CN100413578C - Columbium oxide catalyst for hydrating epoxy ethane to prepare ethandiol - Google Patents
Columbium oxide catalyst for hydrating epoxy ethane to prepare ethandiol Download PDFInfo
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- CN100413578C CN100413578C CNB2004100666273A CN200410066627A CN100413578C CN 100413578 C CN100413578 C CN 100413578C CN B2004100666273 A CNB2004100666273 A CN B2004100666273A CN 200410066627 A CN200410066627 A CN 200410066627A CN 100413578 C CN100413578 C CN 100413578C
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Abstract
The present invention relates to niobium monoxide catalyst for preparing glycol by epoxy ethane catalytic hydration, which mainly solves the problems that the water ratio of the existing epoxy ethane non-catalytic hydration reaction is high, the energy consumption is large and the production cost is high, or the liquid acid catalyst used in catalytic hydration etches equipment and pollutes the environment, and the stability or the stability and the activity of solid acid catalyst can not be simultaneously kept. The present invention solves the problems by adopting the technical scheme that load type niobium is used as oxide catalyst, the oxide raw material of the niobium is selected from one kind of halogenated niobium, alkoxy niobium, hydroxy acid derivative of the niobium, phenol niobium, carboxylic acid niobium and niobium-ammonia complex compounds. The present invention is used in industrial production of glycol.
Description
Technical field
The present invention relates to a kind of columbium oxide catalyst of hydrating epoxy ethane to prepare ethandiol.
Background technology
Ethylene glycol is important aliphatic dihydroxy alcohol, and is of many uses, and main application is to produce mylar, comprises fiber, film and engineering plastics.Also can directly be used as cooling agent and antifreezing agent, also be simultaneously to produce the indispensable materials of product such as alkyd resins, plasticizer, paint, adhesive, surfactant, explosive and capacitor electrolyte.
Industrial preparation ethylene glycol adopts direct hydration method at present.This method is not used catalyst, and the mol ratio of reaction feed water and oxirane (hereinafter to be referred as the water ratio) is 20～25: 1,150～200 ℃ of reaction temperatures, reaction pressure 0.8～2.0MPa, in about 30 minutes of reaction time, the oxirane conversion ratio is near 100%, glycol selectivity 88～90%.Industrial employing pipeline reactor, the length of reactor are 150 meters, owing to do not use catalyst, hydration reaction speed is slower, makes required reactor bigger, has caused the increase of transmission and mass transfer energy.In the reaction, because ethylene glycol and reacting ethylene oxide activity are higher than the reactivity of water and oxirane, unconverted oxirane continues and the glycol product reaction, generates accessory substances such as diethylene glycol (DEG), triethylene glycol, therefore the industrial excessive greatly way of water of taking improves glycol selectivity.Because the consumption of accessory substances such as diethylene glycol, triethylene glycol is little at present, market demand deficiency, and the ethylene glycol demand growth is very fast, therefore, exploitation high activity, high selectivity, low water seem especially necessary than preparation ethylene glycol technology.
The method that ethylene glycol is produced in Industrial Catalysis hydration the earliest once adopted inorganic acid as catalyst, and when making catalyst as use sulfuric acid, oxirane can all transform, and the ethylene glycol yield is 88～90%.But, influence the problem of product quality because inorganic acid catalyst exists etching apparatus, contaminated environment.In addition, in post-processing step, must add alkali sulfuric acid is neutralized, increase unnecessary separation circuit; The selectivity of ethylene glycol is compared with the on-catalytic hydration reaction and be there is no remarkable advantages and can say in addition.Therefore, reaction has obvious catalysis although inorganic acid catalyst is to ethylene oxide hydration, and traditional acid catalysis hydrating process is all eliminated, and does not re-use.
A kind of manufacture method of aryl ethylene glycol is disclosed among the Japanese patent laid-open 06-179633.This patent is that the aryl rings oxidative ethane is handled with niobic acid in water and aqueous solvent, uses this Niobic Acid agent effectively the epoxide ring in the aryl rings oxidative ethane partly to be added water decomposition, and the yield of aryl ethylene glycol is more than 95%.But the shortcoming of this method be water than too high, the existence of big water gaging brings huge energy consumption for the separation of ethylene glycol product.Introduced a kind of columbic acid particle and preparation method thereof among the Japanese patent laid-open 7-53219.Use the niobic acid of this method preparation can be under hydrothermal condition long-time stable existence.But the acidity of this Niobic Acid agent is strong excessively, is H more than 50%
0: the strong acid amount below-5.6 is not suitable for the catalyzing epoxyethane hydration reaction for preparing glycol.
