CN114436828A - Method for simultaneously preparing methyl methoxyacetate and methyl glycolate - Google Patents
Method for simultaneously preparing methyl methoxyacetate and methyl glycolate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- ICPWFHKNYYRBSZ-UHFFFAOYSA-M 2-methoxypropanoate Chemical compound COC(C)C([O-])=O ICPWFHKNYYRBSZ-UHFFFAOYSA-M 0.000 title claims abstract description 32
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 title claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 138
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 235000019256 formaldehyde Nutrition 0.000 claims description 36
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- FERQZYSWBVOPNX-UHFFFAOYSA-N carbonyl dichloride;rhodium;triphenylphosphane Chemical compound [Rh].ClC(Cl)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FERQZYSWBVOPNX-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- XZMMPTVWHALBLT-UHFFFAOYSA-N formaldehyde;rhodium;triphenylphosphane Chemical compound [Rh].O=C.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XZMMPTVWHALBLT-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000000926 separation method Methods 0.000 abstract description 8
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 7
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 7
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 abstract description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 46
- 239000007788 liquid Substances 0.000 description 23
- 230000006315 carbonylation Effects 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 17
- 238000001816 cooling Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000008098 formaldehyde solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000007789 sealing Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229920001429 chelating resin Polymers 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- AACIZACVKFEETJ-UHFFFAOYSA-N O=C=[RhH].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound O=C=[RhH].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 AACIZACVKFEETJ-UHFFFAOYSA-N 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- GOQRKXBLBLOWLQ-UHFFFAOYSA-N methyl 2-acetyloxyacetate Chemical compound COC(=O)COC(C)=O GOQRKXBLBLOWLQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RDNQMPKMUHHSAM-UHFFFAOYSA-N (2-methoxy-2-oxoethyl) propanoate Chemical compound CCC(=O)OCC(=O)OC RDNQMPKMUHHSAM-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MLXDUYUQINCFFV-UHFFFAOYSA-N 2-acetyloxyacetic acid Chemical compound CC(=O)OCC(O)=O MLXDUYUQINCFFV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- RMIODHQZRUFFFF-UHFFFAOYSA-N methoxyacetic acid Chemical compound COCC(O)=O RMIODHQZRUFFFF-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for simultaneously preparing methyl methoxyacetate and methyl glycolate, which comprises the steps of carrying out carbonylation reaction on formaldehyde monomer source substances containing methanol and CO in a mixed solvent under the action of a rhodium carbonyl catalyst; then methanol is added into the product after the solvent is removed to carry out esterification reaction, and methyl methoxyacetate and methyl glycolate are generated. The invention is characterized in that the raw material adopts formaldehyde aqueous solution which is cheap and easy to obtain, trioxymethylene or paraformaldehyde is not needed to be used as a formaldehyde monomer source, the catalyst has no corrosivity to reaction equipment, and the direct separation of the product and the solvent can be realized before the esterification reaction.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for simultaneously preparing methyl methoxyacetate and methyl glycolate.
Background
Methyl methoxyacetate is a valuable intermediate, can be used for the kinetic resolution of chiral amine compounds, the synthesis of vitamin B6, sulfanilamide-5-pyrimidine and the like, can be used as a catalyst for polymerization, can also be hydrogenated and hydrolyzed to prepare ethylene glycol, and is an important ethylene glycol precursor. Methyl glycolate as an important organic chemical raw material can be widely applied to the fields of chemical industry, polymer materials, pesticides, medicines, spices, feeds, dyes and the like. Meanwhile, methyl glycolate is also an important intermediate for preparing ethylene glycol from coal.
The synthesis method of methyl methoxyacetate mainly comprises a carbonylation method (taking dimethoxymethane or formaldehyde as a raw material), a substitution method (taking sodium methoxide and chloroacetic acid as raw materials) and an oxidation method (taking ethylene glycol monomethyl ether as a raw material), wherein the substitution method and the oxidation method are generally used for small-amount synthesis in laboratories, and the carbonylation method can be used for industrially and independently synthesizing methyl methoxyacetate and can also be used as an intermediate process for synthesizing ethylene glycol by a carbonylation method.
