CN102951998A - Method of preparing glycol by using one-step ethylene method - Google Patents
Method of preparing glycol by using one-step ethylene method Download PDFInfo
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- CN102951998A CN102951998A CN2011102479661A CN201110247966A CN102951998A CN 102951998 A CN102951998 A CN 102951998A CN 2011102479661 A CN2011102479661 A CN 2011102479661A CN 201110247966 A CN201110247966 A CN 201110247966A CN 102951998 A CN102951998 A CN 102951998A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method of preparing glycol by using a one-step ethylene method. The method comprises contacting ethylene, and an aqueous hydrogen peroxide solution with a catalyst containing titanium-silicon molecular sieves in an organic solvent under an oxidation reaction condition, wherein the contact is carried out in the presence of a surfactant. The method provided by the invention can directly use the ethylene and the aqueous hydrogen peroxide solution as raw materials, and directly prepare the glycol under the catalysis of the catalyst containing the titanium-silicon molecular sieves; and is high in conversion rate of the ethylene and in selectivity of the target product glycol.
Description
Technical field
The present invention relates to the method that a kind of ethene single stage method prepares ethylene glycol.
Background technology
Ethylene glycol (Ethylene Glycol, be called for short EG), claim again glycol, or ethylene glycol, it is a kind of important Organic Chemicals, after being found to generate polyethylene terephthalate with terephthalic acid (PTA) reaction, can be used as the raw material of trevira and polyester plastics, the consumption of ethylene glycol increases sharply.At present, ethylene glycol is mainly for the production of polyester, frostproofer and lubricant, softening agent, tensio-active agent and explosive etc.
At present domestic and international large-scale ethylene glycol production all adopts direct hydration method also to claim the operational path that pressurized water is legal, this technique be with oxyethane (EO) and water by 1: 20-22 (mol ratio) is made into mixed aqueous solution, in tubular reactor in 130-180 ℃, 1.0-2.5MPa lower reaction 18-30min, EO all is converted into alcohol mixture, the aqueous glycol solution content that generates about about 10% (massfraction), then separates obtaining ethylene glycol and by product glycol ether (DEG) greatly with rectification under vacuum through multiple-effect evaporator dehydration concentrate, triglycol (TEG).The mol ratio of EG, DEG and TEG is about 100: 10: 1 in the alcohol mixture, and total yield of products is 88%.The consumption that increases water can reduce by product, improve simultaneously the transformation efficiency of EO, but production equipment need arrange a plurality of vaporizers, equipment is many, energy consumption is high, directly affects the production cost of ethylene glycol, and this also is the outstanding defective place of direct hydration method.
Have water for EO direct hydration method water: the high shortcoming of EO mol ratio (water ratio), both at home and abroad software engineering researchers invent catalytic hydration, to reduce the water ratio in the direct hydration method process, guarantee simultaneously the selectivity of higher EG.Although, catalytic hydration has solved the water of direct hydration method than high shortcoming, but this has also brought other problem, use (using more catalyzer to have: anionic catalyst such as molybdate, tungstate, vanadate) such as catalyzer in the hydro-combination process has not only strengthened production cost, also environment has been caused certain harm simultaneously.
Also have the investigator to propose NSC 11801 method synthesizing glycol: it is specifically by oxyethane (EO) and carbonic acid gas synthesizing ethylene carbonate (EC), obtain ethylene glycol with the NSC 11801 hydrolysis again, its reaction process is as follows: in the presence of catalyst for esterification reaction, EO and carbonic acid gas react and generate EC, then in the presence of catalyzer, the EC hydrolysis generates EG.This shows, the operation of NSC 11801 method synthesizing glycol is comparatively complicated.
By as can be known aforementioned, the synthetic of ethylene glycol all is as raw material with oxyethane at present, and oxyethane needs to synthesize (more as studying: ethene chlorohydrination and silver-colored catalysis epoxidation legal system are for oxyethane) by other technology, therefore this is undoubtedly so that a whole set of technological process is comparatively complicated, and cost is higher, therefore, can develop on the basis of existing technology and a kind ofly can will have very important Research Significance by the method for the direct synthesizing glycol of ethene.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of environmental friendliness, the simple ethene single stage method of preparation process to prepare the method for ethylene glycol.