Catalysis Today, 8 (1990) 123-132 and Catalysis Letters 5 (1990) 13-16 have reported that respectively niobic acid is as solid acid catalyst catalysis phenyl ethylene oxide and 1, the reaction of 2-epoxides ring opening hydrolysis, and think that niobic acid has stronger surperficial affinity for organic reaction substrate and glassware for drinking water, thereby than SiO
2-Al
2O
3, catalyst such as HZSM-5 and H-silicalite are more suitable in hydrolysis.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past in the document, oxirane on-catalytic hydration reaction water is than higher, energy consumption is big, the liquid acid catalyst that production cost height or catalysis hydration use can etching apparatus, contaminated environment, poor stability or stability and the active problem that can not take into account simultaneously, and a kind of columbium oxide catalyst of new hydrating epoxy ethane to prepare ethandiol is provided.This catalyst is used for ethylene oxide hydration prepared in reaction ethylene glycol process, not only have good activity, selectivity, be suitable for low water than operation, and have good stable simultaneously, can significantly reduce energy energy consumption, the characteristics that reduce production costs significantly.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of columbium oxide catalyst of hydrating epoxy ethane to prepare ethandiol, form by following component by weight percentage:
A) 80～99.9% be selected from least a in aluminium oxide, silica, titanium oxide, zirconia, MCM series molecular sieve, HMS series molecular sieve, spinelle, mullite or the cordierite as carrier; With carry thereon
B) oxide of 0.1～20% niobium;
Wherein the oxide raw material of niobium source is selected from least a in the hydroxy-acid derivative, phenol niobium, niobium ammino-complex of halogenation niobium, niobium alkoxides, niobium, and the hydroxy-acid derivative of niobium is selected from glycolic acid complex, lactic acid complex, malic acid complex, citric acid compound or the tartaric acid complex of niobium.
In the technique scheme, the aluminium oxide preferred version is an Alpha-alumina; MCM series molecular sieve preferred version is selected from MCM-41, MCM-48 or MCM-56 total silicon molecular sieve.The niobium alkoxides preferred version is selected from ethyoxyl niobium, isopropoxy niobium or butoxy niobium; Phenol niobium preferred version is selected from phenol niobium or benzenediol niobium.
Preparation of catalysts method of the present invention can adopt such as chemical vapour deposition technique, sol-gel process, prepared with microemulsion reactor, also can use conventional method such as infusion process, blending method, coprecipitation etc. to make.Catalyst shape can be made different shapes such as cylindric, spherical, disk, tubular, cellular or Raschig ring with conventional method.Concrete preparation process is as follows:
1, niobium source:
With oxide (niobic acid, niobium oxide) of the hydroxy-acid derivative (glycolic acid complex, lactic acid complex, malic acid complex, citric acid compound, tartaric acid complex) of commercially available halogenation niobium (I), niobium alkoxides (ethyoxyl niobium, isopropoxy niobium, butoxy niobium etc.), niobium, phenol niobium (phenol niobium, benzenediol niobium etc.), carboxylic acid niobium (niobium oxalate, acetic acid niobium), niobium ammino-complex, niobium etc. is raw material.
2, support source:
Organic titanium, zirconium, silicon source (the alkyl zirconate is as four n-butoxy zirconiums, alkyl titanate esters such as metatitanic acid four fourth chlorine esters, alkyl silicate such as ethyl orthosilicate etc.), inorganic titanium, zirconium, aluminium, silicon source (aluminum nitrate, chlorine nitrate zirconium, titanium tetrachloride, titanium colloidal sol, zirconium colloidal sol, aluminium colloidal sol, Ludox), MCM series total silicon molecular sieve, HMS series molecular sieve, spinelle, mullite or cordierite, aluminium oxide, silica, titanium dioxide etc.