Chevron in USP3911003 discloses the carbonylation of formaldehyde with hydrofluoric acid as a catalyst. The hydrofluoric acid has strong corrosivity and serious pollution, and the production is stopped after the operation is not long. Formaldehyde is used as a reactant, the formaldehyde generates glycolic acid through carbonylation reaction, and the glycolic acid is further converted into methyl glycolate through methanol esterification. The traditional homogeneous phase method mainly adopts inorganic liquid acid as a catalyst, such as concentrated sulfuric acid, hydrofluoric acid, fluorosulfonic acid and the like. Experiments show that methyl formate is easy to generate in an acidic reaction system. Methanol is produced as a result of the decomposition of methyl formate, and the methanol and formaldehyde in the presence of an acid catalyst can form hemiacetal species which are further hydrogenated to methyl methoxyacetate. In addition, methyl glycolate can also be obtained by dehydration reaction of methyl glycolate with methanol under acid catalysis. Therefore, with formaldehyde as a reactant, methyl glycolate and a small amount of methyl methoxyacetate are simultaneously obtained in the product. This offers the possibility of simultaneously preparing methyl methoxyacetate and methyl glycolate.
In patent CN1064040C, researchers prepared sulfuric acid/metal (e.g. Cu, Ag) carbonyl compounds by absorbing CO in sulfuric acid with metal compounds. Using the above-mentioned catalyst, in strong acid system, carbonylating and esterifying formaldehyde so as to obtain methyl glycolate. The reaction conditions are relatively mild, but the corrosion problem of sulfuric acid on the device still exists. In addition, in the process, the source of the formaldehyde monomer is trioxymethylene or paraformaldehyde to obtain a better reaction result.
The main technical difficulties of the carbonylation reaction are slow reaction speed and low selectivity. The slow reaction rate is due to two reasons: firstly, an efficient catalyst system is lacked, and secondly, the concentration of CO in a solution or a reaction site is not high, so that mass transfer is difficult. Because the development of a high-activity catalyst is difficult, the reaction effect is usually improved by raising the temperature and the pressure and prolonging the reaction time, and the conditions of more side reactions and low selectivity are aggravated by harsh reaction conditions. Therefore, the core of the research on carbonylation reaction lies in two aspects: catalyst development and process intensification, and optimization of the reaction is realized by adopting a novel catalyst with high activity and adjusting a reaction system. Because the pollution of inorganic acid is serious, and the problems that the product is difficult to separate and the device is corroded exist, the development of a new catalyst and a new process become the key research point of the carbonylation of formaldehyde.
In summary, the development of a catalyst with low corrosivity and a process with low raw material cost are problems to be solved urgently in the formaldehyde carbonylation reaction.
Disclosure of Invention
In view of the problems of the prior art as described above, it is an object of the present invention to provide a process for simultaneously preparing methyl methoxyacetate and methyl glycolate, on the one hand to overcome the purity limitation on the formaldehyde monomer source, so that a commercially available aqueous formaldehyde solution (containing a methanol stabilizer) or a formaldehyde solution produced upstream of a plant can be used as a raw material, while a catalyst is not corrosive to reaction equipment, and direct separation of the product from the solvent can be achieved.
The invention provides a method for simultaneously preparing methyl methoxyacetate and methyl glycolate, which comprises the following steps:
(1) under the action of a rhodium carbonyl catalyst, a formaldehyde monomer source substance containing methanol and CO are subjected to carbonylation reaction in a mixed solvent;
(2) separating the solvent in the product obtained in the step (1), and adding methanol into the product after the solvent is removed to carry out esterification reaction to generate methyl methoxyacetate and methyl glycolate.
In the technical scheme, the formaldehyde monomer source substance in the step (1) is a formaldehyde aqueous solution with the mass fraction of 37% -55%. The mass fraction of methanol in the formaldehyde monomer source substance is 10-15%.
