CN105037151B - Preparation method of 3-alkoxy alkyl propionate - Google Patents
Preparation method of 3-alkoxy alkyl propionate Download PDFInfo
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- CN105037151B CN105037151B CN201510289293.4A CN201510289293A CN105037151B CN 105037151 B CN105037151 B CN 105037151B CN 201510289293 A CN201510289293 A CN 201510289293A CN 105037151 B CN105037151 B CN 105037151B
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- acid alkyl
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- alkoxylation
- alkoxypropan
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 15
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 239000002253 acid Substances 0.000 claims description 49
- 125000005907 alkyl ester group Chemical group 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 12
- 150000001340 alkali metals Chemical class 0.000 claims description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 9
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 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
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000006206 glycosylation reaction Methods 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 35
- -1 alkali metal alkoxide Chemical class 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DKJCSMHIPYRALV-UHFFFAOYSA-N methoxymethyl propanoate Chemical compound CCC(=O)OCOC DKJCSMHIPYRALV-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- SSVFMICWXDVRQN-UHFFFAOYSA-N ethanol;sodium Chemical compound [Na].CCO SSVFMICWXDVRQN-UHFFFAOYSA-N 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- YSIKHBWUBSFBRZ-UHFFFAOYSA-N 3-methoxypropanoic acid Chemical class COCCC(O)=O YSIKHBWUBSFBRZ-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VXJPCEOTZNHHOA-UHFFFAOYSA-N [K].OC Chemical compound [K].OC VXJPCEOTZNHHOA-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity 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
- 238000001704 evaporation Methods 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
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- YWOITFUKFOYODT-UHFFFAOYSA-N methanol;sodium Chemical compound [Na].OC YWOITFUKFOYODT-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 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, is related to a kind of preparation method of 3- alkoxypropans acid alkyl ester.
Background technology
3- methoxy methyl propionates and 3- ethoxyl ethyl propionates are the organic solvents of environmental protection, are widely used in electricity
The industries such as son, cleaning, coating, printing-ink, while and organic synthesiss and the important intermediate in pharmaceuticals industry.
Patent CN101906038A discloses the method for preparing 3- methoxy methyl propionates by 1,3-PD catalysis oxidation,
The method is needed to use oxygen in course of reaction, is existed larger using the metal-oxide of carried noble metal gold or palladium as catalyst
Potential safety hazard, and the highest yield only 53% of 3- methoxy methyl propionates.
Document [Qin Bingchang, etc. chemical industry is applied, 2007,36 (6)：596-598.] report acrylic acid methyl ester. and methanol exists
3- methoxy methyl propionates are prepared under the catalytic action of Feldalat NM, excessive 1.2 times in methanol, Feldalat NM consumption is acrylic acid methyl ester.
The 1.3% of quality, reacts 3.5h at 50 DEG C, after the completion of reaction, with glacial acetic acid and Feldalat NM, 3- methoxy methyl propionates
Yield can reach 97%.Document [Zhang Jibo, etc. Jilin Institute of Chemical Technology journal, 2011,28 (3)：1-3.] first by sodium hydroxide,
Methanol and anhydrous sodium sulfate prepare Feldalat NM at 65 DEG C, and then acrylic acid methyl ester. is added in said mixture, wait anti-
After should terminating, then with sodium bisulfate and Feldalat NM.Excessive 1.5 times in methanol, sodium hydroxide concentration is 10%, is reacted at 55 DEG C
The yield of 6h, 3- methoxy methyl propionate can reach more than 97%.Patent CN1258518C discloses a kind of 3- methoxypropionic acids
Feldalat NM or Feldalat KM that methanol and quality are methanol 5.3%~14.3% are being reacted by the preparation method of methyl ester, the method first
Stirring more than 10h in device, then under the conditions of methanol is excessive 2~3 times, reacts 2~6h, after reaction terminates, uses at 45~60 DEG C
Concentrated sulphuric acid and strong phosphoric acid catalyst neutralisation, the yield of methoxy methyl propionate are up to 91.4%.Patent CN101423475B is public
One kind is opened in the presence of alkali metal or alkali metal alkoxide catalyst, ethyl acrylate and ethanol synthesis obtain 3- ethoxy-cs
The method of acetoacetic ester.It it is 0~80 DEG C in reaction temperature, ethanol is 2~3: 1 with the mol ratio of ethyl acrylate, catalyst amount
For the 1.5%~3% of ethyl acrylate quality, under conditions of the response time is 1~16h, the yield of 3- ethoxyl ethyl propionates
It is up to 89.9%.After the completion of reaction, using concentrated sulphuric acid, acetic acid, hydrochloric acid, phosphoric acid, formic acid or nitric acid catalyst neutralisation.
