CN111302895A - Synthesis method of high-purity ethylene glycol - Google Patents
Synthesis method of high-purity ethylene glycol Download PDFInfo
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- CN111302895A CN111302895A CN202010274305.7A CN202010274305A CN111302895A CN 111302895 A CN111302895 A CN 111302895A CN 202010274305 A CN202010274305 A CN 202010274305A CN 111302895 A CN111302895 A CN 111302895A
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- ethylene glycol
- dimethyl oxalate
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 238000001308 synthesis method Methods 0.000 title claims description 16
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 45
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 19
- 238000003786 synthesis reaction Methods 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 230000036571 hydration Effects 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 silicate ester Chemical class 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007910 cell fusion Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing high-purity ethylene glycol, which comprises the following steps: step one, adding a copper sulfate solution into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1 (4-6), and the molar ratio of copper sulfate to dimethyl oxalate is 1 (50-800); and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 4-6g/g cat.h, the temperature is 120-150 ℃ and the pressure is 9-10MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1 (60-80). The method has the advantages of simple synthesis process, easily obtained raw materials, milder reaction, environmental protection, no pollution, high reaction selectivity and conversion rate, and low impurity content of the obtained product glycol.
Description
Technical Field
The invention relates to the field of preparation of ethylene glycol, in particular to a synthesis method of high-purity ethylene glycol.
Background
Ethylene glycol (ethylene glycol) is also known as "glycol" or "1, 2-ethylene glycol", abbreviated as EG. Has a chemical formula of (CH)2OH)2Is the simplest diol. Ethylene glycol is a colorless, odorless, sweet liquid that is toxic to animals and is lethal to humans at a dose of about 1.6 g/kg. Ethylene glycol is miscible with water and acetone, but has low solubility in ethers. Used as solvent, antifreezing agent and raw material for synthesizing terylene. Polyethylene glycol (PEG), a high polymer of ethylene glycol, is a phase transfer catalyst and is also used for cell fusion; the nitrate is an explosive.
Currently, the ethylene glycol preparation method includes the following methods:
(1) the chlorohydrin method is to hydrolyze chloroethanol as a raw material in an alkaline medium to obtain ethylene glycol, and the reaction is carried out at 100 ℃.
(2) The ethylene oxide hydration method includes direct hydration method and catalytic hydration method, and the hydration process can be carried out under normal pressure or under pressure. The normal pressure hydration method generally adopts a small amount of inorganic acid as a catalyst to carry out reaction at 50-70 ℃. The direct hydration method of ethylene oxide is a mature production method for producing glycol in industrial scale at present. Ethylene oxide and water are directly hydrated in liquid phase in a tubular reactor under the conditions of pressurization (2.23MPa) and 200 ℃ at 190 ℃whileby-products of diethylene glycol, triethylene glycol and polyethylene glycol are produced. Wherein the molar ratio of ethylene oxide to water in the pressurized hydration process is higher, above 1:6, to reduce side reactions to ether, which reactions are carried out at a temperature of 150 ℃ and a pressure of 147kPa to hydrate to ethylene glycol.
(3) The gas-phase catalytic hydration method takes silver oxide as a catalyst and alumina as a carrier to react at 150-240 ℃ to generate glycol.
(4) Direct hydration of ethylene in a catalyst (e.g. antimony oxide TeO)2Palladium catalyst) in acetic acid solution to generate monoacetate or diacetate, and further hydrolyzing to obtain glycol.
(5) The ethylene oxide and water are subjected to hydration reaction under the action of a sulfuric acid catalyst, and the reaction liquid is subjected to alkali neutralization, evaporation and rectification to obtain a finished product. Or ethylene oxide and water are used to prepare ethylene glycol at a certain temperature and pressure, and diethylene glycol, triethylene glycol and polyethylene glycol are byproducts. The reaction liquid is evaporated, concentrated, dehydrated and refined to obtain qualified products and byproducts.
(6) The formaldehyde process.
(7) Using industrial ethylene glycol as a raw material, distilling under reduced pressure, and collecting middle distillate under 1333 Pa.