In the above technical scheme, the rhodium carbonyl catalyst in step (1) is one of rhodium dicarbonyl acetylacetonate, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) carbonyl hydride, rhodium tetracarbonyl dichloride and rhodium acetylacetonate triphenylphosphine carbonyl. The dosage of the catalyst is 0.1mol percent to 1mol percent of the formaldehyde monomer source substance.
The mixed solvent is a mixture of an organic solvent and an organic acid. The organic solvent is at least one selected from cyclohexane, n-octane, isooctane and n-pentane. The organic acid is at least one selected from the group consisting of acetic acid, propionic acid and isobutyric acid. The molar ratio of the organic solvent to the organic acid is 10:1-1: 1. The amount of the organic solvent to be added is not particularly limited, and is preferably in a molar ratio of the organic acid to the formaldehyde of 1:2 to 1:1, so as to ensure the dissolution of the reaction mass.
In the technical scheme, the temperature of the carbonylation reaction in the step (1) is 70-140 ℃, the pressure of the carbonylation reaction is 2-8MPa, and the reaction time is 2-6 h. The reaction temperature of the esterification reaction in the step (2) is 80-120 ℃, and the reaction time is 1-4 h.
The invention has the beneficial effects that:
the method is used for simultaneously preparing methyl methoxyacetate and methyl glycolate, and the sum of the yield of the methyl methoxyacetate and the yield of the methyl glycolate can reach 80%. The method has the characteristics of high product yield, no corrosion to reaction equipment, easy separation and recovery of the carbonylation solvent and the like. In addition, the formaldehyde monomer adopted by the method is more economic, and the reaction cost is saved.
Drawings
FIG. 1 is a schematic representation of the stratification of the products of example 1 after carbonylation and before esterification.
FIG. 2 is a schematic diagram of the product of comparative example 1 after the carbonylation reaction and before the esterification reaction.
FIG. 3 is a schematic diagram showing the stratification of the product after the carbonylation reaction and before the esterification reaction in comparative example 3.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following specific embodiments.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The yield of glycolic acid (ester) obtained for the product of the invention is shown as:
yield (%) of glycolic acid (ester) is equal to the molar amount of glycolic acid (ester) produced (theoretical value)/molar amount of formaldehyde as the starting material x 100%
Wherein the molar glycolic acid (ester) yield (theoretical) is all theoretically possible to convert to useful intermediates in the subsequent hydrogenation to ethylene glycol ring, i.e. glycolic acid, methyl glycolate and organic carboxylic acid in solvent protecting glycolic acid (ester) products including but not limited to acetoxyacetic acid, acetoxyacetic acid methyl ester, propionyloxyacetic acid methyl ester etc., if acetic acid is used as glycolic acid protecting agent, the product is calculated as:
yield (%) of glycolic acid (ester) based on the molar amount of produced glycolic acid + methyl glycolate + acetoxyacetic acid methyl ester/amount of charged formaldehyde × 100%
The calculation method of the methyl methoxyacetate comprises the following steps:
yield (%) of methyl methoxyacetate, (% by mole) of methyl methoxyacetate/mole of formaldehyde as a raw material × 100%.
[ example 1 ]
1. Carbonylation reaction
Into a stainless steel autoclave having a volume of 100mL, 8.1g (0.1mol of HCHO) of an aqueous formaldehyde solution (Hu test, containing about 37% of formaldehyde and 10% of methanol) was charged, cyclohexane: isobutyric acid (a 5:1 molar ratio) mixed solvent (50 mL). 0.185g (0.2mmol, 0.2% of CAT/HCHO) of tris (triphenylphosphine) carbonyl rhodium hydride is quickly weighed and put into a kettle, the mixture is fully stirred and uniformly mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 7MPa, and the reaction is carried out for 3 hours at 120 ℃. After the reaction, the reaction vessel was cooled to room temperature, and all the reaction solution was taken out and placed in a separatory funnel, and was allowed to stand until separation was achieved, as shown in fig. 1. Filtering the lower layer of dark liquid through a microporous filter membrane to obtain a light brown yellow carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
As can be seen from FIG. 1, by adopting the method, the direct separation of the product (lower layer) and the solvent (upper layer) can be realized after the carbonylation reaction, so that the processing amount of the next esterification link, the subsequent rectification and other operations is greatly reduced.
