyl ester according to claim 1, is characterized in that: the alkyl alcohol of described low-carbon alcohol to be carbonatoms be 1-6, preferably adopts carbonatoms to be the alkyl alcohol of 1-4; Further, adopt the alkyl alcohol of carbon atom numerical digit 1-3, preferably adopt methyl alcohol or ethanol; Alkyl acrylate is methyl acrylate or ethyl propenoate.
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| CN112279764A (en) * | 2019-07-24 | 2021-01-29 | 万华化学集团股份有限公司 | Preparation method of ethyl 3-ethoxypropionate |
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