The method that above-mentioned employing alkali metal alkoxide catalyst prepares 3- methoxy methyl propionates and 3- ethoxyl ethyl propionates,
Because catalyst is mixed with reactant mixture, belong to homogeneous reaction, be required to, with acid neutralization base catalyst, not only result in catalyst not
Can reuse, improve production cost, and the sodium salt for being formed needs further to process, and have waste water to produce, pollute environment.
The content of the invention
Present invention aim in the existing preparation method of solution, 3- alkoxypropan acid alkyl ester yields are not high or produce into
The disagreeableness problem of this higher, environment, there is provided a kind of alkoxylate prepares the new method of 3- alkoxypropan acid alkyl esters.
To solve the above problems, the present invention is realized using following technical proposals
1. the present invention provides a kind of preparation method of 3- alkoxypropans acid alkyl ester, and the method is carried on alkali metal alcoholates
The solid base obtained on solid carrier is catalyst, with alkyl acrylate and low-carbon alcohols as raw material, is occurred non-after three's mixing
Homogeneous catalysis alkoxylation, is then peeled off obtaining 3- alkoxypropan acid alkyl ester products, specifically includes following steps：1) will
Fresh low-carbon alcohols stream stock, fresh propylene acid alkyl ester stream stock and solid base catalyst, are added in alkoxylation device, occur
Heterogeneous catalysis alkoxylation；Reaction is obtained containing unreacted low-carbon alcohols, alkyl acrylate and product 3- after terminating
The reaction feed liquid stream stock of alkoxypropan acid alkyl ester；
2) alkoxylation feed liquid stream stock is separated in de-light rectification column, obtains unreacted low in recovered overhead
Carbon alcohol and alkyl acrylate light component material stream, obtain the restructuring of the mainly alkoxypropans of 3- containing product acid alkyl ester in tower reactor
Divide material stream；
3) the heavy constituent material stream of the main alkoxypropan acid alkyl esters of 3- containing product is separated in refined rectifying column, in tower
Top obtains the 3- alkoxypropan acid alkyl ester product stream stocks of mass fraction more than 99.5%, is high-boiling components in tower reactor.
Low-carbon alcohols stream stock refers to the stream stock of low-carbon alcohols liquid formation, represents same substance with low-carbon alcohols；Acrylic acid alkyl
Ester stream stock refers to the stream stock of alkyl acrylate formation, represents same substance with alkyl acrylate.
2. it is above-mentioned 1 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, step 2) alkoxylation feed liquid
After stream stock is separated in de-light rectification column, unreacted low-carbon alcohols and alkyl acrylate light component material that tower top is obtained
Stream stock, is entered alkoxylation device, recirculates and use after being merged with fresh low-carbon alcohols stream stock, fresh propylene acid alkyl ester stream stock
In alkoxylation step.
3. it is above-mentioned 1 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, step 2) de-light rectification column (6) institute
Theoretical cam curve is needed to be 6~20 pieces, preferably 9~14 pieces；Required reflux ratio 0.1~7, preferably 0.4~1.2；Required vacuum
Spend for 0.05~0.095MPa, preferably 0.08~0.09MPa.
4. the preparation method of the above-mentioned 1 3- alkoxypropan acid alkyl esters for providing, wherein, step 3) refined rectifying column (9) institute
Theoretical cam curve is needed to be 6~20 pieces, preferably 9~14 pieces；Required reflux ratio 0.1~10, preferably 0.4~1.0；Required vacuum is
0.07~0.1MPa, preferably 0.085~0.095MPa.
5. it is above-mentioned 1 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, alkyl acrylate in alkoxylation
Base ester is 1: 1~1: 2 with low-carbon alcohols mol ratio, 0.5wt%~2wt% of the solid base consumption for alkyl acrylate quality, instead
Temperature is answered to be 0~80 DEG C；In fresh low-carbon alcohols stream stock, fresh propylene acid alkyl ester stream stock, water content is below 0.03%.