[ example 2 ] A method for producing a polycarbonate
1. Recovery of reaction solvent
The upper layer of the liquid after the carbonylation reaction of example 1 was removed and filtered through a microporous membrane for further use.
2. Carbonylation reaction
The filtered upper layer solvent was charged into a 100mL stainless steel autoclave, to which 8.1g (0.1mol) of an aqueous formaldehyde solution (Hu test, containing about 37% formaldehyde and 10% methanol) was added, and 8mL of isobutyric acid was added. 0.185g (0.2mmol, 0.2% of CAT/HCHO) of tris (triphenylphosphine) carbonyl rhodium hydride is quickly weighed and put into a kettle, the mixture is fully stirred and uniformly mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 7MPa, and the reaction is carried out for 3 hours at 120 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, taking out all reaction liquid, placing the reaction liquid in a separating funnel, and standing until layering. Filtering the lower layer of dark liquid through a microporous filter membrane to obtain a light brown yellow carbonylation product for later use.
3. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
As can be seen from Table 1, the product yields in example 2 are comparable to those in example 1, which shows that the solvent (upper layer) recovered after the carbonylation reaction is used for the reaction of the second charge, and the organic carboxylic acid consumed by the reaction can be recycled by only supplementing a small amount of the organic carboxylic acid, thereby achieving the initial reaction yield.
[ example 3 ]
1. Carbonylation reaction
In a stainless steel autoclave having a volume of 100mL, 5.5g (containing 0.1mol of formaldehyde) of an aqueous formaldehyde solution (Shanghai test, containing about 55% of formaldehyde and 15% of methanol), n-octane: isobutyric acid (2: 1) (molar ratio) in 50mL of the mixed solvent. 0.196g (0.4mmol, 0.4% CAT/HCHO) of acetylacetonatocarbonyltriphenylphosphine rhodium is quickly weighed and put into a kettle, the mixture is fully stirred and uniformly mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 7MPa, and the reaction is carried out for 3 hours at 120 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, taking out all reaction liquid, placing the reaction liquid in a separating funnel, and standing until layering. Filtering the lower layer liquid through a microporous filter membrane to obtain a carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
[ example 4 ]
1. Carbonylation reaction
In a stainless steel autoclave having a capacity of 100mL, 6.7g (containing 0.1mol of formaldehyde) of an aqueous formaldehyde solution (Shanghai test, containing about 45% of formaldehyde and 15% of methanol) was charged with n-pentane: 50mL of a mixed solvent of acetic acid and 8:1 (molar ratio). 0.210g (0.8mmol, 0.8% of CAT/HCHO) of rhodium dicarbonyl acetylacetonate is quickly weighed and put into a kettle, after the mixture is fully stirred and uniformly mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 4MPa, and the reaction is carried out for 6 hours at 80 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, taking out all reaction liquid, placing the reaction liquid in a separating funnel, and standing until layering. Filtering the lower layer liquid through a microporous filter membrane to obtain a carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2 hours under stirring at 120 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
[ example 5 ] A method for producing a polycarbonate
1. Carbonylation reaction
Into a stainless steel autoclave having a volume of 100mL, 8.1g (0.1mol of HCHO) of an aqueous formaldehyde solution (Hu test, containing about 37% of formaldehyde and 10% of methanol) was charged, cyclohexane: isobutyric acid (a 5:1 molar ratio) mixed solvent (50 mL). 0.195g (0.5mmol, 0.5% of CAT/HCHO) of dicarbonyl dirhodium dichloride is quickly weighed and put into a kettle, after the mixture is fully stirred and mixed evenly, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 3MPa, and the reaction is carried out for 3 hours at 100 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, taking out all reaction liquid, placing the reaction liquid in a separating funnel, and standing until layering. Filtering the lower layer of dark liquid through a microporous filter membrane to obtain a light brown yellow carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 4 hours at 80 ℃ under stirring, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
By adopting the method, the direct separation of the product (lower layer) and the solvent (upper layer) can be realized after the carbonylation reaction, so that the processing amount of the operations of the next esterification link, the subsequent rectification and the like is greatly reduced.