The present inventor is studying with ethene as raw material, prepare take HTS as catalyzer in the process of ethylene glycol and find, in any case by optimizing the various processing parameters (as selecting suitable solvent, optimizing the condition of oxidizing reaction etc.) in this process, all can't obtain ethylene glycol.Through long-term endeavour, by multiple imagination is put into practice, the present inventor finds finally, can be by adding tensio-active agent, make ethene under solvent and tensio-active agent acting in conjunction, can and be subject to the titanium molecular sieve catalysis effect with the fine dissolving of hydrogen peroxide, thereby generation epoxidation of ethylene, generate the oxyethane of high dispersing in solvent, and the existence because of solvent and tensio-active agent, be dissolved in the contained water of oxidant hydrogen peroxide to newly-generated oxyethane high dispersing, and under the catalysis of HTS acid site hydrated in-situ occurs, thereby almost when generating oxyethane, with regard to the consecutive reaction of initial ring oxidative ethane and water, generating glycol.This ethene arrives the consecutive reaction of ethylene glycol again to oxyethane, avoided the accumulation because of oxyethane, and caused producing other side reactions.Because the oxyethane that reaction produces, at once reaction has generated ethylene glycol, both guaranteed the high conversion of ethene, obtain again the oxyethane of highly selective, because the oxyethane that generates is that high dispersing is given birth to catalyzed reaction with steeping in water for reconstitution in the system of solvent and tensio-active agent, be difficult for producing other side reactions again, so can obtain ethylene glycol by highly selective, thereby can realize that the ethene single stage method prepares ethylene glycol, has finished the present invention based on this discovery.
The invention provides the method that a kind of ethene single stage method prepares ethylene glycol, the method comprises: under oxidation reaction condition, ethene, aqueous hydrogen peroxide solution and the catalyzer that contains HTS are contacted in organic solvent, and wherein, described contact is carried out in the presence of tensio-active agent.
Method of the present invention can be directly take ethene, aqueous hydrogen peroxide solution as raw material, under the katalysis of the catalyzer that contains HTS, directly prepare ethylene glycol, method of the present invention, the transformation efficiency of ethene is high and selectivity target product ethylene glycol is high.
Embodiment
The invention provides the method that a kind of ethene single stage method prepares ethylene glycol, the method comprises: under oxidation reaction condition, ethene, aqueous hydrogen peroxide solution and the catalyzer that contains HTS are contacted in organic solvent, and wherein, described contact is carried out in the presence of tensio-active agent.
All can realize purpose of the present invention according to the aforesaid method of the present invention, in order further to improve the transformation efficiency of reactant ethylene, for the present invention, under the preferable case, by weight, the amount of described tensio-active agent is the 5-50000ppm of organic solvent, is preferably 150-1000ppm, more preferably 150-500ppm.
Among the present invention, as long as can realize goal of the invention of the present invention so that contain tensio-active agent in ethene, aqueous hydrogen peroxide solution and the system that the catalyzer that contains HTS contacts in organic solvent, the adding mode of concrete Surfactant is without particular requirement, for example can in advance tensio-active agent be joined in the solvent and then introduce with solvent, also tensio-active agent can be introduced at last (being about to add again after all reactant feed are mixed), also can after having added the partial reaction raw material, be introduced again.No matter above-mentioned which kind of introduce the mode of tensio-active agent, all can realize goal of the invention of the present invention, and effect is suitable, and for the easy of actual mechanical process, by in advance tensio-active agent being joined in the liquid (such as organic solvent), then be incorporated in the system of contact with liquid on one side.
According to the present invention, as long as so that ethene, contain tensio-active agent in hydrogen peroxide and the system that the catalyzer that contains HTS contacts and can realize goal of the invention of the present invention in organic solvent, optional a wider range of the kind of described tensio-active agent, can also can be water miscible tensio-active agent for oil-soluble tensio-active agent, in order further to improve the selectivity of target product ethylene glycol, under the preferable case, described tensio-active agent is selected from tween (Tween) tensio-active agent, Ni Nale (Ninol) tensio-active agent, sapn (Span) tensio-active agent, TX-10 (alkylphenol polyoxyethylene) tensio-active agent, in OP-10 (Triton X-100) tensio-active agent and AEO-9 (fatty alcohol-polyoxyethylene ether) tensio-active agent one or more; One or more in Tween-60 (Tween-60), tween-80 (Tween-80), Arlacel-60 (Span-60), the Arlacel-80 (Span-80) more preferably.