6. the preparation method of the above-mentioned 1 3- alkoxypropan acid alkyl esters for providing, wherein, step 2) dehydrogenation rectifying column (6) is steady
After fixed, each stream plume rate is 480-500kg/h for alkoxylation feed liquid stream stock (5), and light component material stream (7) is 105-
110kg/h, heavy constituent material stream (8) are 392-395kg/h.
7. the preparation method of the above-mentioned 1 3- alkoxypropan acid alkyl esters for providing, wherein, step 3) refined rectifying column (9) is steady
After fixed, each stream plume rate component materials stream stock (8) of attaching most importance to are 390-395kg/h, and high-boiling components (11) are 3.7-7.28kg/h, 3- first
Epoxide methyl propionate product stream stock (10) is 385.69-390.00kg/h.
8. it is above-mentioned 1 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, the acquisition process of solid base catalyst
It is as follows：Alkali metal alcoholates are dissolved in corresponding alcohol, solid carrier is added in above-mentioned alcoholic solution, while the matter such as addition and alcohol
The toluene of amount, in a nitrogen atmosphere, is stirred at reflux 2~12h；After backflow terminates, room temperature is cooled to, is washed with toluene, will be obtained
Solid matter 5h be vacuum dried at 60~80 DEG C obtain solid base catalyst；The 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 is set according to alkali metal alcoholates, if alkali metal alcoholates are Feldalat NM, corresponding
Alcohol is methanol；If alkali metal alcoholates are Sodium ethylate or potassium ethoxide, corresponding alcohol is ethanol；The like.
9. it is above-mentioned 8 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, the alkali metal alcoholates be Feldalat NM
Or Sodium ethylate or Feldalat KM or potassium ethoxide；10-50% of the quality of the alkali metal alcoholates for solid carrier quality.
10. it is above-mentioned 1 provide 3- alkoxypropan acid alkyl esters preparation method, wherein, the low-carbon alcohols be carbon number
For the alkylol of 1-6, it is preferred to use alkylol of the carbon number for 1-4；Further, using the alkyl of carbon atom numerical digit 1-3
Alcohol, it is preferred to use methanol or ethanol；Alkyl acrylate is acrylic acid methyl ester. or ethyl acrylate.
Relative to the preparation method of traditional 3- alkoxypropans acid alkyl ester, the purpose of the present invention is intended to by reacting and separating
Flow process minute design, improves the service efficiency of reactant and catalyst, reduces loss.It is former according to reaction provided by the present invention
Material, catalyst, reaction condition etc. are limited, and through corresponding steps, obtained target product, are achieved the goal.
Beneficial effects of the present invention：
1. the present invention is by selecting solid base catalyst, optimization reaction raw materials consumption and reaction condition, and product is through 2
Secondary rectifying column is separated, and mass fraction reaches more than 99.5%, is above the purity of prior art acquisition, whole course of reaction letter
It is single, it is easy to operate.
2. the present invention is used raw material, as catalyst solid base after rectifying column separation and recovery, it is not necessary to pass through
Reprocessing, can recycle in directly putting into reaction again, it is to avoid the use of acid neutralizing agent, considerably increase raw material and
The utilization ratio of catalyst, reduces the loss of raw material and catalyst, reduces production cost, does not cause environmental pollution.
3. whole process of the present invention is capable of achieving Automated condtrol, and course of reaction is precisely controllable, reduces human cost, carries
High reaction efficiency, adapts to large-scale industrial production.
Description of the drawings
Fig. 1：The heterogeneous catalysis alkoxylation process chart of 3- alkoxypropan acid alkyl esters
Wherein, 1- low-carbon alcohols stream stock；2- alkyl acrylate stream stocks；3- solid base catalysts；4- alkoxylation devices；
5- alkoxylation feed liquid stream stocks；6- de-light rectification columns；The unreacted low-carbon alcohols of 7- de-light rectification column recovered overheads and propylene
Acid alkyl ester light component material stream；The heavy constituent thing of the main alkoxypropans of 3- containing the product acid alkyl ester of 8- de-light rectification columns tower reactor
Stream stock；9- refines rectifying column；The residual high-boiling components of 10- kettles；11-3- alkoxypropan acid alkyl ester product stream stocks.
Specific embodiment
With reference to embodiment, the present invention will be further described, the experiment side of unreceipted actual conditions in the following example
Method, generally according to the known approaches of this area.