Comparative example 1
This comparative example used trifluoromethanesulfonic acid as the catalyst.
1. Carbonylation reaction
In a stainless steel autoclave having a volume of 100mL, 8.1g (containing 0.1mol of formaldehyde) of an aqueous formaldehyde solution (Hu test, containing about 37% of formaldehyde and 10% -15% of methanol) was charged, cyclohexane: isobutyric acid (50 mL) as a mixed solvent at a molar ratio of 5:1 was added to a reactor by sucking 200. mu.L of trifluoromethanesulfonic acid with a pipette, the mixture was stirred and mixed well, the reactor was sealed, air in the reactor was replaced with CO 3 times, high-pressure CO was introduced to 8MPa, and the reaction was carried out at 120 ℃ for 3 hours. After the reaction was completed, the reaction vessel was cooled to room temperature, and all the reaction solution was taken out and placed in a separatory funnel, as shown in fig. 2, without separation of the liquid.
2. Esterification reaction
Putting all liquid after the carbonylation reaction into a reaction kettle, adding 20mL of methanol, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester), wherein the yields of the methyl methoxyacetate and the glycolic acid (ester) are shown in Table 1.
As can be seen from FIG. 2, the products after the carbonylation reaction are not separated, the products such as glycolic acid, methoxy acetic acid and the like and the solvent are all put into the next esterification reaction, and the processing amount of the operations such as the esterification link, the subsequent rectification and the like is about 3 to 4 times of that of the example 1. In addition, after purification steps such as rectification and methanol washing, a part of methanol is mixed into the solvent (acetic acid, propionic acid, isobutyric acid), which makes recycling of the solvent difficult.
Comparative example 2
In the comparative example, paraformaldehyde was used as the raw material, and trifluoromethanesulfonic acid was used as the catalyst.
1. Carbonylation reaction
In a stainless steel autoclave having a capacity of 100mL, 3g (0.1mol) of paraformaldehyde, cyclohexane: 50mL of a mixed solvent of isobutyric acid and 5:1, sucking 200 mu L of trifluoromethanesulfonic acid by using a liquid transfer gun, putting the mixture into a kettle, fully stirring and uniformly mixing, sealing the reaction kettle, replacing air in the kettle with CO for 3 times, introducing high-pressure CO to 8MPa, and reacting for 3 hours at 120 ℃. After the reaction, the reaction kettle was cooled to room temperature, all the reaction solution was taken out and placed in a separatory funnel, and the liquid was not separated.
2. Esterification reaction
Putting all liquid after the carbonylation reaction into a reaction kettle, adding 20mL of methanol, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester), wherein the yields of the methyl methoxyacetate and the glycolic acid (ester) are shown in Table 1.
The product yield of comparative example 2 is higher than that of comparative example 1, i.e., the homogeneous acid catalyst can exhibit higher carbonylation catalytic activity only when trioxymethylene or paraformaldehyde is used as a reaction raw material.
Comparative example 3
In this comparative example, paraformaldehyde was used as the starting material, and tris (triphenylphosphine) carbonyl rhodium hydride was used as the catalyst.
1. Carbonylation reaction
In a stainless steel autoclave having a capacity of 100mL, 3g (0.1mol) of paraformaldehyde, cyclohexane: 50mL of a mixed solvent of isobutyric acid and 5:1 (molar ratio), 0.185g (0.2mmol, 0.2% CAT/HCHO) of tris (triphenylphosphine) carbonyl rhodium hydride was quickly weighed and charged into a reactor, and after sufficient stirring and uniform mixing, the reactor was sealed, air was replaced with CO for 3 times, high-pressure CO was introduced to 7MPa, and the reaction was carried out at 120 ℃ for 3 hours. After the reaction was completed, the reaction vessel was cooled to room temperature, and all the reaction solution was taken out and placed in a separatory funnel as shown in FIG. 3. Filtering the lower layer of deep color liquid for 2 times by a microporous filter membrane to obtain a carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
As is clear from FIG. 3, black carbonized particles appeared in the carbonylation reaction solution, and the product yield was reduced as compared with example 1 (using an aqueous formaldehyde solution as a raw material). Relatively speaking, the method is more suitable for taking common formaldehyde solution (with low price) as a reaction raw material, meanwhile, the catalyst has no corrosivity to reaction equipment, and the direct separation of the product and the solvent can be realized.
