CN1944365A - Process for synthesizing propylene glycol ether - Google Patents
Process for synthesizing propylene glycol ether Download PDFInfo
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- CN1944365A CN1944365A CN 200610032324 CN200610032324A CN1944365A CN 1944365 A CN1944365 A CN 1944365A CN 200610032324 CN200610032324 CN 200610032324 CN 200610032324 A CN200610032324 A CN 200610032324A CN 1944365 A CN1944365 A CN 1944365A
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- propylene
- hts
- propylene glycol
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000008569 process Effects 0.000 title abstract description 8
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 title abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000006266 etherification reaction Methods 0.000 claims abstract description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- -1 HTS Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 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 9
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000007639 printing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Abstract
The present invention discloses process of synthesizing propylene glycol ether. Alcohol, propylene and hydrogen peroxide in the molar ratio of (1-60) to (0.5-10) to 1 are set inside a reactor with catalyst, propylene and hydrogen peroxide produce epoxidation reaction to produce epoxy propane, and the produced epoxy propane and alcohol produce etherification reaction to produce propylene glycol ether. The reaction conditions include reaction temperature of 0-200 deg.c, reaction pressure of 0.5-8.5 MPa, and space velocity of liquid hydrogen peroxide and alcohol of 0.1-65/hr. The present invention has simple process, environment friendship and propylene glycol ether selectivity up to 90 %.
Description
One, technical field
The present invention relates to a kind of method of synthesis of propylene glycol, particularly relate to a kind of method by propylene one-step synthesis propylene glycol.
Two, background technology
Because on the chemical structure of propylene glycol two groups with strong dissolving power--ehter bond and hydroxyl are arranged, the former has lipophilicity, solubilized hydrophobic nature compound; The latter has wetting ability, and therefore the solubilized water-soluble cpds is the versatility solvent of excellent property, and the title of " omnipotent " solvent is arranged.Its main application is to make industrial solvent, all is widely used at aspects such as coating, cleaning, printing, leathers.Can be used as the solvent of Synolac, Resins, epoxy, acrylic resin, polyurethane paint etc. in coatings industry, the paint paint film that is mixed with has advantages such as bright and clean, smooth, that fastness is good.In printing ink is produced, use propylene glycol, some prescriptions can change into water-soluble, can reduce the toxicity of printing ink, improve operating environment, improve printing quality.In the coating dissolution process, propylene glycol can replace the alcohol solvent, is a kind of good coupling agent.In addition, the propylene glycol series products can be prepared all kinds of purification agents of concentrated type.It still is the major ingredient of novel braking fluid, and its content can be up to more than 70%.
Propylene oxide nearly all is to adopt chlorohydrination and conjugated oxidation production at present in the world, and wherein chlorohydrination accounts for 49%, and conjugated oxidation accounts for 51%.China adopts chlorohydrination production.When adopting the chlorohydrination synthesizing epoxypropane, equipment corrosion is serious, consumes a large amount of Cl
2, and generation contains CaCl in producing
2Waste water, waste residue with organic chloride have caused very big pollution to environment.And production equipment requires to build in the place of chlorine resource and blowdown condition, the production site required relatively stricter.When adopting the conjugated oxidation synthesizing epoxypropane, long flow path, investment is big, and by product is the trimethyl carbinol or vinylbenzene, produces to be subjected to the restriction that the by product outlet is used.Therefore, two kinds of production methods or seriously polluted of existing propylene oxide, otherwise investment is big, the cost height, thus on raw material, limited synthesizing and production of propylene glycol.
China adopts propylene oxide and alcohol reaction to produce propylene glycol and starts from 20th century the mid-1970s, because raw material transportation inconvenience is under-supply, and problem such as backward in technique, causes enterprise's industrial scale less than normal, consume high, cost is high, poor product quality.
At present, consider the supply restriction of propylene oxide, have the scholar to propose not adopt propylene oxide, and adopt propylene one-step synthesis propylene glycol.As U.S. Pat P6,239,315 employing HTS or titaniferous, vanadium, chromium are disclosed, the tin molecular sieve is made epoxidizing agent and solid alkylation catalyst assembly catalyze propylene synthesis of propylene glycol.The Preparation of Catalyst complexity that this patent is used, the temperature of reaction harshness of synthesis of propylene glycol requires to be controlled near 0 ℃, otherwise easily produces a large amount of by products.And epoxidation of propylene is strong exothermic process, temperature of reaction is controlled near 0 ℃, had both needed a large amount of energy consumptions, also be difficult to realize, thereby cause that synthesis of propylene glycol technology is numerous and diverse, severe reaction conditions and product selectivity be low, can't carry out the industrialization production application.
