CN108586239B - Preparation method of methyl 3-hydroxypropionate - Google Patents
Preparation method of methyl 3-hydroxypropionate Download PDFInfo
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- RVGLEPQPVDUSOJ-UHFFFAOYSA-N 2-Methyl-3-hydroxypropanoate Chemical compound COC(=O)CCO RVGLEPQPVDUSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 28
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims abstract description 4
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 30
- 229940071870 hydroiodic acid Drugs 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000012856 packing Methods 0.000 claims description 15
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 235000009518 sodium iodide Nutrition 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000000066 reactive distillation Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 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 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 5
- 239000003755 preservative agent Substances 0.000 abstract description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000004310 lactic acid Substances 0.000 abstract description 2
- 235000014655 lactic acid Nutrition 0.000 abstract description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 10
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- ALRHLSYJTWAHJZ-UHFFFAOYSA-M 3-hydroxypropionate Chemical compound OCCC([O-])=O ALRHLSYJTWAHJZ-UHFFFAOYSA-M 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 0.000 description 4
- -1 carbonyl methyl Chemical group 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 3
- XZGHPJWDJDHITH-UHFFFAOYSA-N 3-methoxypropyl formate Chemical compound COCCCOC=O XZGHPJWDJDHITH-UHFFFAOYSA-N 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920000704 biodegradable plastic Polymers 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000013589 supplement Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OTLLISYHVPWWCF-UHFFFAOYSA-N prop-2-enal;hydrate Chemical compound O.C=CC=O OTLLISYHVPWWCF-UHFFFAOYSA-N 0.000 description 2
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of methyl 3-hydroxypropionate, which comprises the following steps: s1, etherifying hydriodic acid, and carrying out the etherifying reaction on the methyl 3-methoxypropionate and the hydriodic acid at the temperature of 105-110 ℃ according to the molar ratio of 1:1.05-1.10 to obtain the methyl 3-hydroxypropionate, the 3-hydroxypropionic acid and methyl iodide; s2, rectifying and separating, namely rectifying and separating the mixed product of the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid obtained in the step S1 to respectively obtain the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid. The preparation method has the advantages of safe and reliable raw materials and preparation process, mild reaction conditions, simple steps, short synthetic route, low cost, high product yield and suitability for industrial batch production; in addition, the produced by-product 3-hydracrylic acid is an isomer of lactic acid (2-hydracrylic acid), and the isomer has active chemical properties and can be used for synthesizing various important chemical substances or used as additives and preservatives of food or feed.
Description
Technical Field
The invention belongs to the technical field of chemical product production, relates to a preparation method of methyl 3-hydroxypropionate, and particularly relates to a novel method for preparing methyl 3-hydroxypropionate and co-producing 3-hydroxypropionic acid.
Background
1, 3-propanediol (1,3-PDO) is an important organic chemical raw material, has an application field similar to other dihydric alcohols, is mainly used as a monomer of polyester and polyurethane, a solvent, an antifreeze agent or a protective agent and the like, and is also used for synthesizing medicines and used as an organic synthesis intermediate. Research in recent years shows that the Polyester (PTT) synthesized by taking 1, 3-propanediol as a monomer has better characteristics than the Polyester (PET) synthesized by taking ethylene glycol as a monomer and has wide application prospect.
At present, the preparation process of 1, 3-propylene glycol mainly comprises an acrolein water and hydrogenation method, biological fermentation and a carbonyl methyl esterification method, wherein the carbonyl methyl esterification method is a method for synthesizing methyl 3-hydroxypropionate (3-HPE) by carbonyl methyl esterification reaction of ethylene oxide, carbon monoxide and methanol, and then hydrogenating to obtain 1,3-PDO, and the methyl 3-hydroxypropionate is an important raw material for preparing 1, 3-propylene glycol. The carbonyl methyl esterification method can avoid the problem of instability of acrolein water and the intermediate 3-hydroxypropionaldehyde in the hydrogenation process. However, the raw materials of the methyl carbonyl esterification method mainly comprise ethylene oxide and carbon monoxide, so the reaction risk is extremely high, and the industrial popularization is not facilitated.