Comparative example 4
This comparative example did not employ a mixed solvent in the carbonylation reaction.
1. Carbonylation reaction
A stainless steel autoclave having a volume of 100mL was charged with 8.1g (0.1mol of HCHO) of an aqueous formaldehyde solution (Hu test, containing about 37% of formaldehyde and 10% of methanol) and 50mL of sulfolane. 0.185g (0.2mmol, 0.2% of CAT/HCHO) of tris (triphenylphosphine) carbonyl rhodium hydride is quickly weighed and put into a kettle, the mixture is fully stirred and uniformly mixed, the reaction kettle is sealed, air in the kettle is replaced by CO for 3 times, high-pressure CO is introduced to 7MPa, and the reaction is carried out for 3 hours at 120 ℃. And after the reaction is finished, cooling the reaction kettle to room temperature, taking out all reaction liquid, placing the reaction liquid in a separating funnel, standing until the reaction liquid is layered, and filtering the lower-layer dark liquid through a microporous filter membrane to obtain a light brown yellow carbonylation product for later use.
2. Esterification reaction
Putting the filtered lower-layer carbonylation product into a reaction kettle, adding 20mL of methanol and 1g of Amberlite IR 120 resin, sealing the reaction kettle, reacting for 2h under stirring at 100 ℃, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the kettle, and analyzing by using gas chromatography and high performance liquid chromatography to obtain the products of methyl methoxyacetate and glycolic acid (ester) with the yield shown in Table 1.
TABLE 1 reaction conditions and product yields
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for simultaneously preparing methyl methoxyacetate and methyl glycolate is characterized by comprising the following steps:
(1) under the action of a rhodium carbonyl catalyst, a formaldehyde monomer source substance containing methanol and CO are subjected to carbonylation reaction in a mixed solvent;
(2) separating the solvent in the product obtained in the step (1), and adding methanol into the product after the solvent is removed to carry out esterification reaction to generate methyl methoxyacetate and methyl glycolate.
2. The method according to claim 1, wherein the formaldehyde monomer source substance in the step (1) is a formaldehyde aqueous solution with a mass fraction of 37% -55%, and the mass fraction of methanol in the formaldehyde monomer source substance is 10% -15%.
3. The process of claim 1, wherein the rhodium carbonyl catalyst in step (1) is one of rhodium dicarbonyl acetylacetonate, rhodium bis (triphenylphosphine) carbonyl chloride, rhodium tris (triphenylphosphine) carbonyl hydride, rhodium tetracarbonyl dichloride, and rhodium acetylacetonate triphenylphosphine carbonyl.
4. The method of claim 1, wherein the catalyst is used in an amount of 0.1 mol% to 1 mol% based on the formaldehyde monomer source.
5. The method according to claim 1, wherein the mixed solvent is a mixture of an organic solvent and an organic acid.
6. The method of claim 5, wherein the molar ratio of organic solvent to organic acid is from 10:1 to 1: 1.
7. The process according to claim 5 or 6, wherein the organic solvent is selected from at least one of cyclohexane, n-octane, iso-octane and n-pentane.
8. The method of claim 5 or 6, wherein the organic acid is selected from at least one of acetic acid, propionic acid, and isobutyric acid.
9. The method according to claim 1, wherein the temperature of the carbonylation reaction in the step (1) is 70-140 ℃, the pressure of the carbonylation reaction is 2-8MPa, and the reaction time is 2-6 h.
10. The method of claim 1, wherein the esterification reaction in step (2) is carried out at a reaction temperature of 80 ℃ to 120 ℃ for a reaction time of 1 to 4 hours.
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