Specific embodiment：
Alkoxylation body product 3m in following examples3；De-light rectification column is with refined rectifying column diameter
500mm。
Embodiment 1：
10kg Feldalat NMs are dissolved in 200kg methanol, 20kgMCM-41 are added in above-mentioned alcoholic solution, at the same add with
The toluene of the quality such as alcohol, in a nitrogen atmosphere, is stirred at reflux 2h；After backflow terminates, room temperature is cooled to, 3 is washed with 200kg toluene
After secondary, the solid matter for obtaining is vacuum dried at 80 DEG C the solid base catalyst (methanol that 5h obtains methanol sodium content 50%
Sodium content is the mass ratio of Feldalat NM and carrier MCM-41).
In 3m3Alkoxylation device in, add fresh propylene acid methyl ester 1200kg, fresh methanol 893kg, MCM-41
50% sodium methoxide catalyst 6kg of load, reacts 2h at 30 DEG C, after reaction terminates, filtering catalyst, and product is through gas
The quality group of analysis of hplc, acrylic acid methyl ester., methanol, 3- methoxy methyl propionates and high-boiling components into respectively 0.11%,
20.68%th, 78.91% and 0.3%, the conversion ratio of acrylic acid methyl ester. is 99.81%, and the yield of methoxy methyl propionate is
99.29%.The alkoxylation liquid for obtaining sequentially passes through dehydrogenation rectifying column with the flow rate of 500kg/h and refined rectifying column is continuous
Separate, refined rectifying column to reach and obtain product methoxy methyl propionate, quality point from refined rectifying column tower top distillation after stablizing
Number reaches 99.90%.
Rectifying column operating parameter：De-light rectification column theoretical cam curve is 12, reflux ratio 0.45, vacuum 0.08MPa, charging
The 6th block of position column plate；Refined theoretical number of plates of rectifying tower is 9, reflux ratio 0.41, vacuum 0.09MPa, the 7th piece of feed entrance point
Column plate.
Rectifying column reaches each stream plume rate after stablizing and is shown in Table 1.
Table 1
Embodiment 2：
10kg Feldalat KMs are dissolved in 100kg methanol, 100kg SBA-15 are added in above-mentioned alcoholic solution, while adding
With the toluene of the quality such as alcohol, in a nitrogen atmosphere, 2h is stirred at reflux；After backflow terminates, room temperature is cooled to, is washed with 100kg toluene
After washing 3 times, the solid matter for obtaining is vacuum dried at 80 DEG C the solid base catalyst (first that 5h obtains methanol potassium content 10%
Alcohol potassium content is the mass ratio of Feldalat KM and carrier S BA-15).
In 3m3Alkoxylation device in, add fresh propylene acid methyl ester 1780kg, fresh methanol 268.1kg, and
The mixture 429.2kg of acrylic acid methyl ester and methanol, wherein acrylic acid methyl ester. 20kg, methanol 401.9kg amount to acrylic acid
Methyl ester, the consumption of methanol are 1800kg and 676kg respectively.10% Feldalat KM catalyst 27kg of SBA-15 loads, at 80 DEG C
Reaction 0.2h, after reaction terminates, filters out catalyst, and product is through gas chromatographic analysiss, acrylic acid methyl ester., methanol, 3-
The quality group of methoxy methyl propionate and high-boiling components into respectively 0.51%, 20.08%, 78.91% and 0.5%, acrylic acid first
The conversion ratio of ester is 99.13%, and the yield of methoxy methyl propionate is 98.27%.The alkoxylation liquid for obtaining with
The flow rate of 500kg/h sequentially passes through dehydrogenation rectifying column and refined rectifying column is continuously separated, and rectifying column is reached after stablizing from treating column
Overhead obtains product methoxy methyl propionate, and mass fraction reaches 99.75%.
Rectifying column operating parameter：De-light rectification column theoretical cam curve is 10, reflux ratio 1.0, vacuum 0.085MPa, charging
The 5th block of position column plate；Refined theoretical number of plates of rectifying tower is 8, reflux ratio 0.6, vacuum 0.09MPa, the 6th piece of tower of feed entrance point
Plate.
Rectifying column reaches each stream plume rate after stablizing and is shown in Table 2.
Table 2
Embodiment 3：
20kg potassium ethoxides are dissolved in 700kg dehydrated alcohol, 100kg ZSM-5 are added in above-mentioned alcoholic solution, while
The toluene of the quality such as addition and alcohol, in a nitrogen atmosphere, is stirred at reflux 2h；After backflow terminates, room temperature is cooled to, 100kg first is used
After benzene washs 3 times, the solid matter for obtaining is vacuum dried at 80 DEG C the catalyzed by solid base that 5h obtains ethanol potassium content 20%
Agent (potassium ethoxide is containing the mass ratio for potassium ethoxide and carrier ZSM-5).