3, Preparation of Catalyst
The concrete preparation method of catalyst of the present invention is mainly chemical vapour deposition technique, sol-gel process, micro emulsion method, infusion process, blending method, coprecipitation.Chemical vapour deposition technique is that above-mentioned niobium source is placed the lower end of carrier, under 200～600 ℃ of temperature and 100～0.1Pa vacuum gasified in the niobium source or sublimes up into carrier surface, through heat treatment and roasting, makes catalyst again.Sol-gel process is that niobium source solution, auxiliary agent are joined in the support source, under stirring, brute force forms the mixture of homogeneous, form colloidal sol by the interface interaction between organic matter and the inorganic matter, after aging, form gel, drying and roasting under certain atmosphere makes catalyst for hydration of epoxy ethane to prepare ethandiol at last.The micro emulsion method is meant the Thermodynamically stable that forms with two kinds of immiscible liquid, isotropic, appearance transparent or translucent dispersion, on the microcosmic be by the surfactant interface film the droplet of stable one or both liquid.Can make by the preparation microemulsion to contain the water-soluble formation droplet of required metal ion and stablized, thereby prepare nano level small catalyst granules by surfactant.
Catalyst sintering temperature of the present invention generally is controlled at 100～1000 ℃, preferable range is 200～700 ℃, roasting time is 1～10 hour, preferable range is 1～7 hour, calcination atmosphere is preferably in the mixture of nitrogen, hydrogen, carbon dioxide, ammonia, oxygen, air, water vapour or above-mentioned several gases and carries out, and also can give roasting under vacuum.Catalyst after the roasting cools off naturally, obtains the catalyst finished product.The sintering temperature of catalyst is bigger to the activity of such catalysts influence.When 300～600 ℃ of following temperature roastings, activity of such catalysts is higher, but active difference is little.Activity will reduce under higher sintering temperature, active decline obviously when especially sintering temperature is higher than 700 ℃.Selection of catalysts is the highest when 300～600 ℃ of sintering temperatures.
Catalyst of the present invention is mainly used in the industrial useful ethylene glycol product of preparation, and reaction raw materials is water and oxirane, and raw water is not had specific (special) requirements, can be the recirculated water in distilled water, deionized water, cooling water and this course of reaction.Make raw water and oxirane enter blender according to a certain percentage by measuring pump, enter preheater after fully mixing, raw material after the preheating enters in the fixed bed reactors that catalyst of the present invention is housed, the reactor that uses in the present invention's examination is the stainless steel tube of 8 millimeters of internal diameters, 300 millimeters of length, filler is housed up and down, reactor adopts the external heating mode heating, and 3 parallel thermocouples are equipped with control and measurement heating and reaction temperature in the outside.Reaction process condition: water/oxirane mol ratio is 1～10: 1, and reaction temperature is 150 ℃, and reaction pressure is 1.5MPa, and the reactant liquor air speed is 3.0～5.0 hours
-1, product obtains the ethylene glycol product through conventional partition method separation.
Support type columbium oxide catalyst of the present invention has good heat endurance in water.The catalyst D of preparation in the embodiment of the invention 4 for example was 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours
-1Under the condition, carry out the test of 1000 hours hydrothermal after, be loaded in the fixed bed reactors and estimate, estimate process conditions: reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water: oxirane mol ratio 8, liquid air speed 4.0 hours
-1, trend does not fall in the conversion ratio of catalyst and selectivity as follows, shows that catalyst of the present invention is specially adapted to the inefficient high temperature aqueous reaction of general solid acid system, and has good reactivity worth and advantages of excellent stability.
As main active constituent, raw material sources and preparation method by the control niobium oxide make catalyst particle in the carrier surface high degree of dispersion to catalyst of the present invention, have made the oxide of high activity niobium catalytic by load niobium oxide on some carriers.Simultaneously, carrier used in the present invention can produce cooperative effect with niobium oxide, makes the catalyst that makes have good reactivity worth, is used for the hydrating epoxy ethane to prepare ethandiol reaction, has following advantage:
1, activity of such catalysts is good, the selectivity height, and 150 ℃ of reaction temperatures, reaction pressure 1.5MPa, water/oxirane mol ratio 1～10: 1, liquid air speed 3.0～5.0 hours
-1Prepare ethylene glycol under the process conditions, the oxirane conversion ratio reaches 100%, glycol selectivity 91～93.5%;
2, operation water uses catalyst of the present invention can make reaction water than reduction significantly than low, and by 20～25 of prior art: 1 reduces to 1～10: 1, and reduce energy consumption significantly, thereby significantly reduced production cost.
3, catalyst reaction good stability, the life-span is long.But successive reaction is more than 1500 hours, and activity of such catalysts is not seen reduction, and the selectivity of ethylene glycol remains unchanged substantially.