Therefore, development of a production method with mild production conditions and high safety is important for industrialization of 1, 3-propanediol by using it as a raw material for producing 1, 3-propanediol.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the conventional method for preparing the 1, 3-propylene glycol reaction raw material 3-methyl hydroxypropionate has high reaction risk coefficient and is not beneficial to industrial production, so that the preparation method of the 3-methyl hydroxypropionate has mild preparation conditions, is safe and environment-friendly, has low cost and high yield and quality.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a preparation method of methyl 3-hydroxypropionate, which comprises the following steps:
s1, etherifying hydriodic acid, and carrying out the etherifying reaction on the methyl 3-methoxypropionate and the hydriodic acid at the temperature of 105-110 ℃ according to the molar ratio of 1:1.05-1.10 to obtain the methyl 3-hydroxypropionate, the 3-hydroxypropionic acid and methyl iodide;
s2, rectifying and separating, namely rectifying and separating the mixed product of the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid obtained in the step S1 to respectively obtain the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid.
Preferably, the step S2 is followed by a step S3 of cracking methyl iodide to produce hydrogen iodide, and absorbing the produced hydrogen iodide with water to obtain hydroiodic acid.
Preferably, the step S2 is a vacuum distillation separation, and the fractions at 80 ℃ and 150 ℃ are collected under a high vacuum of 10mmHg to obtain methyl 3-hydroxypropionate and 3-hydroxypropionic acid respectively.
Preferably, the step S3 is to prepare hydrogen iodide by catalytic cracking, the catalytic cracking temperature is 300-600 ℃, and the catalyst is HZSM-5 molecular sieve.
Preferably, the step S1 is performed by using a reactive distillation device with a stirring system, the reactive distillation device further comprises a water separator and a reflux mechanism, the stirring speed in the step S1 is 200-300r/min, and the reaction time is 300-400 min.
Preferably, the rectification separation in step S2 is performed in a high-efficiency rectification column having an electric heating device and a pressure reduction function, and the number of theoretical plates of the high-efficiency rectification column is 40.
Preferably, a rectification column is arranged in the high-efficiency rectification tower, the rectification column is made of stainless steel, the packing of the rectification column is 3 theta ring packing, and the height of the packing is 2 m.
Preferably, the hydroiodic acid etherification solution in the step S1 is performed in an acidic system consisting of hydroiodic acid, sodium iodide and phosphoric acid, wherein the mass ratio of the hydroiodic acid, the sodium iodide and the phosphoric acid is 100-: 130-150:80-100.
Preferably, the concentration of hydroiodic acid is not less than 55%.
Preferably, the hydroiodic acid produced in step S3 is recycled to step S1.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the preparation method of the methyl 3-hydroxypropionate comprises the following steps: s1, etherifying hydriodic acid, and carrying out the etherifying reaction on the methyl 3-methoxypropionate and the hydriodic acid at the temperature of 105-110 ℃ according to the molar ratio of 1:1.05-1.10 to obtain the methyl 3-hydroxypropionate, the 3-hydroxypropionic acid and methyl iodide; s2, rectifying and separating, namely rectifying and separating the mixed product of the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid obtained in the step S1 to respectively obtain the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid. The preparation method has the advantages of safe and reliable raw materials and preparation process, mild reaction conditions, simple steps, short synthetic route, low cost, high product yield and suitability for industrial batch production; in addition, the produced by-product 3-hydracrylic acid is an isomer of lactic acid (2-hydracrylic acid), and the isomer has active chemical properties and can be used for synthesizing various important chemical substances or used as additives and preservatives of food or feed.
(2) The preparation method of methyl 3-hydroxypropionate comprises the step S3 of preparing hydrogen iodide by cracking methyl iodide after the step S2, wherein the prepared hydrogen iodide is absorbed by water to obtain hydroiodic acid, the methyl iodide is continuously distilled out while the etherolysis reaction is carried out in the step S1 to obtain methyl iodide with higher purity, the methyl iodide is prepared into hydrogen iodide through the cracking reaction, the hydrogen iodide is absorbed by water to obtain hydroiodic acid, and the hydroiodic acid can be recycled to the step S1 and used for the etherolysis reaction again, so that the materials are recycled, and the production cost of the methyl 3-hydroxypropionate is further reduced.
