CN1944365A - Process for synthesizing propylene glycol ether - Google Patents

Process for synthesizing propylene glycol ether Download PDF

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Publication number
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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reactor
reaction
propylene
hts
propylene glycol
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CN 200610032324
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CN100556880C (en
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王伟
林榕伟
何驰剑
伍小驹
高计皂
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Hunan Changlian New Material Technology Co ltd
Lin Rongwei
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Hunan Changling Petrochemical Technology Development Co Ltd
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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

A kind of method of synthesis of propylene glycol
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.
CNB2006100323249A 2006-09-23 2006-09-23 A kind of method of synthesis of propylene glycol Active CN100556880C (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
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

Cited By (26)

* Cited by examiner, † Cited by third party
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
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
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
CN105085201B (en) * 2014-05-08 2017-03-29 中国石油化工股份有限公司 A kind of 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
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
CN105439815B (en) * 2014-08-21 2017-12-22 中国石油化工股份有限公司 A kind of method for preparing propane diols
CN105439826B (en) * 2014-08-25 2017-12-22 中国石油化工股份有限公司 A kind of preparation method of propylene glycol monomethyl ether
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
CN110156571A (en) * 2018-02-13 2019-08-23 中国石油化工股份有限公司 Propylene method for oxidation
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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