4, columbium oxide catalyst of the present invention does not have corrosion to equipment, and environmentally safe has been obtained better technical effect.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
TEOS (ethyl orthosilicate) is mixed according to certain ratio with titanium oxide sol, add 5% polyvinyl alcohol water solution simultaneously and stir.Isopropyl alcohol niobium solution is joined in the above-mentioned solution, the powerful stirring 30 minutes, then static to forming gel at 60 ℃.Placed under the room temperature 48 hours, 80 ℃ aging 16 hours, 120 ℃ of dryings 4 hours, roasting is 8 hours in 500 ℃ of oxygen atmospheres, obtains catalyst A, catalyst is formed and is seen Table 1.
[embodiment 2]
15 gram phenol niobiums, 70 gram silica and 30 gram zirconium dioxides are fully mixed in kneading machine, add 60 milliliters in rare nitric acid of weight concentration 1% then, mediate and form the bulk material, extruded moulding, roasting is 4 hours in 700 ℃ of air, obtains catalyst B.The catalyst composition sees Table 1.
[embodiment 3]
The niobium amine complex is dissolved in water, makes the solution that concentration is 0.12 grams per milliliter, with this solution impregnation Ti-HMS molecular sieve, the maceration extract solid volume is than 2.5: 1, dip time 2 hours, elimination solution, in 120 ℃ of dryings 2 hours, roasting was 4 hours in 600 ℃ of ammonia atmospheres, obtains catalyst C.The catalyst composition sees Table 1.
[embodiment 4]
With former powder 113 grams of aluminium hydroxide, titanium dioxide 4.2 grams, 5 gram graphite, 5 gram sesbania powder fully mix, and add 60 milliliters in rare nitric acid of 4% (weight) then, fully mediate in kneading machine, form the bulk material, extruded moulding, under the room temperature dry 24 hours, 150 ℃ of dryings 2 hours, 1200 ℃ of roastings 4 hours obtain the bar shaped carrier.Above-mentioned carrier powder is broken to 40～60 orders, the CVD reactor epimere of packing into.Reactor is the crystal reaction tube of 10 millimeters of internal diameters, 300 millimeters of length.Reactor is divided into two sections, and the centre is equipped with sintered glass respectively.Reactor adopts the external heating mode heating, and 2 parallel thermocouples are equipped with to control and to measure the heating-up temperature of hypomere on the reactor respectively in the outside.The reactor epimere is used for the loading catalyst carrier, and the niobium source is loaded in the lower end.The Manufactured carrier of 10 grams is encased in the CVD reactor, the upper ends carrier, columbium pentachloride is placed in the lower end.The reactor epimere is heated to 50 ℃ of temperature, under pressure 1.0Pa, vacuumized cool to room temperature 3 hours.Then heat the hypomere reactor with 5 ℃ of/minute clock rate of speed, and be warming up to 200 ℃, insulation is 10 hours under this temperature.Then be cooled to 150 ℃, under this temperature, feed the saturated hydrogen of water vapour, be incubated 5 hours once more, under nitrogen protection, be warming up to 400 ℃ of roastings 4 hours at last, obtain catalyst D.The catalyst composition sees Table 1
[embodiment 5]
A certain amount of niobium oxalate solution is mixed with the mixing material of being made up of a certain amount of normal octane, n-hexyl alcohol and polyoxyethylene 9～10 octyl phenyl ethers (emulsifying agent), fully stir down at 50 ℃, then add a certain amount of TEOS as the Si source, after reacting 0.5 hour under 80 ℃, after filtration, filter cake is washed two to three times with ethanol, 120 ℃ of vacuum drying 2 hours, 500 ℃ of vacuum bakings made required catalyst E in 4 hours, and the catalyst composition sees Table 1.
[embodiment 6]
Method by embodiment 2 prepares catalyst F, and different is that employing citric acid niobium is the niobium source in the preparation process, and carrier is a magnesium aluminate spinel.The following 600 ℃ of roastings of nitrogen atmosphere 4 hours obtain catalyst F, and the catalyst composition sees Table 1.
[embodiment 7]
Method by embodiment 4 prepares catalyst G, and different is that the iodate niobium is adopted in the niobium source in the preparation process, and carrier is 60% α-Al
2O
3+ 40%MCM-41.After carrier powder is broken to 40～60 orders, be loaded in the CVD reactor.The CVD reactor epimere is heated to 50 ℃ of temperature, under pressure 0.1Pa, vacuumized cool to room temperature 3 hours.Then heat the hypomere reactor with 5 ℃ of/minute clock rate of speed, and be warming up to 250 ℃, insulation is 10 hours under this temperature.Then be cooled to 150 ℃, feed water vapour under this temperature, be incubated 5 hours once more, be warming up to 500 ℃ of roastings 4 hours at last under nitrogen protection, obtain catalyst G, the catalyst composition sees Table 1.
