CN115108887A - Preparation method of ethylene glycol - Google Patents
Preparation method of ethylene glycol Download PDFInfo
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- CN115108887A CN115108887A CN202210992729.6A CN202210992729A CN115108887A CN 115108887 A CN115108887 A CN 115108887A CN 202210992729 A CN202210992729 A CN 202210992729A CN 115108887 A CN115108887 A CN 115108887A
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- ethylene glycol
- glycolaldehyde
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- hydrogenation reaction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
Abstract
The invention provides a preparation method of ethylene glycol, which comprises the following steps: and (2) carrying out hydrogenation reaction on glycolaldehyde and a solvent under the action of a metal nickel catalyst to obtain the ethylene glycol. In the process of preparing the ethylene glycol, the glycolaldehyde is used as a raw material, the metal nickel catalyst is adopted, and the ethylene glycol is prepared by hydrogenation, so that the catalyst is low in cost, mild in catalytic reaction conditions, simple in product separation, and has the advantages of high selectivity and high yield of the ethylene glycol.
Description
Technical Field
The invention relates to the technical field of ethylene glycol, in particular to a preparation method of ethylene glycol.
Background
Ethylene glycol is also known as ethylene glycol, 1, 2-ethylene glycol; has a chemical formula of (CH) 2 OH) 2 Is the simplest diol. Ethylene glycol is a colorless, odorless, sweet liquid, has low toxicity to animals, can be dissolved with water and acetone, but has low solubility in ethers. Ethylene glycol is a very important basic organic chemical raw material, has wide application, and can be used for synthesizing various chemical products, such as polyester fibers, unsaturated polyester resin, a plasticizer, a moisture absorbent, a nonionic surfactant, cosmetics, an antifreeze, a lubricant and the like.
The method for industrially producing ethylene glycol is mainly characterized by that it is made up by using petroleum to prepare ethylene, oxidizing ethylene to prepare ethylene oxide and further directly hydrating ethylene oxide. In recent years, as people have increasingly demanded more and less energy and petroleum resources are increasingly deficient, researchers have developed a low-cost and abundant-resource process route for preparing ethylene glycol from coal or natural gas, i.e., synthesis gas (CO, H) is prepared from coal 2 ) The intermediate product dimethyl oxalate is prepared by synthetic gas, and then the ethylene glycol is prepared by directly hydrogenating the dimethyl oxalate. According to the current energy situation of 'rich coal and lean oil' in China, the process route for preparing ethylene glycol from coal is more suitable for China, but the process has a great defect that impurities in products are more, which can influence the downstream industry of ethylene glycol, and mainly comprises the steps of preparing polyethylene succinate and polyethylene terephthalate by polymerizing ethylene glycol.
The ethylene glycol prepared by using coal as a raw material can be prepared from dimethyl oxalate and can also be prepared from coal-prepared methanol-methanolThe process route for preparing the formaldehyde-formaldehyde to the glycolaldehyde-the glycolaldehyde to the ethylene glycol is realized, and the process route is described in detail in patent CN 105085211B. In patent CN 105085211B, a case of preparing ethylene glycol by hydrogenating glycolaldehyde is provided, in a high-pressure reactor, with diphenyl ether (Ph) 2 O) is used as solvent, HRuCl (CO) (PPh) is used under the conditions that the temperature is 120 ℃ and the pressure is 2MPa 3 ) 3 And HRh (CO) (PPh) 3 ) 3 The mixed composition is used as a catalyst for reaction for 5 hours, the conversion rate of glycolaldehyde is 93%, the selectivity of ethylene glycol is 97%, and the yield of ethylene glycol is about 90%. In patent CN 108368014A, a high-pressure reaction kettle is adopted and TiO is used 2 -ZrO 2 Loaded with 0.4% Ru or Si doped ZrO 2 Loading 0.4% Ru as catalyst, water as solvent, reacting at 195 deg.C and 10MPa at 1450rpm for 75min, and obtaining glycol yield of over 80%. In patent CN 106470965a, a gas phase composition of C1-3 oxygen-containing compounds (formaldehyde, glycolaldehyde, glyoxal, methylglyoxal, acetol) is used in the presence of a catalyst, Ru/C is used as the catalyst, under the conditions of 80 ℃ and 9MPa, the conversion rate of the C2 oxygen-containing compounds is 100%, and the yield of ethylene glycol is more than 90%. In patent WO 2017137355A 1, a mixture of glycolaldehyde and glucose is used as a raw material, and ethylene glycol can be obtained through two hydrogenation reactors; the first hydrogenation reaction temperature is 160-270 ℃, the pressure is 2-18MPa, the catalyst adopts a compound or complex containing tungsten or molybdenum, the reaction is carried out for about 5min, and the hydrogenation is continued after the reaction is finished and cooled; the reaction temperature of the second hydrogenation is 150 ℃, the catalyst adopts Raney nickel or Raney ruthenium, the reaction is carried out for 90min, the ethylene glycol can be obtained, and the selectivity of the ethylene glycol reaches about 90 percent.