In 5m3Alkoxylation device in, add fresh propylene acetoacetic ester 2000kg, ZSM-5 load 20% ethanol
Potassium catalyst 40kg, at 0 DEG C enters 1288kg fresh ethanols Deca in reactor, and time for adding is 4h altogether, is dripped
Insulation reaction 2h after finishing, after reaction terminates, filters out catalyst, and product is through gas phase colour analysiss, ethyl acrylate, second
The quality group of alcohol, 3- ethoxyl ethyl propionates and high-boiling components into respectively 0.41%, 20.18%, 79.01% and 0.4%, propylene
The conversion ratio of acetoacetic ester is 98.53% for the yield of 99.25%, 3- ethoxyl ethyl propionates.The alkoxylation liquid for obtaining
Dehydrogenation rectifying column is sequentially passed through with the flow rate of 500kg/h and refined rectifying column is continuously separated, rectifying column reach it is stable after from refined
Column overhead distillation obtains product 3- ethoxyl ethyl propionates, and mass fraction reaches 99.62%.
Rectifying column operating parameter：De-light rectification column theoretical cam curve is 12, reflux ratio 1.2, vacuum 0.085MPa, charging
The 4th block of position column plate；Refined theoretical number of plates of rectifying tower is 12, reflux ratio 0.8, vacuum 0.085MPa, the 7th piece of feed entrance point
Column plate.
Rectifying column reaches each stream plume rate after stablizing and is shown in Table 3.
Table 3
Embodiment 4：
20kg Sodium ethylate is dissolved in 500kg dehydrated alcohol, by 50kg SiO2It is added in above-mentioned alcoholic solution, while plus
Enter the toluene with the quality such as alcohol, in a nitrogen atmosphere, be stirred at reflux 2h；After backflow terminates, room temperature is cooled to, 100kg toluene is used
After washing 3 times, the solid matter for obtaining is vacuum dried at 80 DEG C the solid base catalyst that 5h obtains ethanol sodium content 40%
(ethanol sodium content is Sodium ethylate and carrier S iO2Mass ratio).
In 3m3Alkoxylation device in, add fresh propylene acetoacetic ester 1780kg, Propylene recovery acetoacetic ester and ethanol
Mixture 248.1kg, wherein acrylic acid ethanol 20kg, ethanol 225.8kg (1: 3).SiO2The ethanol sodium catalyst of load
18kg, at 50 DEG C enters 1274.2kg fresh ethanols Deca in reactor, and time for adding is 2h altogether, is protected after completion of dropping
Temperature reaction 2h, after reaction terminates, filters out catalyst, and product is through gas phase colour analysiss, ethyl acrylate, ethanol, 3- second
The quality group of epoxide ethyl propionate and high-boiling components into respectively 0.31%, 20.48%, 78.91% and 0.3%, ethyl acrylate
Conversion ratio be 99.43%, the conversion ratio of ethyl acrylate is 99.45%, and the yield of ethoxyl ethyl propionate is 98.88%.
The alkoxylation liquid for obtaining sequentially passes through dehydrogenation rectifying column with the flow rate of 500kg/h and refined rectifying column is continuously separated, essence
Evaporating after tower reaches stably and product 3- ethoxyl ethyl propionates being obtained from treating column overhead, mass fraction can reach
99.76%.
Rectifying column operating parameter：De-light rectification column theoretical cam curve is 14, reflux ratio 0.6, vacuum 0.09MPa, charging
The 4th block of position column plate；Refined rectifying tower plates number is 10, reflux ratio 1.0, vacuum 0.095MPa, the 6th piece of tower of feed entrance point
Plate.Rectifying column reaches each stream plume rate after stablizing and is shown in Table 4.
Table 4
It is recognised that the illustrative embodiments that above-described embodiment is adopted only for illustrating inventive principle, but this
Bright to be not limited only to this, those skilled in the art can make various improvement and change under without departing from real situation of the present invention, this
A little improvement and change fall within protection scope of the present invention.