[embodiment 8]
Method by embodiment 4 prepares catalyst H, and columbium pentachloride is adopted in the niobium source.Mullite is commercial 1 mm granules.The mullite carrier is encased in the CVD reactor, the upper ends carrier, the columbium pentachloride powder is placed in the lower end.The CVD reactor epimere is heated to 50 ℃ of temperature, under pressure 30Pa, vacuumized cool to room temperature 3 hours.Then heat the hypomere reactor with 5 ℃ of/minute clock rate of speed, and be warming up to 250 ℃, insulation is 10 hours under this temperature.Then be cooled to 150 ℃, under this temperature, feed steam, be incubated 5 hours once more, at last in the mist of forming by 10% hydrogen and 90% carbon dioxide (volume ratio) in 300 ℃ of roastings 4 hours, obtain catalyst H, catalyst is formed and to be seen Table 1.
[embodiment 9]
Method by embodiment 4 prepares catalyst I, and the ethyoxyl niobium is adopted in the niobium source.Cordierite is commercial 1 mm granules.Cordierite carrier is encased in the CVD reactor, the upper ends carrier, the niobium chloride powder is placed in the lower end.The CVD reactor epimere is heated to 50 ℃ of temperature, under pressure 20Pa, vacuumized cool to room temperature 3 hours.Then heat the hypomere reactors with 5 ℃ of/minute heating rates, and be warming up to 250 ℃, insulation is 10 hours under this temperature.Then be cooled to 150 ℃, under this temperature, feed steam, be incubated 5 hours once more, at last in the mist of forming by 80% hydrogen and 20% nitrogen (volume ratio) in 400 ℃ of roastings 4 hours, obtain catalyst I, catalyst is formed and to be seen Table 1.
[embodiment 10]
Get the catalyst A～I of embodiment 1～9 preparation, being pulverized, sieve and get granularity respectively is each 10 milliliters of 40～60 purpose catalyst, and filling in internal diameter one by one is 8 millimeters, in long 300 millimeters the stainless steel fixed bed reactors, the filler of packing into up and down carries out the evaluation of catalyst.Use metering pump massage that than 1～10: 1 charging raw water and oxirane, at reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, liquid air speed 3.0～5.0 hours
-1Prepared in reaction ethylene glycol under the condition carries out qualitative, quantitative analysis with the HP5890 gas-chromatography to product, ring oxidative ethane conversion ratio, glycol selectivity.Reaction result is listed in table 1.
[embodiment 11]
With catalyst F 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours
-1Carry out hydrothermal test in 1000 hours under the condition, then catalyst being loaded into internal diameter is 8 millimeters, estimates in long 300 millimeters the stainless steel fixed bed reactors, estimate process conditions: reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water be than 7, liquid air speed 5 hours
-1, the conversion ratio of oxirane is 100%, and the selectivity of ethylene glycol is 93.5%, and trend does not fall in the conversion ratio of catalyst and selectivity as follows, and this catalyst has good stable.
[comparative example 1]
With granularity is that to fill in internal diameter be 8 millimeters to 10 milliliters on 20～40 purpose porcelain rings, in long 300 millimeters the stainless steel fixed bed reactors, with raw water and oxirane your ratio of metering pump massage charging in 10: 1, at reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, liquid air speed are 2.0 hours
-1Prepared in reaction ethylene glycol under the condition carries out qualitative, quantitative analysis with the HP5890 gas-chromatography to product, ring oxidative ethane conversion ratio, glycol selectivity.Reaction result is listed in table 1.
[comparative example 2]
Prepare ethylene glycol, difference according to the method identical with comparative example 1: raw material feed water ratio is 22: 1.Reaction result is listed in table 1.