Three, summary of the invention
The objective of the invention is to propose a kind of method by propylene one-step synthesis propylene glycol, this procedure is simple, product selectivity is high, and environmental friendliness, realizes easily.
The objective of the invention is to be achieved through the following technical solutions: a kind of method of synthesis of propylene glycol, it is characterized in that: mol ratio (1～60): (0.5～10): 1 alcohol, propylene and hydrogen peroxide are in being equipped with the reactor of catalyzer, propylene and hydrogen peroxide initial ring oxidizing reaction, the propylene oxide mixture that generates need not to separate and purification, further with alcohol generation etherification reaction, obtain propylene glycol, described reaction conditions is 0 ℃～200 ℃ of temperature of reaction, reaction pressure 0.5～8.5Mpa, liquid (hydrogen peroxide and alcohol) air speed 0.1～65h
-1
The molecular formula of described alcohol is CnH
2n+1OH, R in the formula 〉=1, low-carbon alcohol such as particular methanol, ethanol, butanols.
Described reactor can be the pipeline flow reactor, or fixed-bed reactor, or slurry bed reactor, or still formula batch reactor, or fluidized-bed reactor, or their combination.
Described catalyzer can be a kind of in HTS, modifying titanium-silicon molecular sieve, HTS and alkali, HTS, sodium alkoxide or the potassium alcoholate or their mixture.
Described alkali can be solid alkali, liquid base, organic bases or mineral alkali.
Described sodium alkoxide (or potassium alcoholate) can be sodium methylate (or potassium methylate), sodium ethylate (or potassium ethylate), sodium butylate organic sodium alkoxide (or organic potassium alcoholate) or their mixtures such as (or butanols potassium).
Described reaction comprises epoxidation reaction and etherification reaction: propylene at first with hydrogen peroxide initial ring oxidizing reaction, generate propylene oxide, propylene oxide need not separate directly further and alcohol generation etherification reaction, generates propylene glycol.For these two kinds of reactions are carried out more fully, obtain more propylene glycol, can select two reactors in series for use.
It also can be two reactors that separate that described reactor can be one, and the temperature of reaction of second reactor, reaction pressure can be identical with first reactor, also can be different.0 ℃～200 ℃ of the temperature of reaction of second reactor, reaction pressure 0.5～8.5Mpa, the charging air speed of the mixture that comes out from first reactor is 0.1～65h
-1
Described catalyzer can be contained in respectively in two reactors, and the catalyzer of second reactor can be identical with the catalyzer of first reactor, also can be different.The catalyzer of second reactor can be a kind of in HTS, modifying titanium-silicon molecular sieve, HTS, alkali, HTS, sodium alkoxide or the potassium alcoholate or their mixture.
The present invention adopts the method for propylene one-step synthesis propylene glycol, defectives such as existing production propylene oxide process complexity, cost height, equipment corrosion are serious, discharging harmful substance had both been improved, propylene oxide separation, purification and process such as refining have been saved again, and directly reaction mixture is carried out etherificate, whole process is simple, pollution-free, and the selectivity of propylene glycol can reach more than 90%.
Four, embodiment:
The present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1:
With the 15g titanium-silicon molecular sieve catalyst, with being loaded in the fixed-bed reactor after the dilution of 10g quartz sand.Methyl alcohol and hydrogen peroxide mol ratio 50: 1, propylene and hydrogen peroxide mol ratio 1: 1, methyl alcohol and hydrogen peroxide are gone into reactor with the metering infusion respectively, and propylene enters reactor by mass-flow gas meter, three kinds of reactants and titanium-silicon molecular sieve catalyst contact reacts, the synthesizing propanediol monomethyl ether.Reaction conditions: 0 ℃ of temperature of reaction, reaction pressure 0.5MPa, reaction bed liquid air speed 65h
-1Products therefrom is through stratographic analysis, and the propylene glycol monomethyl ether selectivity is 93.25%, and the hydrogen peroxide transformation efficiency is 98.36%.
