CN114853592B - Method for preparing glycollic acid by hydrolyzing alkoxy acetate - Google Patents
Method for preparing glycollic acid by hydrolyzing alkoxy acetate Download PDFInfo
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- CN114853592B CN114853592B CN202110148663.8A CN202110148663A CN114853592B CN 114853592 B CN114853592 B CN 114853592B CN 202110148663 A CN202110148663 A CN 202110148663A CN 114853592 B CN114853592 B CN 114853592B
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- acetate
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 63
- -1 alkoxy acetate Chemical compound 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 85
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 230000002378 acidificating effect Effects 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 9
- 235000019439 ethyl acetate Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- 229960004275 glycolic acid Drugs 0.000 description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- ICPWFHKNYYRBSZ-UHFFFAOYSA-M 2-methoxypropanoate Chemical compound COC(C)C([O-])=O ICPWFHKNYYRBSZ-UHFFFAOYSA-M 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- MDEDOIDXVJXDBW-UHFFFAOYSA-N methoxymethyl acetate Chemical compound COCOC(C)=O MDEDOIDXVJXDBW-UHFFFAOYSA-N 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000005810 carbonylation reaction Methods 0.000 description 9
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 9
- 230000006315 carbonylation Effects 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004633 polyglycolic acid Substances 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 3
- 229940106681 chloroacetic acid Drugs 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- OORRCVPWRPVJEK-UHFFFAOYSA-N 2-oxidanylethanoic acid Chemical compound OCC(O)=O.OCC(O)=O OORRCVPWRPVJEK-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IWPATTDMSUYMJV-UHFFFAOYSA-N butyl 2-methoxyacetate Chemical compound CCCCOC(=O)COC IWPATTDMSUYMJV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- CKSRFHWWBKRUKA-UHFFFAOYSA-N ethyl 2-ethoxyacetate Chemical compound CCOCC(=O)OCC CKSRFHWWBKRUKA-UHFFFAOYSA-N 0.000 description 1
- JLEKJZUYWFJPMB-UHFFFAOYSA-N ethyl 2-methoxyacetate Chemical compound CCOC(=O)COC JLEKJZUYWFJPMB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FIABMSNMLZUWQH-UHFFFAOYSA-N propyl 2-methoxyacetate Chemical compound CCCOC(=O)COC FIABMSNMLZUWQH-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002407 tissue scaffold Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a method for preparing glycolic acid by hydrolyzing alkoxy acetate. The method comprises the steps of reacting raw materials containing alkoxyl acetate and water in the presence of an acidic molecular sieve catalyst to obtain glycolic acid; the alkoxy acetic ester is at least one selected from substances with structural formulas shown in a formula I; in formula I, R 1 、R 2 Independently selected from C 1 ～C 5 Any one of alkyl groups. The glycollic acid production method can be realized by using a traditional fixed bed reactor under normal pressure, and is very suitable for continuous production.
Description
Technical Field
The application relates to a method for preparing glycolic acid by hydrolyzing alkoxy acetate, belonging to the field of chemical product preparation.
Background
Glycolic acid (glycine), also known as glycolic acid (hydroxyacetic acid), is the simplest α -hydroxycarboxylic acid compound. Glycolic acid has a molecular structure containing both hydroxyl and carboxyl groups, and is capable of self-polymerization to form polyglycolic acid (PGA). The polyglycolic acid not only has good biocompatibility, but also has safe biodegradability. Therefore, the plastic material can be widely applied to medical surgical sutures, drug slow-release materials, degradable human tissue scaffolds and the like, and can also be used for producing common plastic products. Today, conventional nondegradable plastic products have caused serious environmental pollution, so biodegradable polyglycolic acid-based plastics are expected to solve this problem. Glycolic acid can be copolymerized with lactic acid, hydroxy propionic acid and other monomers to form a polymer material with excellent performance and wide application. In addition, glycolic acid is also an excellent chemical cleaner and cosmetic raw material.