(8) The ethylene glycol was vacuum distilled and the resulting main fraction was dried over anhydrous sodium sulfate for a long time and then vacuum distilled again using a good fractionating column.
(9) The potential process routes of preparing ethylene glycol by hydrogenating dimethyl oxalate and preparing ethylene glycol by coal can be divided into a direct synthesis method and an indirect synthesis method. The direct synthesis method is to synthesize CO and H in the synthesis gas2Synthesizing into glycol in one step. The indirect synthesis method is mainly divided into methanol formaldehyde and oxalate as intermediate products, and then ethylene glycol is obtained by hydrogenation. In contrast, the research on the synthesis of the methanol-formaldehyde route is not deep and is far from industrialization; the oxalate hydrogenation synthesis method has strong practicability and is suitable for industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the synthesis method of the high-purity ethylene glycol, and the synthesis method has the advantages of simple synthesis process, easily obtained raw materials, milder reaction, environmental protection, no pollution, high reaction selectivity and conversion rate and low impurity content of the obtained product ethylene glycol.
According to one aspect of the present invention, there is provided a method for synthesizing high purity ethylene glycol, comprising the steps of:
step one, adding a copper sulfate solution into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1 (4-6), and the molar ratio of copper sulfate to dimethyl oxalate is 1 (50-800);
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 4-6g/g cat.h, the temperature is 120-150 ℃ and the pressure is 9-10MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1 (60-80).
Preferably, the molar ratio of the copper sulfate to the dimethyl oxalate is 1: 500.
Preferably, the molar ratio of the copper sulfate to the ammonia water is 1: 5.5.
Preferably, the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Preferably, the liquid hourly space velocity is 5.5g/g cat.h.
Preferably, the temperature is 135 ℃.
Preferably, the pressure is 9 MPa.
Preferably, in the step one, after the copper sulfate solution is added to the dimethyl oxalate, the silicon source is added before the ammonia water is added dropwise.
Preferably, the silicon source is any one of silicate ester, white carbon black or silica sol.
Compared with the prior art, the invention has the following beneficial effects:
(1) the synthesis method of the high-purity ethylene glycol has high reaction selectivity and conversion rate, and the obtained product ethylene glycol has low impurity content;
(2) the synthesis method of the high-purity ethylene glycol has the advantages of high reaction rate, full contact of reactants, thorough reaction, high product yield, simple and convenient synthesis operation, low requirement on equipment strength and simple operation;
(3) the synthesis method of the high-purity ethylene glycol has the advantages of simple synthesis process, easily obtained raw materials and low cost investment;
(4) the synthesis method of the high-purity ethylene glycol has the advantages of stable product yield, basically no wastewater discharge in the synthesis process, environmental protection, no pollution and good industrial application prospect;
(5) the synthesis method of the high-purity ethylene glycol has the advantages of simple reaction, ingenious design, obvious effect, low cost and strong practicability, and is suitable for large-scale popularization.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:5.5, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 500;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 5.5g/g cat.h, the temperature is 135 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Example 2
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silicate ester into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:5.5, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 500;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 5.5g/g cat.h, the temperature is 135 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Example 3
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and white carbon black into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:5.5, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 500;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 5.5g/g cat.h, the temperature is 135 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Example 4
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silica sol into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:5.5, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 500;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 5.5g/g cat.h, the temperature is 135 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Example 5
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silica sol into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:4, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 50;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 4g/g cat.h, the temperature is 120 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 60.
Example 6
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silica sol into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:6, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 800;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 6g/g cat.h, the temperature is 150 ℃ and the pressure is 10MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Example 7
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silica sol into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:4, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 200;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 6g/g cat.h, the temperature is 140 ℃ and the pressure is 9.8MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 70.
Example 8
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and silica sol into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:6, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 600;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 5g/g cat.h, the temperature is 135 ℃ and the pressure is 9MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 75.
Example 9
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution and white carbon black into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:4.8, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 300;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 4.8g/g cat.h, the temperature is 130 ℃ and the pressure is 9.5MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 65.