In summary, the preparation of ethylene glycol by the hydrogenation of glycolaldehyde is a viable process route. However, most of the currently used catalysts are noble metal materials, the preparation cost of the catalysts is high, and the reaction conditions are harsh, which limits the industrial application of the direct hydrogenation of glycolaldehyde to prepare ethylene glycol.
Disclosure of Invention
The invention aims to provide a preparation method of ethylene glycol, and the preparation method provided by the invention has the advantages of low catalyst preparation cost, mild catalytic reaction conditions and simple subsequent product separation.
In view of the above, the present application provides a method for preparing ethylene glycol, comprising:
and (2) carrying out hydrogenation reaction on glycolaldehyde and a solvent under the action of a metal nickel catalyst to obtain the ethylene glycol.
Preferably, the solvent is selected from one or more of water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, N-butanol, N-pentanol, isopentanol, t-pentanol, hexanol, octanol, isooctanol, polyethylene glycol, acetone, butanone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 2-methylpyrrolidone, dioxane, dioxolane, tetrahydrofuran, acetonitrile and dimethyl sulfoxide.
Preferably, the metallic nickel catalyst is selected from supported metallic nickel or Raney metallic nickel.
Preferably, the supported metal in the supported metal nickel is selected from the combination of one or more of Cu, Mo, Al, Fe, Co and Zn and Ni, and the carrier is selected from alumina, activated carbon or silica.
Preferably, the mesh number of the Raney type metal nickel is 20-50 meshes.
Preferably, the temperature of the hydrogenation reaction is 20-200 ℃.
Preferably, the pressure of the hydrogenation reaction is 0.1-20 MPa.
Preferably, the liquid hourly space velocity of the glycolaldehyde is 0.1-10 h -1 。
Preferably, in the hydrogenation reaction, the molar ratio of hydrogen to glycolaldehyde is (1-100): 1.
preferably, the hydrogenation reaction is carried out in a solid bed.
The application provides a preparation method of ethylene glycol, which comprises the following steps: and (2) carrying out hydrogenation reaction on glycolaldehyde and a solvent under the action of a metal nickel catalyst to obtain the ethylene glycol. In the process of preparing the ethylene glycol, the glycolaldehyde is used as a raw material, the metal nickel catalyst is adopted, and the ethylene glycol is prepared by hydrogenation, so that the catalyst is low in cost, mild in catalytic reaction conditions, simple in product separation, and has the advantages of high selectivity and high yield of the ethylene glycol.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Aiming at the problems of high catalyst preparation cost, high temperature and high pressure of catalytic reaction conditions in the process of preparing the ethylene glycol by hydrogenating the glycolaldehyde, the novel method for preparing the ethylene glycol by hydrogenating the glycolaldehyde is provided. The method has the advantages of low catalyst preparation cost, mild catalytic reaction conditions and simple subsequent product separation, and has good industrial application background. Specifically, the embodiment of the invention discloses a preparation method of ethylene glycol, which comprises the following steps:
and (2) carrying out hydrogenation reaction on glycolaldehyde and a solvent under the action of a metal nickel catalyst to obtain the ethylene glycol.
In the process of preparing ethylene glycol herein, the solvent is selected from one or more of water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, N-butanol, N-pentanol, isopentanol, t-pentanol, hexanol, octanol, isooctanol, polyethylene glycol, acetone, butanone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 2-methylpyrrolidone, dioxane, dioxolane, tetrahydrofuran, acetonitrile, and dimethyl sulfoxide; the metal nickel catalyst is selected from supported metal nickel or Raney metal nickel, the supported metal in the supported metal nickel is selected from one or more of Cu, Mo, Al, Fe, Co and Zn and the combination of Ni, and the carrier is selected from alumina, activated carbon or silicon dioxide; the mesh number of the Raney type metal nickel is 20-50 meshes.