The production and preparation method of the glycollic acid mainly comprises a chloroacetic acid hydrolysis method, a formaldehyde carbonylation method, an oxalate hydrogenation/hydrolysis method and the like. The chloroacetic acid hydrolysis method not only has large pollution in the preparation process of raw material chloroacetic acid, but also generates a large amount of waste salt in the hydrolysis process, has serious pollution and poor product quality, and is basically eliminated at present. The formaldehyde carbonylation method, although the raw materials are cheap and easy to obtain, needs to be carried out under the conditions of high temperature, high pressure, strong liquid acid and organic solvent; equipment is easy to corrode, the product purification difficulty is high, and the industrial production cost is high. The oxalate hydrogenation/hydrolysis method is to hydrogenate oxalate part into methyl glycolate, and then hydrolyze the methyl glycolate to prepare glycolic acid. However, on one hand, oxalate partial hydrogenation catalysts are still immature, low in conversion efficiency and poor in stability; on the other hand, the oxalate production flow is long and the cost is high; these problems severely limit the development of oxalate hydrogenation/hydrolysis processes.
Disclosure of Invention
According to the prior art glycolic acid (HOCH) 2 COOH) production technology, the invention develops a method for preparing glycolic acid by hydrolyzing alkoxy acetate. The method is particularly suitable for methylal in coal chemical production, and methoxy methyl acetate is generated through carbonylation reaction, and then glycollic acid is prepared through hydrolysis.
A method for preparing glycollic acid by hydrolyzing alkoxy acetate comprises the steps of reacting raw materials containing alkoxy acetate and water in the presence of an acidic molecular sieve catalyst to obtain glycollic acid;
the alkoxy acetic ester is at least one selected from substances with structural formulas shown in a formula I;
in formula I, R 1 、R 2 Independently selected from C 1 ～C 5 Any one of alkyl groups.
The application discloses a method for preparing glycolic acid by hydrolyzing alkoxyl acetate, which is to prepare glycolic acid by reacting raw materials alkoxyl acetate and water in a reaction zone loaded with an acidic molecular sieve catalyst under certain reaction conditions. The hydrolysis catalyst used in the application is a molecular sieve catalyst, and has long service life and high hydrolysis efficiency. The glycolic acid production method can be realized by using a traditional fixed bed reactor under normal pressure, and is very suitable for continuous production. The raw material alkoxy acetate can be prepared by a green and economical acetal carbonylation method. When the raw material in the application is methoxy methyl acetate, the three-step reaction combination of the reaction of preparing methylal by condensing methanol and formaldehyde, the reaction of preparing methoxy methyl acetate by carbonylation and the reaction of preparing glycolic acid by hydrolyzing methoxy methyl acetate can be used for efficiently, environmentally-friendly and economically converting the coal chemical industry platform substance methanol into glycolic acid.
Preferably, said R 1 Any one selected from methyl, ethyl, propyl and butyl;
the R is 2 Selected from any one of methyl, ethyl, propyl and butyl.
Specifically, the alkoxyl acetate is any one selected from methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate and ethyl ethoxyacetate.
Further preferably, the alkoxy acetate is methoxy methyl acetate.
In recent years, the reaction of methylal carbonylation to methyl methoxyacetate has received a lot of attention. The reaction is based on a molecular sieve catalyst, can be realized at a lower reaction temperature, and has high atom economy. The raw material methylal has high production efficiency, mature industrial technology and low price. In the application, the ether bond and the ester bond of the methoxy methyl acetate are hydrolyzed to prepare the glycollic acid, so that the glycollic acid becomes a green and economic glycollic acid production path.
Optionally, the acidic molecular sieve catalyst comprises an acidic molecular sieve.
Optionally, the acidic molecular sieve is at least one selected from an acidic MFI structure molecular sieve, an acidic FAU structure molecular sieve, an acidic FER structure molecular sieve, an acidic BEA structure molecular sieve, an acidic MOR structure molecular sieve, and an acidic MWW structure molecular sieve.