Table 1
| The catalyst numbering | Catalyst is formed | Water is than (mole) | Air speed/hour -1 | Oxirane conversion ratio % | Glycol selectivity % |
| A | 2％Nb 2O 5/10％SiO 2+90％TiO 2 | 2 | 3 | 100 | 88 |
| B | 12％Nb 2O 5/70％SiO 2+30％ZrO 2 | 5 | 5 | 100 | 91 |
| C | 20％Nb 2O 5/Ti-HMS | 10 | 5 | 100 | 89 |
| D | 7％Nb 2O 5/95％α-Al 2O 3+5％TiO 2 | 8 | 4 | 100 | 92 |
| E | 5％Nb 2O 5/SiO 2 | 6 | 5 | 100 | 93 |
| F | 18％Nb 2O 5/ spinelle | 7 | 5 | 100 | 93.5 |
| G | 15％Nb 2O 5/60％α-Al 2O 3+ 40%MCM-41 (total silicon) | 3 | 5 | 100 | 91 |
| H | 8％Nb 2O 5/ mullite | 9 | 4 | 100 | 92 |
| I | 5％Nb 2O 5/ cordierite | 4 | 3 | 100 | 90 |
| Comparative example 1 | / | 10 | 2.0 | 92 | 75 |
| Comparative example 2 | / | 22 | 2.0 | 100 | 90 |
Claims (4)
1. the columbium oxide catalyst of a hydrating epoxy ethane to prepare ethandiol, form by following component by weight percentage:
A) 80～99.9% be selected from least a in aluminium oxide, silica, titanium oxide, zirconia, MCM series molecular sieve, HMS series molecular sieve, spinelle, mullite or the cordierite as carrier; With carry thereon
B) oxide of 0.1～20% niobium;
Wherein the oxide raw material of niobium source is selected from least a in the hydroxy-acid derivative, phenol niobium, niobium ammino-complex of halogenation niobium, niobium alkoxides, niobium, and the hydroxy-acid derivative of niobium is selected from glycolic acid complex, lactic acid complex, malic acid complex, citric acid compound or the tartaric acid complex of niobium.
2. according to the columbium oxide catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that described aluminium oxide is an Alpha-alumina.
3. according to the columbium oxide catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that described MCM series molecular screening is from MCM-41, MCM-48 or MCM-56 total silicon molecular sieve.
4. according to the columbium oxide catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that niobium alkoxides is selected from ethyoxyl niobium, isopropoxy niobium or butoxy niobium.
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| CN102078808A (en) * | 2010-11-29 | 2011-06-01 | 华东理工大学 | Catalyst used for synthesizing o-ethoxyphenol and preparation method thereof |
| CN104923265A (en) * | 2015-05-13 | 2015-09-23 | 安徽金邦医药化工有限公司 | Recyclable compound solid acid catalyst and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06179633A (en) * | 1993-04-15 | 1994-06-28 | Agency Of Ind Science & Technol | Production of arylethylene glycol |
| CN1463791A (en) * | 2002-06-12 | 2003-12-31 | 中国石油化工股份有限公司 | Solid acid catalyst for preparing ethandiol by epoxyethane hydration |
| CN1463960A (en) * | 2002-06-12 | 2003-12-31 | 中国石油化工股份有限公司 | Process for preparing ethandiol by catalyzing epoxyethane hydration |
-
2004
- 2004-09-24 CN CNB2004100666273A patent/CN100413578C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06179633A (en) * | 1993-04-15 | 1994-06-28 | Agency Of Ind Science & Technol | Production of arylethylene glycol |
| CN1463791A (en) * | 2002-06-12 | 2003-12-31 | 中国石油化工股份有限公司 | Solid acid catalyst for preparing ethandiol by epoxyethane hydration |
| CN1463960A (en) * | 2002-06-12 | 2003-12-31 | 中国石油化工股份有限公司 | Process for preparing ethandiol by catalyzing epoxyethane hydration |
Non-Patent Citations (4)
| Title |
|---|
| In situ vibrational spectroscopy studies of supported niobiumoxide catalysts.. Loyd J.Burcham, et al.Journal of Physical Chemistry B,,Vol.103, . 1999 |
| In situ vibrational spectroscopy studies of supported niobiumoxide catalysts.. Loyd J.Burcham, et al.Journal of Physical Chemistry B,,Vol.103, . 1999 * |
| Selective catalytic hydration of ethylene oxide over niobiumoxide supported on α-alumina.. Yingcheng Li, et al.Applied Catalysis A:General,,Vol.272, . 2004 |
| Selective catalytic hydration of ethylene oxide over niobiumoxide supported on α-alumina.. Yingcheng Li, et al.Applied Catalysis A:General,,Vol.272, . 2004 * |
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