Detailed Description
In order that the present disclosure may be more readily and clearly understood, reference will now be made in detail to the present disclosure as illustrated in the accompanying drawings.
Example 1
The embodiment provides a preparation method of methyl 3-hydroxypropionate, which comprises the following steps:
s1, etherifying hydriodic acid, namely adding 2.36kg (20mol) of methyl 3-methylpropionate (MMP) into a reaction rectifying tower with a stirring system, a water separator and a reflux device, raising the temperature to 105 ℃, dropwise adding 4.88kg (21mol) of commercial hydriodic acid with the volume concentration of not less than 55% into 3-methoxy propyl formate, and when the flow rate of distilled methyl iodide is reduced, beginning to supplement sodium iodide and phosphoric acid until the mass ratio of the hydriodic acid to the sodium iodide to the phosphoric acid is 100:130:80, the stirring speed is 200r/min and the reaction time is 300min in the etherifying process. And generating a product of methyl 3-hydroxypropionate, a small amount of by-product of 3-hydroxypropionate, and collecting the by-product of methyl iodide at the top of the reaction rectifying tower. The reaction equation for this reaction is:
CH3OCH2CH2COOCH3+HI→HOCH2CH2COOCH3+HOCH2CH2COOH+CH3I。
the reaction conversion rate was calculated by analyzing the recovered methyl iodide, and in this example, the reaction conversion rate was not less than 98%, and the product was analyzed by chromatography on the material in the reactive distillation column, and the result showed that the product contained unreacted raw material MMP 3%, methyl 3-hydroxypropionate 62%, 3-hydroxypropionic acid 25%, and about 10% of the other components.
S2, rectifying and separating the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid, wherein an efficient rectifying tower with a pressure reduction function is adopted, a tower body of the efficient rectifying tower is provided with an electric heating device and can heat substances in the tower body, the theoretical plate number of the efficient rectifying tower is 40, a rectifying column which is a 304 stainless steel rectifying column of DN40 is arranged in the rectifying tower, the packing of the rectifying column adopts 3 theta ring packing, and the height of the packing is 2 m. The rectification process is specifically as follows: under the high vacuum condition of 10mmHg, fractions at 80 ℃ and 150 ℃ are respectively collected to respectively obtain methyl 3-hydroxypropionate and 3-hydroxypropionic acid. The recovered by-product 3-hydroxypropionic acid is an isomer of lactic acid (2-hydroxypropionic acid), which is chemically more active due to the difference in the positions of the hydroxyl groups. A plurality of important chemical substances such as acrylic acid and malonic acid, as well as biodegradable plastic poly-3-hydroxypropionic acid can be synthesized through oxidation, dehydration, esterification reaction and the like, and the compound can also be used as an additive and a preservative of food or feed.
S3, cracking methyl iodide, namely, enabling methyl iodide collected at the top of the reaction rectifying tower in the step S1 to pass through a fixed bed reactor, performing thermal cracking at the temperature of 300 ℃ under the catalysis of an HZSM-5 catalyst to obtain hydrogen iodide, absorbing a small amount of ethylene and propylene by water to obtain hydroiodic acid, wherein the hydroiodic acid can be recycled to the step S1 and used as a reaction raw material for the etherolysis.