Preferably, the acidic molecular sieve is selected from any one of an acidic MFI structure molecular sieve and an acidic FER structure molecular sieve.
Optionally, the acidic molecular sieve is at least one selected from acidic ZSM-5 molecular sieve, acidic Y molecular sieve, acidic ZSM-35 molecular sieve, acidic beta molecular sieve, acidic mordenite, and acidic MCM-22 molecular sieve.
Preferably, the acidic molecular sieve is at least one selected from hydrogen-type ZSM-5 molecular sieve, hydrogen-type Y molecular sieve, hydrogen-type ZSM-35 molecular sieve, hydrogen-type beta molecular sieve, hydrogen-type mordenite and hydrogen-type MCM-22 molecular sieve.
Further preferably, the acidic molecular sieve is selected from any one of hydrogen-form ZSM-5 molecular sieve and hydrogen-form ZSM-35 molecular sieve.
Optionally, the atomic ratio of silicon to aluminum in the acidic molecular sieve is 3-500.
Specifically, the upper limit of the silicon to aluminum atomic ratio in the acidic molecular sieve is selected from 10, 20, 50, 100, 500; the lower limit of the silicon-aluminum atomic ratio in the acidic molecular sieve is selected from 3, 10, 20, 50 and 100.
Optionally, the acidic molecular sieve catalyst also contains a forming agent;
the forming agent is an oxide.
Optionally, the oxide is at least one selected from alumina and silica.
Optionally, in the acidic molecular sieve catalyst, the content of the forming agent is m, and the value range of m is more than 0 and less than or equal to 50wt%.
Specifically, the upper limit of the content of the forming agent in the acidic molecular sieve catalyst is selected from 10wt%, 20wt%, 40wt% and 50wt%; the lower limit of the content of the forming agent in the acidic molecular sieve catalyst is selected from 5wt%, 10wt%, 20wt% and 40wt%.
Preferably, the forming agent is present in the acidic molecular sieve catalyst in an amount of 15 to 25wt%.
Alternatively, the conditions of the reaction are:
the reaction temperature is 60-260 ℃;
the reaction pressure is 0.1-10 MPa;
the molar ratio of the alkoxy acetate to the water is 1:20-20:1;
the mass airspeed of the alkoxy acetic ester is 0.1 to 3h -1 。
Specifically, the upper limit of the reaction temperature is selected from 100 ℃, 150 ℃ and 260 ℃; the lower limit of the reaction temperature is selected from 60 ℃, 100 ℃ and 150 ℃.
The upper limit of the reaction pressure is selected from 0.3MPa, 0.5MPa, 1MPa, 4MPa and 10MPa; the lower limit of the reaction pressure is selected from 0.1MPa, 0.3MPa, 0.5MPa, 1MPa and 4MPa.
The upper limit of the molar ratio of alkoxyacetate to water is selected from 1:10, 1:8, 1:4, 1:2, 1:1, 10:1, 20:1; the lower limit of the molar ratio of alkoxyacetate to water is selected from 1:20, 1:10, 1:8, 1:4, 1:2, 1:1, 10:1.
The upper limit of the mass space velocity of the oxyacetate is selected from 0.3h -1 、1.0h -1 、3.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The lower limit of the mass space velocity of the alkoxyacetate is selected from 0.1h -1 、0.3h -1 、1.0h -1 。
Preferably, the conditions of the reaction are:
the reaction temperature is 130-260 ℃;
the reaction pressure is 0.1-0.3 MPa;
the molar ratio of the alkoxy acetate to the water is 1:2-1:8;
the mass airspeed of the alkoxy acetic ester is 0.3 to 1h -1 。
Optionally, the reaction is carried out in at least one fixed bed reactor;
a plurality of the fixed bed reactors are connected in series and/or parallel.
Optionally, the reaction is carried out in an inert atmosphere;
the inert atmosphere includes any one of nitrogen and inert gas.
In particular, the inert gas may be argon.