Among the present invention, the described catalyzer that contains HTS can and/or contain the preformed catalyst of HTS for HTS.Generally speaking, rhythmic reaction adopts HTS as catalyzer, and successive reaction adopts and contains the preformed catalyst of HTS as catalyzer.
Among the present invention, the described preformed catalyst that contains HTS generally contains carrier and HTS, and take total catalyst weight as benchmark, the content of described carrier is 10-90%, and the content of HTS is 10-90%.
Described carrier can be this area various heat-resisting porous material commonly used, and particularly, described heat-resisting porous material can be heat-resisting inorganic oxide and/or silicate, and the present invention, is not described in detail in this without particular requirement this.
The method according to this invention, HTS described in the present invention can be the HTS (such as TS-1) of MFI structure, the HTS of MEL structure (such as TS-2), the HTS of BEA structure (such as Ti-Beta), the HTS of MWW structure (such as Ti-MCM-22), the HTS of two dimension hexagonal structure is (such as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (such as Ti-MOR), at least a in the HTS (such as Ti-ZSM-48) of the HTS of TUN structure (such as Ti-TUN) and other structures.
Under the preferable case, described HTS is one or more in the HTS of the HTS of HTS, MEL structure of MFI structure and BEA structure, the HTS of MFI structure more preferably, more preferably described HTS is the MFI structure, HTS crystal grain is hollow structure, the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under 1 hour the condition at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and the desorption isotherm.
In the present invention, described HTS can be commercially available, and also can prepare, and prepares the method for described HTS for conventionally known to one of skill in the art, does not repeat them here.
The present invention to the condition of described oxidizing reaction without particular requirement, can for routine with the reaction conditions of HTS as the oxidation system of catalyzer, because ethylene oxide hydration need to consume the water of part among the present invention, and when existing with gaseous form, hydrogen peroxide easily explodes, therefore as previously mentioned, the present invention preferably with aqueous hydrogen peroxide solution as oxygenant.According to of the present invention preferred embodiment a kind of, the described catalyzer that contains HTS is HTS, and the mol ratio that the condition of described oxidizing reaction generally comprises ethene and hydrogen peroxide is 1: 0.1-10 is preferably 1: 1-8, more preferably 1: 2-6; The mass ratio of organic solvent, water, catalyzer and ethene is 0.1-100: 0.01-100: 0.001-1: 1, be preferably 0.1-10: 0.1-50: 0.01-0.8: and 1,1-5: 2-20: 0.01-0.5 more preferably: 1; The temperature of contact is 20-260 ℃, is preferably 30-95 ℃; Pressure is 0.1-9MPa, is preferably 0.1-1.5MPa.Under these conditions, can select as required the time of required contact, be generally 0.1-20h, be preferably 0.3-4h.The previous reaction condition generally is fit to the rhythmic reaction system, also can be used for successive reaction, such as the reaction in the slurry bed.
Without particular requirement, for the present invention, the concentration of the hydrogen peroxide in the preferred described aqueous hydrogen peroxide solution is the 20-80 % by weight, is preferably the 30-70 % by weight to the concentration of hydrogen peroxide in the described aqueous hydrogen peroxide solution in the present invention.For example can be the hydrogen peroxide of 30 commercially available % by weight, 50 % by weight or 70 % by weight.