Example 2
The embodiment provides a preparation method of methyl 3-hydroxypropionate, which comprises the following steps:
s1, etherifying hydriodic acid, namely adding 1.18kg (10mol) of methyl 3-methylpropionate (MMP) into a reaction rectifying tower with a stirring system, a water separator and a reflux device, raising the temperature to 110 ℃, dropwise adding 2.56kg (11mol) of commercial hydriodic acid with the volume concentration of not less than 55% into 3-methoxy propyl formate, and when the flow rate of distilled methyl iodide is reduced, beginning to supplement sodium iodide and phosphoric acid until the mass ratio of the hydriodic acid to the sodium iodide to the phosphoric acid is 130:150:100, the stirring speed is 300r/min and the reaction time is 400min in the etherifying process. And generating a product of methyl 3-hydroxypropionate, a small amount of by-product of 3-hydroxypropionate, and collecting the by-product of methyl iodide at the top of the reaction rectifying tower. The reaction equation for this reaction is:
CH3OCH2CH2COOCH3+HI→HOCH2CH2COOCH3+HOCH2CH2COOH+CH3I
the reaction conversion rate was calculated by analyzing the recovered methyl iodide, and in this example, the reaction conversion rate was not less than 97%, and the product was analyzed by chromatography on the material in the reactive distillation column, and the result showed that the product contained unreacted raw material MMP 0.5%, methyl 3-hydroxypropionate 73.5%, 3-hydroxypropionate 16%, and about 10% of other components.
S2, rectifying and separating the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid, wherein an efficient rectifying tower with a pressure reduction function is adopted, a tower body of the efficient rectifying tower is provided with an electric heating device and can heat substances in the tower body, the theoretical plate number of the efficient rectifying tower is 40, a rectifying column which is a 304 stainless steel rectifying column of DN40 is arranged in the rectifying tower, the packing of the rectifying column adopts 3 theta ring packing, and the height of the packing is 2 m. The rectification process is specifically as follows: under the high vacuum condition of 10mmHg, fractions at 80 ℃ and 150 ℃ are respectively collected to respectively obtain methyl 3-hydroxypropionate and 3-hydroxypropionic acid. The recovered by-product 3-hydroxypropionic acid is an isomer of lactic acid (2-hydroxypropionic acid), which is chemically more active due to the difference in the positions of the hydroxyl groups. A plurality of important chemical substances such as acrylic acid and malonic acid, as well as biodegradable plastic poly-3-hydroxypropionic acid can be synthesized through oxidation, dehydration, esterification reaction and the like, and the compound can also be used as an additive and a preservative of food or feed.
S3, cracking methyl iodide, namely, enabling methyl iodide collected at the top of the reaction rectifying tower in the step S1 to pass through a fixed bed reactor, performing thermal cracking at the temperature of 600 ℃ under the catalysis of an HZSM-5 catalyst to obtain hydrogen iodide, absorbing a small amount of ethylene and propylene by water to obtain hydroiodic acid, wherein the hydroiodic acid can be recycled to the step S1 and used as a reaction raw material for the etherolysis.
Example 3
The embodiment provides a preparation method of methyl 3-hydroxypropionate, which comprises the following steps:
s1, etherifying hydriodic acid, namely adding 3.54kg (30mol) of methyl 3-methylpropionate (MMP) into a reaction rectifying tower with a stirring system, a water separator and a reflux device, raising the temperature to 105 ℃, dropwise adding 7.53kg (32.4mol) of commercial hydriodic acid with the volume concentration of not less than 55% into 3-methoxy propyl formate, and when the flow rate of distilled methyl iodide is reduced, beginning to supplement sodium iodide and phosphoric acid until the mass ratio of the hydriodic acid, the sodium iodide and the phosphoric acid is 115:140:92, wherein the stirring speed is 250r/min and the reaction time is 350min in the etherifying process. And generating a product of methyl 3-hydroxypropionate, a small amount of by-product of 3-hydroxypropionate, and collecting the by-product of methyl iodide at the top of the reaction rectifying tower. The reaction equation for this reaction is:
CH3OCH2CH2COOCH3+HI→HOCH2CH2COOCH3+HOCH2CH2COOH+CH3I。
the reaction conversion rate was calculated by analyzing the recovered methyl iodide, and in this example, the reaction conversion rate was not less than 98%, and the product contained unreacted raw material MMP 1.5%, methyl 3-hydroxypropionate 68.5%, 3-hydroxypropionate 20%, and about 10% of other components, as a result of chromatographic analysis of the material in the reactive distillation column.