In the process of hydrogenation reaction, the temperature of the hydrogenation reaction is 20-200 ℃, and the pressure is 0.1-E20 MPa; the liquid hourly space velocity of the glycolaldehyde is 0.1-10 h -1 (ii) a The molar ratio of hydrogen to glycolaldehyde is (1-100): 1. the hydrogenation reaction described herein is carried out in a solid bed.
The technical scheme provided by the invention can show that the method for preparing the ethylene glycol by adopting the glycolaldehyde has the characteristics of low preparation cost of the catalyst, mild catalytic reaction operating conditions and simple product separation, and has good industrial application value.
For further understanding of the present invention, the following examples are provided to illustrate the preparation of ethylene glycol of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
The embodiment provides a method for preparing ethylene glycol by hydrogenating glycolaldehyde, which comprises the steps of adopting a nickel-loaded copper catalyst in a fixed bed reactor, using alumina as a carrier, using 10 wt% of glycolaldehyde aqueous solution as reaction liquid, and enabling the liquid hourly space velocity to be 2h at 90 ℃, 3MPa and the liquid hourly space velocity -1 The hydrogen and the glycolaldehyde are subjected to catalytic reaction under the condition that the molar ratio of the hydrogen to the glycolaldehyde is 10:1, and a reaction product is detected by gas chromatography. The reaction results obtained were: the conversion of glycolaldehyde was 67.25%, the selectivity to ethylene glycol was 26.52%, and the yield of ethylene glycol was 17.83%.
Example 2
Compared with the example 1, the example adopts the supported nickel catalyst, the carrier is alumina, the fixed bed reactor is adopted, and the reaction result is obtained by the catalytic reaction: the conversion of glycolaldehyde was 46.76%, the selectivity to ethylene glycol was 41.66%, and the yield of ethylene glycol was 19.48%.
Example 3
Compared with examples 1 and 2, the example adopts the supported nickel and zinc catalysts, adopts a fixed bed reactor, and obtains the reaction results through catalytic reaction: the conversion of glycolaldehyde was 71.89%, the selectivity to ethylene glycol was 7.49%, and the yield of ethylene glycol was 5.38%.
Example 4
In contrast to examples 1,2 and 3, this example uses a raney nickel catalyst and a fixed bed reactor to obtain the following reaction results by catalytic reaction: the conversion of glycolaldehyde was 95.76%, the selectivity to ethylene glycol was 72.29%, and the yield of ethylene glycol was 69.22%.
Example 5
Compared with example 4, the reaction results obtained by the present example using methanol as solvent and a fixed bed reactor through catalytic reaction are as follows: the conversion of glycolaldehyde was 79.01%, the selectivity to ethylene glycol was 70.28%, and the yield of ethylene glycol was 55.53%.
Example 6
In contrast to examples 4 and 5, the present example uses isopropanol as solvent and a fixed bed reactor to obtain the following reaction results by catalytic reaction: the conversion of glycolaldehyde was 97.92%, the selectivity to ethylene glycol was 96.04%, and the yield of ethylene glycol was 94.04%.
Example 7
In contrast to examples 4, 5 and 6, this example obtained the following reaction results by catalytic reaction using N, N-dimethylacetamide as solvent and a fixed bed reactor: the conversion of glycolaldehyde was 96.51%, the selectivity to ethylene glycol was 93.78%, and the yield of ethylene glycol was 90.51%.
Example 8
In contrast to example 7, the reaction temperature of this example was 110 ℃, and the reaction results obtained by catalytic reaction using a fixed bed reactor were: the conversion of glycolaldehyde was 96.76%, the selectivity to ethylene glycol was 85.56%, and the yield of ethylene glycol was 82.79%.
Example 9
In contrast to examples 7 and 8, the reaction temperature of this example was 70 ℃, and the reaction results obtained by catalytic reaction using a fixed bed reactor were: the conversion of glycolaldehyde was 48.68%, the selectivity to ethylene glycol was 76.68%, and the yield of ethylene glycol was 37.33%.
Example 10
In comparison with example 7, the reaction pressure of this example is 1MPa, and the reaction results obtained by catalytic reaction using a fixed bed reactor are: the conversion of glycolaldehyde was 86.42%, the selectivity to ethylene glycol was 94.51%, and the yield of ethylene glycol was 81.68%.
Example 11
In contrast to examples 7 and 10, the reaction pressure of this example was 5MPa, and the reaction results obtained by catalytic reaction using a fixed bed reactor were: the conversion of glycolaldehyde was 95.92%, the selectivity to ethylene glycol was 93.62%, and the yield of ethylene glycol was 89.80%.