According to another embodiment of the invention, the described catalyzer that contains HTS is the preformed catalyst that contains HTS, and it is 20-260 ℃ that the condition of described oxidizing reaction generally comprises temperature, is preferably 50-95 ℃; Pressure is 0.1-9MPa, is preferably 1.5-4.0MPa; Liquid hourly space velocity is 0.01-10h
-1, be preferably 0.1-3h
-1The mol ratio of ethene and hydrogen peroxide is 1: 0.1-10 is preferably 1: 1-8, more preferably 1: 2-6; The mass ratio of organic solvent, water and ethene is 0.1-100: 0.01-100: 1, be preferably 0.1-10: 0.1-50: and 1,1-5: 2-20 more preferably: 1; The agent oil volume is preferably 0.5-5 than for 0.01-10.The previous reaction condition generally is fit to the successive reaction system, such as successive reaction systems such as fixed beds.Liquid hourly space velocity described in the present invention is the definition of the conventional liquid hourly space velocity of using in this area, it is a kind of representation of air speed, its meaning is the per hour volume for the treatment of solution phase reaction thing of unit reaction volume (for the reaction of adopting solid catalyst, then being per volume of catalyst).The agent oil volume is the cumulative volume of catalyzer and the ratio of the cumulative volume of all liquid phase materials than the definition for the conventional agent oil volume ratio that uses in this area among the present invention.
The present invention to the described preformed catalyst of HTS that contains without particular requirement, can be the various moulding titanium-silicon molecular sieve catalysts that can be applicable to the successive reaction system, under the preferable case, the described preformed catalyst that contains HTS comprises carrier and HTS, wherein, take total catalyst weight as benchmark, the content of carrier is the 10-90 % by weight, and the content of HTS is the 10-90 % by weight.
The present invention to the carrier in the described preformed catalyst that contains HTS without particular requirement, can be the carrier of various preformed catalysts commonly used, for example heat-resistant inorganic oxide and/or the silicate of porous can be, concrete in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast, beryllium oxide and the clay one or more can be.More preferably, described carrier is one or more in aluminum oxide, silicon oxide, magnesium oxide and the zirconium white.
Among the present invention, the described forming method that contains the preformed catalyst of HTS can adopt technology well known in the art to carry out, can be prepared according to the method for the preformed catalyst of routine, mainly comprise the steps such as making beating, granulation and roasting, the present invention to this all without particular requirement.
As everyone knows, with HTS/H
2O
2Catalytic oxidation system, the effect of solvent mainly are in order to make reaction solution be homogeneous phase.Under this basic premise, the sterically hindered of solvent self can not be too large, can guarantee like this to react to carry out efficiently.And in the chosen process of solvent, those skilled in the art generally can select according to mentioned above principle, but the scope of selecting can not be confined to above-mentioned requirements, specifically must select according to concrete oxidizing reaction system.The present inventor's discovery, in the oxidation of ethylene system, at the solvent system that satisfies on the basis of aforementioned requirement, ethene all can be converted into target product ethylene glycol, but the yield of its transformation efficiency and target product is still limited.And the present inventor further finds, reaction effect is better during as solvent with in ketone, alcohols, carboxylic-acid and the halogenated organic alkane one or more, more preferably one or more in the halogenated organic alkane of the carboxylic acid of the alcohol of the ketone of C3-C10, C1-C10, C1-C10 and C1-C10; One or more in the halogenated organic alkane of the pure and mild C1-C6 of the ketone of C3-C6, C2-C6 more preferably are particularly preferably in acetone, butanone, ethanol, propylene glycol, the trimethyl carbinol, acetic acid and the trichloromethane one or more.
As previously mentioned, method provided by the invention can adopt periodical operation, also can operate continuously etc., the present invention to this without particular requirement.Feed way also can be any suitable way well known by persons skilled in the art, as when andnon-continuous operation manner is carried out, solvent, catalyzer can be added reactor after, add ethene continuously, hydrogen peroxide reacts; When in closed tank reactor, carrying out rhythmic reaction, catalyzer, solvent, ethene and hydrogen peroxide can be added hybrid reaction in the still simultaneously.Can adopt the reactor commonly used such as fixed-bed reactor, slurry bed reactor when continuous mode carries out, when carrying out in fixed-bed reactor, feed way can add solvent, ethene and hydrogen peroxide behind the catalyzer of packing into continuously; When in slurry bed reactor, carrying out, can be with adding ethene, hydrogen peroxide react continuously after the catalysts and solvents making beating; The present invention, does not give unnecessary details at this all without particular requirement one by one to this.