As used herein, "alkyl" refers to groups formed by the loss of any one of the hydrogen atoms from the molecule of an alkane compound, including cycloalkanes, straight chain alkanes, branched alkanes;
“C 1 ～C 5 the "subscript" refers to the number of carbon atoms contained in the group.
The beneficial effects that this application can produce include:
1) The hydrolysis catalyst used in the invention is a molecular sieve catalyst, and has long service life and high hydrolysis efficiency.
The glycollic acid production method can be realized by using a traditional fixed bed reactor under normal pressure, and is very suitable for continuous production. The raw material alkoxy acetate in the invention can be prepared by an environment-friendly and economical acetal carbonylation method.
2) When the raw material in the invention is methoxy methyl acetate, the three steps of reaction of preparing methylal by condensing methanol and formaldehyde, reaction of preparing methoxy methyl acetate by carbonylation of methylal and reaction of preparing glycollic acid by hydrolyzing methoxy methyl acetate are combined, so that the coal chemical platform substance methanol can be efficiently, environmentally-friendly and economically converted into glycollic acid.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were purchased commercially.
The following describes possible embodiments
Specifically, the invention provides a method for preparing glycollic acid by hydrolyzing alkoxy acetate, which comprises the steps of passing the alkoxy acetate and water through a reaction zone loaded with a catalyst containing an acidic molecular sieve, and reacting under certain reaction conditions to prepare glycollic acid;
the structural formula of the alkoxy acetate is as follows:
wherein R is 1 Is methyl (CH) 3 ) Ethyl (C) 2 H 5 ) Propyl (C) 3 H 7 ) Butyl (C) 4 H 9 ) Any one of R 2 Is methyl (CH) 3 ) Ethyl (C) 2 H 5 ) Propyl (C) 3 H 7 ) Butyl (C) 4 H 9 ) Any one of R 1 And R is 2 May be the same or different;
the acidic molecular sieve is a molecular sieve with acidity;
the reaction zone comprises a fixed bed reactor or a plurality of fixed bed reactors connected in series and/or parallel;
the reaction conditions are as follows: the reaction temperature is 60-260 ℃, the mol ratio of the alkoxy acetate in the raw materials to the water is 1:20-20:1, the reaction pressure is 0.1-10 MPa, and the mass airspeed of the alkoxy acetate in the raw materials is 0.1-3 h -1 。
The alkoxy acetate hydrolysis reaction equation is:
R 1 OCH 2 COOR 2 +2H 2 O＝R 1 OH+R 2 OH+HOCH 2 COOH (1)
simultaneously, two partial hydrolysis reactions of the alkoxy acetic ester exist, namely:
R 1 OCH 2 COOR 2 +H 2 O＝R 2 OH+R 1 OCH 2 COOH (2)
R 1 OCH 2 COOR 2 +H 2 O＝R 1 OH+HOCH 2 COOR 2 (3)
the two partial hydrolysates can be further hydrolyzed under the same catalyst and reaction conditions to generate glycolic acid, which are respectively:
R 1 OCH 2 COOH+H 2 O＝R 1 OH+HOCH 2 COOH (4)
HOCH 2 COOR 2 +H 2 O＝R 2 OH+HOCH 2 COOH (5)
at the same time, hydrolytically produced alcohols R 1 OH and R 2 The OH can also be partially dehydrated to form the corresponding ether.
The acidic molecular sieve is one or more of an acidic MFI structure molecular sieve, an acidic FAU structure molecular sieve, an acidic FER structure molecular sieve, an acidic BEA structure molecular sieve, an acidic MOR structure molecular sieve or/and an acidic MWW structure molecular sieve.
The acidic molecular sieve is one or more of acidic ZSM-5 molecular sieve, acidic Y molecular sieve, acidic ZSM-35 molecular sieve, acidic beta molecular sieve, acidic mordenite or/and acidic MCM-22 molecular sieve.
The acidic molecular sieve is one or more of hydrogen ZSM-5 molecular sieve, hydrogen Y molecular sieve, hydrogen ZSM-35 molecular sieve, hydrogen beta molecular sieve, hydrogen mordenite or/and hydrogen MCM-22 molecular sieve.