Example 12
In contrast to example 7, the liquid hourly space velocity of glycolaldehyde of this example was 1h -1 The method adopts a fixed bed reactor and carries out catalytic reaction, and the obtained reaction result is as follows: the conversion of glycolaldehyde was 96.21%, the selectivity to ethylene glycol was 90.41%, and the yield of ethylene glycol was 86.99%.
Example 13
The liquid hourly space velocity of glycolaldehyde of this example was 4h compared to examples 7 and 13 -1 The method adopts a fixed bed reactor and carries out catalytic reaction, and the obtained reaction result is as follows: the conversion of glycolaldehyde was 82.34%, the selectivity to ethylene glycol was 94.18%, and the yield of ethylene glycol was 77.55%.
Example 14
In contrast to example 7, the molar ratio of hydrogen to glycolaldehyde in this example was 20:1, and the reaction results obtained by catalytic reaction using a fixed bed reactor were: the conversion of glycolaldehyde was 96.57%, the selectivity to ethylene glycol was 93.79%, and the yield of ethylene glycol was 90.57%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for preparing ethylene glycol, comprising:
and (2) carrying out hydrogenation reaction on glycolaldehyde and a solvent under the action of a metal nickel catalyst to obtain the ethylene glycol.
2. The method according to claim 1, wherein the solvent is selected from one or more of water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, glycerol, N-butanol, N-pentanol, isopentanol, t-pentanol, hexanol, octanol, isooctanol, polyethylene glycol, acetone, butanone, cyclopentanone, cyclohexanone, ethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 2-methylpyrrolidone, dioxane, dioxolane, tetrahydrofuran, acetonitrile and dimethyl sulfoxide.
3. The method of claim 1, wherein the metallic nickel catalyst is selected from supported metallic nickel and raney metallic nickel.
4. The preparation method according to claim 3, wherein the supported metal in the supported metallic nickel is selected from the group consisting of one or more of Cu, Mo, Al, Fe, Co and Zn in combination with Ni, and the support is selected from the group consisting of alumina, activated carbon and silica.
5. The method according to claim 3, wherein the Raney type nickel metal has a mesh size of 20 to 50 mesh.
6. The method according to claim 1, wherein the temperature of the hydrogenation reaction is 20 to 200 ℃.
7. The preparation method according to claim 1, wherein the pressure of the hydrogenation reaction is 0.1 to 20 MPa.
8. The preparation method according to claim 1, wherein the liquid hourly space velocity of glycolaldehyde is 0.1-10 h -1 。
9. The preparation method according to claim 1, wherein in the hydrogenation reaction, the molar ratio of hydrogen to glycolaldehyde is (1-100): 1.
10. the production method according to any one of claims 1 to 9, wherein the hydrogenation reaction is carried out in a solid bed.
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| CN202210992729.6A CN115108887A (en) | 2022-08-18 | 2022-08-18 | Preparation method of ethylene glycol |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894188A (en) * | 2003-12-16 | 2007-01-10 | 国际壳牌研究有限公司 | Process of preparing glycolaldehyde |
| CN106470965A (en) * | 2014-06-30 | 2017-03-01 | 托普索公司 | The method preparing ethylene glycol from sugar |
| CN109641191A (en) * | 2016-06-03 | 2019-04-16 | 爱荷华谷类推广协会 | Convert the carbohydrate for generating aldohexose to highly selectively the continuation method of ethylene glycol |
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- 2022-08-18 CN CN202210992729.6A patent/CN115108887A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1894188A (en) * | 2003-12-16 | 2007-01-10 | 国际壳牌研究有限公司 | Process of preparing glycolaldehyde |
| CN106470965A (en) * | 2014-06-30 | 2017-03-01 | 托普索公司 | The method preparing ethylene glycol from sugar |
| CN109641191A (en) * | 2016-06-03 | 2019-04-16 | 爱荷华谷类推广协会 | Convert the carbohydrate for generating aldohexose to highly selectively the continuation method of ethylene glycol |
Non-Patent Citations (1)
| Title |
|---|
| LIKUN ZHOU ET AL.: "Selective Production of 1, 2-Propylene Glycol from Jerusalem Artichoke Tuber using Ni-W2C/AC Catalysts", CHEMSUSCHEM, vol. 5, pages 932 - 938, XP055225020, DOI: 10.1002/cssc.201100545 * |
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