Following embodiment will be further described the present invention, but therefore not limit content of the present invention.In embodiment and the Comparative Examples, used reagent is commercially available chemically pure reagent.
Used HTS (TS-1) catalyzer is (TS-1) sieve sample of preparing by the method described in the document [Zeolites, 1992, Vol.12 943-950 page or leaf], and titanium oxide content is 2.5 % by weight.
Used hollow HTS HTS is that (Hunan is built long company and made for the Industrial products of the described HTS of CN1301599A among the embodiment, be the HTS of MFI structure through X-ray diffraction analysis, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is the 15-180 nanometer; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
Among the present invention, adopt gas-chromatography to carry out each analysis that forms in the system, undertaken quantitatively all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the evaluation indexes such as the yield of transformation efficiency, product of reactant and selectivity.
In Comparative Examples and embodiment:
Embodiment 1
Be that (hydrogen peroxide provided with the aqueous hydrogen peroxide solution of 30 % by weight in 1: 2 with ethene, hydrogen peroxide, solvent acetone (containing tensio-active agent Tween-60 250ppm and Arlacel-80 200ppm) and catalyzer (TS-1) according to the mol ratio of ethene and hydrogen peroxide, following examples are roughly the same) send into and carry out successive reaction in the reactor, and the mass ratio of ethene and catalyzer is 20: 1, the mass ratio of ethene and solvent is 1: 1.5, is that 30 ℃, pressure are to react under the 1.5MPa in temperature.Reacted 3.5 hours: conversion of ethylene is 97.9%, and glycol selectivity is 99.2%.
Embodiment 2
Be to send at 1: 4 to carry out successive reaction in the reactor with ethene, hydrogen peroxide, solvent trichloromethane (containing tensio-active agent tween-80 130ppm and Arlacel-60 75ppm) and catalyzer (TS-1) according to the mol ratio of ethene and hydrogen peroxide, and the mass ratio of ethene and catalyzer is 40: 1, the mass ratio of ethene and solvent 1: 1.5 is that 40 ℃, pressure are to react under the 0.5MPa in temperature.Reacted 1.5 hours: conversion of ethylene is 98.7%, and glycol selectivity is 99.1%.
Embodiment 3
Be the mixture (containing tensio-active agent tween-80 280ppm, TX-10120ppm and AEO-960ppm) of acetone and trichloromethane and catalyzer (TS-1) according to the mol ratio of ethene and hydrogen peroxide with ethene, hydrogen peroxide, solvent be to send at 1: 5 to carry out successive reaction in the reactor, the mass ratio of ethene and catalyzer is 80: 1, the mass ratio of ethene and solvent acetone 1: 0.8, the mass ratio of ethene and solvent trichloromethane 1: 0.4 is that 50 ℃, pressure are to react under the 1.0MPa in temperature.Reacted 3 hours: conversion of ethylene is 99.1%, and glycol selectivity is 99.0%.
Embodiment 4
Be the mixture (containing Ni Nale tensio-active agent 50ppm and Arlacel-80 110ppm) of the trimethyl carbinol and acetic acid and catalyzer (TS-1) according to the mol ratio of ethene and hydrogen peroxide with ethene, hydrogen peroxide, solvent be to send at 1: 5.5 to carry out successive reaction in the reactor, and the mass ratio of ethene and catalyzer is 2: 1, the mass ratio of ethene and solvent tertiary butanol 1: 0.2, the mass ratio of ethene and solvent acetic acid 1: 1.4 is that 70 ℃, pressure are to react under the 1.5MPa in temperature.Reacted 0.5 hour: conversion of ethylene is 99.5%, and glycol selectivity is 98.5%.
Embodiment 5
Identical with the method for embodiment 1, different is that TS-1 is replaced by HTS, and reacted 0.5 hour: conversion of ethylene is 99.3%, and glycol selectivity is 99.6%.
Embodiment 6
Identical with the method for embodiment 1, different is, TS-1 (is to press prior art Corma etc. by Ti-MCM-41, Chem.Commun., method preparation described in 1994, the 147-148, titanium oxide content is 3 % by weight) replace, reacted 6 hours: conversion of ethylene is 95.2%, and glycol selectivity is 92.4%.