The silicon-aluminum ratio Si/Al of the acidic molecular sieve is 3-500.
The catalyst containing the acidic molecular sieve also contains a catalyst forming agent; the forming agent is one of alumina and silicon oxide, and the weight percentage is 0-50%.
The catalyst containing the acidic molecular sieve is prepared by mixing a catalyst forming agent with the acidic molecular sieve and then extruding and forming.
R in the alkoxy acetic ester 1 And R is R 2 Are all methyl groups, i.e. the alkoxy acetate is methoxy methyl acetate (CH 3 OCH 2 COOCH 3 )。
The methoxy methyl acetate is prepared by a methylal carbonylation method.
When the alkoxyacetate is methyl methoxyacetate, the hydrolysis product includes glycolic acid and methoxyacetic acid (CH) as known from the above-described principles of reactions (1) to (5) 3 OCH 2 COOH), methyl glycolate (HOCH) 2 COOCH 3 ) Methanol and dimethyl ether. Wherein, methoxy acetic acid and methyl glycolate can be continuously hydrolyzed into glycollic acid, and methanol and dimethyl ether can be returned to the methylal synthesis reactor to synthesize methylal.
When the alkoxyl acetate is methyl methoxyacetate, the selectivity of the glycolic acid hydrolysis product can reach 50% according to the carbon number calculation theory according to the principles of the reactions (1) to (5).
The reaction conditions are preferably: the reaction temperature is 130-200 ℃, the mol ratio of the alkoxy acetate to the water in the raw materials is 1:8-1:2, the reaction pressure is 0.1-0.3 MPa, and the mass airspeed of the alkoxy acetate in the raw materials is 0.3-1 h -1 。
The raw material contains one of nitrogen and argon inert carrier gas in the process of passing through a reaction zone loaded with an acidic molecular sieve catalyst.
The analytical methods, conversions, selectivities in the examples were calculated as follows:
products other than glycolic acid and unreacted starting materials were analyzed using an Agilent7890B gas chromatograph with its FID detector attached to the DB-FFAP capillary column and its TCD detector attached to the Porapak Q packed column. Glycolic acid analysis by liquid chromatograph, separation column C 18 The column and the detector are ultraviolet detectors.
In the examples of the present invention, the conversion and selectivity were both calculated on a carbon mole basis:
conversion of alkoxyacetate= [ (moles of alkoxyacetate carbon in feed) - (moles of alkoxyacetate carbon in discharge) ] ≡ (moles of alkoxyacetate carbon in feed) ×100%
Product selectivity = (moles of carbon for product in the draw)/(sum of moles of carbon for all carbonaceous products in the draw) ×100%;
the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
Catalyst Performance test
Example 1
An acidic H-ZSM-5 molecular sieve with a silicon-aluminum ratio of Si/Al=20 produced by catalyst factories of the new technology (Dalian) of the middle-family catalysis is selected, crushed and sieved into particles with the diameter of 0.4-0.8 mm, 2g is taken and put into a stainless steel reaction tube with the inner diameter of 8mm, and activated for 4 hours at 500 ℃ with 50mL/min nitrogen for reaction under the following conditions: reaction temperature (T) =150 ℃, reaction pressure (P) =0.1 MPa, and the molar ratio of methyl methoxyacetate to water in the raw material is (methyl methoxyacetate: water) =1:4; mass space velocity (WHSV) of the starting methyl methoxyacetate=1.0 h -1 . After 24 hours of reaction, the product was analyzed by gas chromatography and liquid chromatography, and the results of the reaction based on the carbon number are shown in Table 1.
Examples 2 to 9
The catalyst, reaction conditions and reaction results are shown in Table 1. The other operations are the same as in example 1.
TABLE 1 catalytic reaction results in examples 1-9
As can be seen from Table 1, the hydrogen type molecular sieve catalyst has high conversion rate of methyl methoxyacetate and high selectivity of glycollic acid in the reaction of preparing glycollic acid by hydrolyzing methyl methoxyacetate, and has excellent catalytic performance.