Embodiment 2:
HTS is loaded in the slurry bed reactor, and total liquid volume is 3 liters, and loaded catalyst accounts for 5% of total amount of liquid.Ethanol and hydrogen peroxide mol ratio 60: 1, propylene and hydrogen peroxide mol ratio 0.5: 1, reaction conditions: 60 ℃ of temperature of reaction, reaction pressure 8.5MPa, reaction bed liquid air speed 8.0h
-1, other steps are with embodiment 1.Products therefrom is through stratographic analysis, and the dihydroxypropane single-ether selectivity is 90.10%, and the hydrogen peroxide transformation efficiency is 95.21%.
Embodiment 3:
10g HTS and 10g sodium ethylate are mixed,, be loaded in the fixed-bed reactor with the dilution of 20g quartz sand.Propyl alcohol and hydrogen peroxide mol ratio 1: 1, propylene and hydrogen peroxide mol ratio 6: 1, reaction conditions: 80 ℃ of temperature of reaction, reaction pressure 2.1MPa, reaction bed liquid air speed 0.1h
-1, other step is with embodiment 1.Products therefrom is through stratographic analysis, and the propylene glycol monopropyl ether selectivity is 92.32%, and the hydrogen peroxide transformation efficiency is 99.5%.
Embodiment 4:
HTS is loaded in first reactor of fixed bed, and loaded catalyst is 25g, and catalyzer is loaded on solid base catalyst in second reactor of fixed bed with the dilution of 5g quartz sand, and loaded catalyst is 15g, also with the dilution of 10g quartz sand.Methyl alcohol and hydrogen peroxide mol ratio 3: 1, propylene and hydrogen peroxide mol ratio 10: 1, methyl alcohol and hydrogen peroxide enter first reactor by volume pump respectively, and propylene is gone into first reactor by infusion, three kinds of reactants and titanium-silicon molecular sieve catalyst contact reacts, the synthesizing propanediol monomethyl ether.The reaction conditions of first reactor: 30 ℃ of temperature, pressure 2.0MPa, reaction bed liquid air speed 5.34h
-1The mixture that comes out from first reactor directly enters second reactor, the reaction conditions of second reactor without separating: 200 ℃ of temperature, pressure 1.0MPa, the charging air speed 5.34h of mixture
-1Products therefrom is through stratographic analysis, and the propylene glycol monomethyl ether selectivity is 98.2%, and the hydrogen peroxide transformation efficiency is 99.4%.
Embodiment 5:
With the 25g titanium-silicon molecular sieve catalyst, with being loaded in first fixed-bed reactor after the dilution of 15g quartz sand.Butanols and hydrogen peroxide mol ratio 5: 1, propylene and hydrogen peroxide mol ratio 1.5: 1, the reaction conditions of first reactor: 30 ℃ of temperature of reaction, reaction pressure 2.0MPa, reaction bed liquid air speed 20h.The gained mixture directly feeds second the reaction conditions of second reactor is housed in the 10g HTS slurry bed reactor: 95 ℃ of temperature of reaction, reaction pressure 3.5MPa, the charging air speed 20h of mixture
-1, other steps are with embodiment 4.Products therefrom is through stratographic analysis, and the propylene glycol monobutyl ether selectivity is 92.23%, and the hydrogen peroxide transformation efficiency is 93.43%.
Claims (6)
1, a kind of method of synthesis of propylene glycol, it is characterized in that: mol ratio (1～60): (0.5～10): 1 alcohol, propylene and hydrogen peroxide are in being equipped with the reactor of catalyzer, propylene and hydrogen peroxide initial ring oxidizing reaction, the propylene oxide that generates further with alcohol generation etherification reaction, obtain propylene glycol, described reaction conditions is 0～200 ℃ of a temperature of reaction, reaction pressure 0.5～8.5Mpa, liquid (hydrogen peroxide and alcohol) air speed 0.1～65h
-1
2, method according to claim 1 is characterized in that: low-carbon alcohol such as described pure particular methanol, ethanol, butanols.
3, method according to claim 1 is characterized in that: described reactor can be the pipeline flow reactor, or fixed-bed reactor, or slurry bed reactor, or still formula batch reactor, or fluidized-bed reactor, or their combination.
4, method according to claim 1 is characterized in that: described catalyzer can be a kind of in HTS, modifying titanium-silicon molecular sieve, HTS, alkali, HTS, sodium alkoxide or the potassium alcoholate or their mixture.
5, according to claim 1,2 described methods, it is characterized in that: described reactor can be two reactors that separate, 0 ℃～200 ℃ of the temperature of reaction of second reactor, reaction pressure 0.5～8.5Mpa, the charging air speed of the mixture that comes out from first reactor is 0.1～65h
-1
6, method according to claim 5 is characterized in that: the catalyzer of second reactor can be a kind of in HTS, modifying titanium-silicon molecular sieve, HTS, alkali, HTS, sodium alkoxide or the potassium alcoholate or their mixture.