Embodiment 7
Identical with the method for embodiment 1, different is, TS-1 (is by J.Chem.Soc. such as prior art Takashi Tatsumi by Ti-Beta, Chem.Commun.1997, method preparation described in the 677-678, titanium oxide content is 2.6 % by weight) replace, reacted 4 hours: conversion of ethylene is 96.1%, glycol selectivity is 93.5%.
Embodiment 8
Identical with the method for embodiment 1, different is, contains tensio-active agent Tween-60 2500ppm and Arlacel-80 2000ppm in the solvent acetone, and reacted 3.5 hours: conversion of ethylene is 93.7%, and glycol selectivity is 87.4%.
Embodiment 9
Identical with the method for embodiment 1, different is: solvent is acetonitrile (containing tensio-active agent Tween-60 250ppm and Arlacel-80 200ppm).Reacted 3.5 hours: conversion of ethylene is 76.8%, and glycol selectivity is 46.4%.
Comparative Examples 1
Identical with the method for embodiment 1, different is not contain tensio-active agent in the solvent, and reacted 3.5 hours: conversion of ethylene is 72.3%, and glycol selectivity is 4.2%.
Can find out from embodiment and Comparative Examples: method target product selectivity of the present invention is high, and environmental friendliness, this shows, method of the present invention is very suitable for the industrial production of serialization.
Claims (10)
1. an ethene single stage method prepares the method for ethylene glycol, the method comprises: under oxidation reaction condition, ethene, aqueous hydrogen peroxide solution and the catalyzer that contains HTS are contacted in organic solvent, it is characterized in that, described contact is carried out in the presence of tensio-active agent.
2. method according to claim 1, wherein, by weight, the amount of described tensio-active agent is the 5-50000ppm of organic solvent, is preferably 150-1000ppm, more preferably 150-500ppm.
3. method according to claim 1 and 2, wherein, described tensio-active agent is selected from one or more in tween surfactants, Ni Nale tensio-active agent, sapn tensio-active agent, TX-10 tensio-active agent, OP-10 tensio-active agent and the AEO-9 tensio-active agent; One or more in Tween-60, tween-80, Arlacel-60, the Arlacel-80 more preferably.
4. method according to claim 1 and 2, wherein, the described catalyzer that contains HTS is HTS and/or the preformed catalyst that contains HTS.
5. method according to claim 4, wherein, described HTS is at least a in the HTS of the HTS of HTS, TUN structure of HTS, the MOR structure of HTS, the MWW structure of HTS, the BEA structure of HTS, the MEL structure of MFI structure and two-dimentional hexagonal structure.
6. method according to claim 5, wherein, described HTS is the MFI structure, and crystal grain is hollow structure, and the radical length of the cavity part of this hollow structure is the 5-300 nanometer, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under 1 hour the condition at least 70 milligrams/gram, have hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and the desorption isotherm.
7. method according to claim 1 and 2, wherein, the described catalyzer that contains HTS is HTS, the condition of described oxidizing reaction comprises that the mol ratio of ethene and hydrogen peroxide is 1: 0.1-10 is preferably 1: 1-8; The mass ratio of organic solvent, water, catalyzer and ethene is 0.1-100: 0.01-100: 0.001-1: 1, be preferably 0.1-10: 0.1-50: 0.01-0.8: 1; The temperature of contact is 20-260 ℃, is preferably 30-95 ℃; Pressure is 0.1-9MPa, is preferably 0.1-1.5MPa; Time is 0.1-20h, is preferably 0.3-4h.
8. method according to claim 1 and 2, wherein, the described catalyzer that contains HTS is the preformed catalyst that contains HTS, the condition of described oxidizing reaction comprises that temperature is 20-100 ℃, is preferably 50-90 ℃; Pressure is 0.1-9MPa, is preferably 1.5-4MPa; Liquid hourly space velocity is 0.01-10h
-1, be preferably 0.1-3h
-1The mol ratio of ethene and hydrogen peroxide is 1: 0.1-10 is preferably 1: 1-8; The mass ratio of organic solvent, water and ethene is 0.1-100: 0.01-100: 1, be preferably 0.1-10: 0.1-50: 1; The agent oil volume is preferably 0.5-5 than for 0.01-10.