Examples 10 to 13
The reaction results are shown in Table 2, except that the methyl methoxyacetate as a raw material in example 1 was changed to other alkoxyl acetate under the same conditions and operation.
TABLE 2 catalytic reaction results in examples 1 and 10-13
It can be seen from table 2 that the hydrogen form of the molecular sieve catalyst is capable of hydrolyzing a variety of alkoxyacetates to glycolic acid.
Examples 14 to 15
The acidic H-ZSM-5 molecular sieve having a silica to alumina ratio of Si/al=20 in example 1 was molded by extrusion molding with alumina or silica, respectively, the content of alumina or silica in the molded catalyst was 20wt%, and other conditions and operations were unchanged, and the reaction results are shown in table 3.
TABLE 3 catalytic reaction results in examples 1, 14 and 15
It can be seen from table 3 that the catalytic activity of the acidic molecular sieve catalyst is substantially maintained after shaping with alumina or silica.
Example 16
An acidic H-ZSM-5 molecular sieve with a silicon-aluminum ratio of Si/Al=20 produced by catalyst factories of the new technology (Dalian) of the middle-family catalysis is selected, crushed and sieved into particles with the diameter of 0.4-0.8 mm, 2g is taken and put into a stainless steel reaction tube with the inner diameter of 8mm, and activated for 4 hours at 500 ℃ with 50mL/min nitrogen for reaction under the following conditions: reaction temperature (T) =150 ℃, reaction pressure (P) =0.1 MPa, and the molar ratio of methyl methoxyacetate to water in the raw material is (methyl methoxyacetate: water) =1:4; mass space velocity (WHSV) of the starting methyl methoxyacetate=1.0 h -1 . The products were analyzed by gas chromatography and liquid chromatography for different times and the results of the reactions based on carbon number are shown in Table 4.
TABLE 4 catalytic reaction results in example 16
From Table 4, it can be seen that the acidic molecular sieve catalyst has good stability in the reaction of preparing glycollic acid by hydrolyzing methyl methoxyacetate, and can meet the industrial use requirements.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (4)
1. A method for preparing glycollic acid by hydrolyzing alkoxy acetate is characterized in that raw materials containing alkoxy acetate and water react in the presence of an acidic molecular sieve catalyst to obtain glycollic acid;
the alkoxy acetic ester is at least one selected from substances with structural formulas shown in a formula I;
a formula I;
in the formula I, the compound of the formula I,
the R is 1 Any one selected from methyl, ethyl, propyl and butyl;
the R is 2 Any one selected from methyl, ethyl, propyl and butyl;
the acidic molecular sieve is at least one selected from hydrogen ZSM-5 molecular sieve, hydrogen Y molecular sieve, hydrogen ZSM-35 molecular sieve, hydrogen beta molecular sieve, hydrogen mordenite and hydrogen MCM-22 molecular sieve;
the atomic ratio of silicon to aluminum in the acidic molecular sieve is 20-50;
the reaction conditions are as follows: the reaction temperature is 100-260 ℃; the reaction pressure is 0.1-0.3 MPa;
the molar ratio of the alkoxy acetate to the water is 1:2-8;
the mass airspeed of the alkoxy acetic ester is 0.3-3 h -1 ；
The reaction is carried out in an inert atmosphere.
2. The method of claim 1, wherein the acidic molecular sieve catalyst further comprises a shaping agent;
the forming agent is oxide;
the oxide is at least one of aluminum oxide and silicon oxide;
in the acidic molecular sieve catalyst, the content of the forming agent is m, and the value range of m is more than 0 and less than or equal to 50wt%.
3. The process according to claim 1, wherein the reaction is carried out in at least one fixed bed reactor;
a plurality of the fixed bed reactors are connected in series and/or parallel.
4. The method of claim 1, wherein the inert atmosphere comprises any one of nitrogen and an inert gas.
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