Example 10
This example provides a process for the synthesis of high purity ethylene glycol comprising the steps of:
step one, adding a copper sulfate solution into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1:6, and the molar ratio of copper sulfate to dimethyl oxalate is 1: 800;
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 6g/g cat.h, the temperature is 150 ℃ and the pressure is 10MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1: 80.
Examples 1-10 have the following beneficial effects:
(1) the selectivity and the conversion rate of the reaction are high, and the impurity content of the obtained product ethylene glycol is low;
(2) the reaction rate is high, reactants are fully contacted, the reaction is thorough, the product yield is high, the synthesis operation is simple and convenient, the required intensity on equipment is low, and the operation is simple;
(3) the synthesis process is simple, the raw materials are easy to obtain, and the cost investment is low;
(4) the product yield is stable, the synthetic process basically has no wastewater discharge, the environment is protected, no pollution is caused, and the method has good industrial application prospect;
(5) the reaction is simple, the design is ingenious, the effect is obvious, the cost is low, the practicability is high, and the method is suitable for large-scale popularization.
The ethylene glycol prepared under the conditions described in example 4 had the best performance, with the following test results:
from the analysis in the above table, it can be seen that, compared with the ethylene glycol prepared by other methods, the ethylene glycol prepared by the conditions described in example 4 has a content of 99.98% (m/m), a diethylene glycol content of only 0.0021% (m/m), and a moisture content of 0.018% (m/m), and thus, the ethylene glycol prepared by the method has a high content, and the obtained product ethylene glycol has a low content of impurities, which indicates that the preparation method can fully contact the reactants, the reaction is relatively thorough, and the product yield is high; the appearance is transparent liquid, no mechanical impurities exist, and the chroma reaches 1 level; meanwhile, the absorption rate of other properties, the initial boiling point, the dry point, the density at 20 ℃ and the like all meet the requirements of detection standards, and the detection method is superior.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. The synthesis method of the high-purity ethylene glycol is characterized by comprising the following steps:
step one, adding a copper sulfate solution into dimethyl oxalate, and dropwise adding ammonia water under stirring, wherein the molar ratio of copper sulfate to ammonia water is 1 (4-6), and the molar ratio of copper sulfate to dimethyl oxalate is 1 (50-800);
and step two, introducing hydrogen into the mixed solution prepared in the step one under the reaction conditions that the liquid hourly space velocity is 4-6g/g cat.h, the temperature is 120-150 ℃ and the pressure is 9-10MPa, and converting dimethyl oxalate into ethylene glycol, wherein the molar ratio of the dimethyl oxalate to the hydrogen is 1 (60-80).
2. The method for synthesizing high purity ethylene glycol according to claim 1, wherein the molar ratio of copper sulfate to dimethyl oxalate is 1: 500.
3. The method for synthesizing high purity ethylene glycol according to claim 1, wherein the molar ratio of copper sulfate to aqueous ammonia is 1: 5.5.
4. The method of synthesizing high purity ethylene glycol according to claim 1, wherein the molar ratio of dimethyl oxalate to hydrogen is 1: 80.
5. The process of claim 1, wherein the liquid hourly space velocity is 5.5g/g cat.h.
6. The method of synthesizing high purity ethylene glycol according to claim 1, wherein the temperature is 135 ℃.
7. The method of synthesizing high purity ethylene glycol according to claim 1, wherein the pressure is 9 MPa.
8. The method for synthesizing high-purity ethylene glycol according to claim 1, wherein in the first step, after the copper sulfate solution is added to dimethyl oxalate, the silicon source is added before ammonia water is added dropwise.
9. The method for synthesizing high-purity ethylene glycol according to claim 8, wherein the silicon source is any one of silicate, white carbon black, and silica sol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911053862 | 2019-10-31 | ||
| CN201911053862X | 2019-10-31 |
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| CN101993341A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing glycol through hydrogenation of oxalic ester |
| CN102649691A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101993341A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for producing glycol through hydrogenation of oxalic ester |
| CN102649691A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester |
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