9. method according to claim 1 and 2, wherein, the concentration of the hydrogen peroxide in the described aqueous hydrogen peroxide solution is the 20-80 % by weight, is preferably the 30-70 % by weight.
10. method according to claim 1 and 2, wherein, described organic solvent is one or more in the halogenated organic alkane of the carboxylic acid of alcohol, C1-C10 of ketone, the C1-C10 of C3-C10 and C1-C10, be preferably in the halogenated organic alkane of pure and mild C1-C6 of ketone, C2-C6 of C3-C6 one or more, more preferably one or more in acetone, butanone, ethanol, propylene glycol, the trimethyl carbinol, acetic acid and the trichloromethane.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193636A (en) * | 2013-04-15 | 2013-07-10 | 湖南长岭石化科技开发有限公司 | Method for synthetizing 2,3-butanediol ester |
| CN103980116A (en) * | 2014-05-23 | 2014-08-13 | 山东联创节能新材料股份有限公司 | 2,3-butanediol ester and preparation method thereof |
| WO2019000264A1 (en) * | 2017-06-28 | 2019-01-03 | Solvay Sa | Process for manufacture of ethylene glycol |
| WO2019000266A1 (en) * | 2017-06-28 | 2019-01-03 | Solvay Sa | Process for manufacture of ethylene glycol |
| CN112851477A (en) * | 2019-11-26 | 2021-05-28 | 广州大有精细化工厂 | Method for preparing ethylene glycol by ethylene oxidation |
| CN113773169A (en) * | 2021-09-14 | 2021-12-10 | 湖南长岭石化科技开发有限公司 | Method for synthesizing dihydric alcohol |
| CN114272955A (en) * | 2022-01-05 | 2022-04-05 | 北京化工大学 | Preparation method of core-shell type magnetic titanium-silicon molecular sieve catalyst, product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209650A (en) * | 1976-05-28 | 1980-06-24 | Halcon International, Inc. | Process for producing ethylene glycol |
| CN101279959A (en) * | 2008-05-21 | 2008-10-08 | 湖南长岭石化科技开发有限公司 | Method for synthesizing epoxypropane |
-
2011
- 2011-08-24 CN CN201110247966.1A patent/CN102951998B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4209650A (en) * | 1976-05-28 | 1980-06-24 | Halcon International, Inc. | Process for producing ethylene glycol |
| CN101279959A (en) * | 2008-05-21 | 2008-10-08 | 湖南长岭石化科技开发有限公司 | Method for synthesizing epoxypropane |
Non-Patent Citations (1)
| Title |
|---|
| HAO LI, ET AL.: ""One-pot synthesis of ethylene glycol and its mono-methyl ether from ethylene using Al-TS-1 catalyst"", 《CATALYSIS COMMUNICATIONS》 * |
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| CN103193636A (en) * | 2013-04-15 | 2013-07-10 | 湖南长岭石化科技开发有限公司 | Method for synthetizing 2,3-butanediol ester |
| CN103980116A (en) * | 2014-05-23 | 2014-08-13 | 山东联创节能新材料股份有限公司 | 2,3-butanediol ester and preparation method thereof |
| WO2019000264A1 (en) * | 2017-06-28 | 2019-01-03 | Solvay Sa | Process for manufacture of ethylene glycol |
| WO2019000266A1 (en) * | 2017-06-28 | 2019-01-03 | Solvay Sa | Process for manufacture of ethylene glycol |
| CN112851477A (en) * | 2019-11-26 | 2021-05-28 | 广州大有精细化工厂 | Method for preparing ethylene glycol by ethylene oxidation |
| CN113773169A (en) * | 2021-09-14 | 2021-12-10 | 湖南长岭石化科技开发有限公司 | Method for synthesizing dihydric alcohol |
| CN113773169B (en) * | 2021-09-14 | 2024-04-30 | 湖南长炼新材料科技股份公司 | Synthesis method of dihydric alcohol |
| CN114272955A (en) * | 2022-01-05 | 2022-04-05 | 北京化工大学 | Preparation method of core-shell type magnetic titanium-silicon molecular sieve catalyst, product and application thereof |
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