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|---|---|---|---|
| CNB2006100323249A CN100556880C (en) | 2006-09-23 | 2006-09-23 | A kind of method of synthesis of propylene glycol |
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|---|---|---|---|
| CNB2006100323249A CN100556880C (en) | 2006-09-23 | 2006-09-23 | A kind of method of synthesis of propylene glycol |
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| CN1944365A true CN1944365A (en) | 2007-04-11 |
| CN100556880C CN100556880C (en) | 2009-11-04 |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452908A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing glycol monoether from ethylene |
| CN102952003A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN102964222A (en) * | 2012-11-13 | 2013-03-13 | 宁波杭州湾新区珠峰企业管理服务有限公司 | Method for synthesizing propylene glycol ether |
| CN103012077A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing alcoholysis of propylene epoxide |
| CN103012078A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
| CN104211584A (en) * | 2014-09-10 | 2014-12-17 | 百川化工(如皋)有限公司 | Method for preparing dipropylene glycol methyl ether |
| CN104557479A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether |
| CN105085201A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether |
| CN105399609A (en) * | 2014-09-15 | 2016-03-16 | 中国石油化工股份有限公司 | Propylene glycol monomethyl ether preparation method |
| CN105439815A (en) * | 2014-08-21 | 2016-03-30 | 中国石油化工股份有限公司 | Method for preparing propylene glycol |
| CN105439826A (en) * | 2014-08-25 | 2016-03-30 | 中国石油化工股份有限公司 | A preparing method of propylene glycol monomethyl ether |
| CN107501053A (en) * | 2017-09-19 | 2017-12-22 | 山东理工大学 | A kind of green synthesis method by the step alcohol ether of alkene one |
| CN110156571A (en) * | 2018-02-13 | 2019-08-23 | 中国石油化工股份有限公司 | Propylene method for oxidation |
| CN110759809A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN111099973A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Propylene oxidation process |
-
2006
- 2006-09-23 CN CNB2006100323249A patent/CN100556880C/en active Active
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452908B (en) * | 2010-10-15 | 2014-04-02 | 中国石油化工股份有限公司 | Method for preparing glycol monoether from ethylene |
| CN102452908A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing glycol monoether from ethylene |
| CN102952003A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethylene glycol monomethyl ether by using one-step ethylene method |
| CN103012078B (en) * | 2011-09-28 | 2015-07-01 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
| CN103012077A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing alcoholysis of propylene epoxide |
| CN103012078A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide |
| CN103012077B (en) * | 2011-09-28 | 2015-02-25 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether by catalyzing alcoholysis of propylene epoxide |
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| CN104557479A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether |
| CN104557479B (en) * | 2013-10-29 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of method preparing propylene glycol monomethyl ether |
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| CN105085201A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Method for preparing propylene glycol monomethyl ether |
| CN105439815A (en) * | 2014-08-21 | 2016-03-30 | 中国石油化工股份有限公司 | Method for preparing propylene glycol |
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| CN105439826A (en) * | 2014-08-25 | 2016-03-30 | 中国石油化工股份有限公司 | A preparing method of propylene glycol monomethyl ether |
| CN104211584A (en) * | 2014-09-10 | 2014-12-17 | 百川化工(如皋)有限公司 | Method for preparing dipropylene glycol methyl ether |
| CN104211584B (en) * | 2014-09-10 | 2016-06-29 | 百川化工(如皋)有限公司 | A kind of method preparing dipropylene glycol methyl ether |
| CN105399609B (en) * | 2014-09-15 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of method for preparing propylene glycol monomethyl ether |
| CN105399609A (en) * | 2014-09-15 | 2016-03-16 | 中国石油化工股份有限公司 | Propylene glycol monomethyl ether preparation method |
| CN107501053A (en) * | 2017-09-19 | 2017-12-22 | 山东理工大学 | A kind of green synthesis method by the step alcohol ether of alkene one |
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| CN110156571B (en) * | 2018-02-13 | 2022-03-11 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN110759809A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN110759809B (en) * | 2018-07-27 | 2023-03-24 | 中国石油化工股份有限公司 | Propylene oxidation process |
| CN111099973A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Propylene oxidation process |
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