Claims (9)
1. a kind of preparation method of 3- alkoxypropans acid alkyl ester, it is characterised in that：The method is carried on solid with alkali metal alcoholates
The solid base obtained on body carrier is catalyst, with alkyl acrylate and low-carbon alcohols as raw material, is occurred non-equal after three's mixing
Phase catalysing any alkoxylation reacts, and is then peeled off obtaining 3- alkoxypropan acid alkyl ester products, specifically includes following steps：1) will be new
Fresh low-carbon alcohols stream stock (1), fresh propylene acid alkyl ester stream stock (2) and solid base catalyst (3), are added to alkoxylation device
(4), in, there is heterogeneous catalysis alkoxylation；Reaction is obtained containing unreacted low-carbon alcohols, acrylic acid alkyl after terminating
Reaction feed liquid stream stock (5) of ester and product 3- alkoxypropan acid alkyl esters；
2) alkoxylation feed liquid stream stock (5) is separated in de-light rectification column (6), obtains unreacted in recovered overhead
Low-carbon alcohols and alkyl acrylate light component material stream (7), obtain the mainly alkoxypropans of 3- containing product acid alkyl ester in tower reactor
Heavy constituent material stream (8)；
3) the heavy constituent material stream (8) of the main alkoxypropan acid alkyl esters of 3- containing product is separated in refined rectifying column (9),
Tower top obtains 3- alkoxypropans acid alkyl ester product stream stock (11) of mass fraction more than 99.5%, is high-boiling components in tower reactor
(10)；The low-carbon alcohols are methanol or ethanol；Alkyl acrylate is acrylic acid methyl ester. or ethyl acrylate.
2. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Step 2) alkoxylate is anti-
After answering feed liquid stream stock (5) to be separated in de-light rectification column (6), unreacted low-carbon alcohols and acrylic acid alkyl that tower top is obtained
Ester light component material stream (7), enters alcoxyl after merging with fresh low-carbon alcohols stream stock (1), fresh propylene acid alkyl ester stream stock (2)
Glycosylation reaction device (4), recirculates in alkoxylation step.
3. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Step 2) de-light rectification column
(6) theoretical cam curve needed for is 10~14 pieces；Required reflux ratio is 0.45~1.2；Required vacuum is 0.08~0.09MPa.
4. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Step 3) refined rectifying column
(9) theoretical cam curve needed for is 8~12 pieces；Required reflux ratio is 0.4~1.0；Required vacuum is 0.085~0.095MPa.
5. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Third in alkoxylation
Olefin(e) acid Arrcostab is 1 with low-carbon alcohols mol ratio:1~1:2, solid base consumption for alkyl acrylate quality 0.5wt%~
2wt%, reaction temperature are 0~80 DEG C；In fresh low-carbon alcohols stream stock (1), fresh propylene acid alkyl ester stream stock (2), water content is low
In 0.03%.
6. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Step 2) de-light rectification column
(6), after stable, each stream plume rate is 480-500kg/h for alkoxylation feed liquid stream stock (5), light component material stream (7)
For 105-110kg/h, heavy constituent material stream (8) is 392-395kg/h.
7. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Step 3) refined rectification
After tower (9) is stable, each stream plume rate component materials stream stock (8) of attaching most importance to are 390-395kg/h, and high-boiling components (10) are 3.7-
7.28kg/h, 3- alkoxypropan acid alkyl ester product stream stock (11) are 385.69-390.00kg/h.
8. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 1, it is characterised in that：Solid base catalyst (3)
Acquisition process it is as follows：Alkali metal alcoholates are dissolved in corresponding alcohol, solid carrier is added in above-mentioned alcoholic solution, while plus
Enter the toluene with the quality such as alcohol, in a nitrogen atmosphere, be stirred at reflux 2~12h；After backflow terminates, room temperature is cooled to, is washed with toluene
Wash, the solid matter for obtaining is vacuum dried into 5h at 60~80 DEG C and obtains solid base catalyst (3)；The solid carrier is oxygen
SiClx or siliceous molecular sieve, molecular sieve are MCM-41, SBA-15, ZSM-5.
9. the preparation method of the 3- alkoxypropan acid alkyl esters described in claim 8, it is characterised in that：The alkali metal alcoholates are
Feldalat NM or Sodium ethylate or Feldalat KM or potassium ethoxide；10-50% of the quality of the alkali metal alcoholates for solid carrier quality.
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| CN107413374B (en) * | 2017-05-26 | 2020-07-28 | 南京工业大学 | Solid base catalyst for synthesizing 3-alkoxy alkyl propionate |
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