S2, rectifying and separating the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid, wherein an efficient rectifying tower with a pressure reduction function is adopted, a tower body of the efficient rectifying tower is provided with an electric heating device and can heat substances in the tower body, the theoretical plate number of the efficient rectifying tower is 40, a rectifying column which is a 304 stainless steel rectifying column of DN40 is arranged in the rectifying tower, the packing of the rectifying column adopts 3 theta ring packing, and the height of the packing is 2 m. The rectification process is specifically as follows: under the high vacuum condition of 10mmHg, fractions at 80 ℃ and 150 ℃ are respectively collected to respectively obtain methyl 3-hydroxypropionate and 3-hydroxypropionic acid. The recovered by-product 3-hydroxypropionic acid is an isomer of lactic acid (2-hydroxypropionic acid), which is chemically more active due to the difference in the positions of the hydroxyl groups. A plurality of important chemical substances such as acrylic acid and malonic acid, as well as biodegradable plastic poly-3-hydroxypropionic acid can be synthesized through oxidation, dehydration, esterification reaction and the like, and the compound can also be used as an additive and a preservative of food or feed.
S3, cracking methyl iodide, namely, enabling methyl iodide collected at the top of the reaction rectifying tower in the step S1 to pass through a fixed bed reactor, performing thermal cracking at the temperature of 450 ℃ under the catalysis of an HZSM-5 catalyst to obtain hydrogen iodide, absorbing a small amount of ethylene and propylene by water to obtain hydroiodic acid, wherein the hydroiodic acid can be recycled to the step S1 and used as a reaction raw material for the etherolysis.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. A preparation method of methyl 3-hydroxypropionate is characterized by comprising the following steps:
s1, etherifying hydriodic acid, and carrying out the etherifying reaction on the methyl 3-methoxypropionate and the hydriodic acid at the temperature of 105-110 ℃ according to the molar ratio of 1:1.05-1.10 to obtain the methyl 3-hydroxypropionate, the 3-hydroxypropionic acid and methyl iodide;
s2, rectifying and separating, namely rectifying and separating the mixed product of the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid obtained in the step S1 to respectively obtain the methyl 3-hydroxypropionate and the 3-hydroxypropionic acid;
the hydroiodic acid etherification solution in the step S1 is performed in an acidic system, wherein the acidic system consists of hydroiodic acid, sodium iodide and phosphoric acid, and the mass ratio of the hydroiodic acid to the sodium iodide to the phosphoric acid is 100-: 130-150:80-100.
2. The method of claim 1, further comprising a step S3 of cracking methyl iodide to produce hydrogen iodide after the step S2, wherein the produced hydrogen iodide is absorbed by water to obtain hydroiodic acid.
3. The method according to claim 2, wherein the step S2 is a rectification separation under reduced pressure, and the fractions at 80 ℃ and 150 ℃ are collected under a high vacuum of 10mmHg to obtain methyl 3-hydroxypropionate and 3-hydroxypropionic acid, respectively.
4. The method as claimed in claim 3, wherein the step S3 is a step of preparing hydrogen iodide by catalytic cracking at 300-600 ℃ and the catalyst is HZSM-5 molecular sieve.
5. The method for preparing methyl 3-hydroxypropionate according to any one of claims 1 to 4, wherein the step S1 is performed by using a reactive distillation apparatus with a stirring system, the reactive distillation apparatus further comprises a water separator and a reflux mechanism, the stirring speed in the step S1 is 200-300r/min, and the reaction time is 300-400 min.
6. The process for producing methyl 3-hydroxypropionate according to claim 5, wherein the rectification separation in step S2 is carried out in a high-efficiency rectification column having an electric heating device and having a theoretical plate number of 40 plates, and having a pressure-reducing function.
7. The preparation method of methyl 3-hydroxypropionate according to claim 6, wherein a rectification column is arranged in the high-efficiency rectification column, the rectification column is made of stainless steel, the packing of the rectification column is 3 theta ring packing, and the height of the packing is 2 m.
8. The method of producing methyl 3-hydroxypropionate according to claim 7, wherein the concentration of the hydroiodic acid is not less than 55%.
9. The method of claim 8, wherein the hydroiodic acid produced in step S3 is recycled to step S1.
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