CN1181913C - Solid acid catalyst for preparing ethandiol by epoxyethane hydration - Google Patents

Solid acid catalyst for preparing ethandiol by epoxyethane hydration Download PDF

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Publication number
CN1181913C
CN1181913C CNB021120382A CN02112038A CN1181913C CN 1181913 C CN1181913 C CN 1181913C CN B021120382 A CNB021120382 A CN B021120382A CN 02112038 A CN02112038 A CN 02112038A CN 1181913 C CN1181913 C CN 1181913C
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catalyst
solid acid
acid catalyst
ethylene glycol
reaction
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CN1463791A (en
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李应成
何文军
费泰康
李道贵
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

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Abstract

The present invention relates to a solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration. The present invention mainly solves the defects in the prior art for preparing ethylene glycol by non catalytic hydration: the water ratio in the reaction is relatively high; the catalysts used for preparing ethylene glycol by using ethylene oxide pollute the environment, influence the product quality, and are poor in stability, and the water ratio in catalytic reaction is relatively high; thereby, the consumption of energy sources is large, and the production cost is high. The present invention provides a solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration. The catalyst used in the ethylene oxide hydration reaction has favorable activity, selectivity and stability, is particularly suitable for low water ratio operation, can greatly reduce energy consumption, efficiency reduces production cost, and can be applied to the industrial production of ethylene glycol.

Description

The solid acid catalyst of hydrating epoxy ethane to prepare ethandiol
Technical field
The present invention relates to a kind of solid acid catalyst that is used for ethylene oxide hydration prepared in reaction ethylene glycol, especially for a kind of Niobic Acid agent of ethylene oxide hydration prepared in reaction ethylene glycol.
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.
With oxirane is feedstock production ethylene glycol, mainly be divided into two kinds of methods, a kind of is direct hydration method, i.e. direct under certain condition the and water reaction generation ethylene glycol of oxirane, reaction does not need catalyst just can carry out, and is divided into two kinds of technologies of catalysis hydration and on-catalytic hydration; Another kind method is the ethylene carbonate method, promptly oxirane under catalyst action, elder generation and CO 2Reaction generates ethylene carbonate, and hydrolysis generates ethylene glycol then.
Present industrial preparation ethylene glycol adopts the on-catalytic hydrating process of direct hydration method, also claim the pressurization hydration, this method is not used catalyst, 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, oxirane conversion ratio be near 100%, glycol selectivity about 90%.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 water of taking is big excessive way, improves glycol selectivity.The disadvantage of this method is that lot of energy is used for the moisture content of evaporation product more than 85% in producing.For example, in ethylene glycol product purification step, when the feed water ratio is 20, remove the no water that is approximately 19 times of ethylene glycol by evaporation, required heat is counted 170 kilocalories with every mole of ethylene glycol, mean that producing 1 ton of ethylene glycol need consume about 5.5 tons of steam, cause this method energy consumption huge, production cost is higher.Therefore, in order to reduce the reaction water ratio, cut down the consumption of energy, the researcher has competitively carried out the research of multiple catalyzing epoxyethane hydration reaction technology both at home and abroad.
The method of ethylene glycol is produced in Industrial Catalysis hydration the earliest, with inorganic acid or alkali as a catalyst, as with sulfuric acid or phosphoric acid etc. during as catalyst, oxirane can all transform, the ethylene glycol yield is about 90%, but inorganic acid catalyst causes corrosion to equipment, contaminated environment; When using inorganic alkali as a catalyst, easily promote to produce the accessory substance of some HMWs, reduce product selectivity.Therefore, although acid, alkali has obvious catalysis to ethylene oxide hydration, traditional acid-base catalysis hydrating process is all eliminated, and does not re-use.
For overcoming the shortcoming of inorganic acid and base catalysis hydration, people have carried out many-sided improvement research to the catalyst that is used for ethylene oxide hydration.
Spent ion exchange resin is made catalyst, and a class is to have-SO 3H ,-PO (OH) 2The storng-acid cation exchange resin of group, another kind of is the alkalescence anion-exchange resin that contains quaternary amine, and based on the anion exchange resin of metal oxygen-containing acid group catalytic action.As US Patent 5,874,653 a kind of anion exchange resin that has quaternary ammonium group by styrene and divinyl benzene crosslinked is disclosed as the ethylene oxide hydration catalyst.At 80～200 ℃ of reaction temperatures, reaction pressure 200～3000KPa, water is than 1～15: react under 1 the condition, the conversion ratio of oxirane is near 100%, the selectivity 95% of ethylene glycol.But the remarkable shortcoming of this catalyst system and catalyzing is that the resin catalyst heat resistance is poor, even in lower temperature range (＜95 ℃), the expansion of catalyst is still more serious, thereby it is very fast to cause the reactor bed pressure drop to be risen, catalyst is changed frequent, and it is unfavorable to bring to industrial production.Although thereby above-mentioned research work obtained remarkable progress, but still limited its range of application.
Compound with heteropolyacid salt is made catalyst, discloses a kind of K as JP82106631 2MoO 4-KI catalyst makes oxirane and carbon dioxide generate ethylene carbonate, oxirane conversion ratio 99.9%, glycol selectivity 100% 160 ℃ of reactions; Be catalyst then with the aluminium oxide, 140 ℃ of reaction temperatures, under the reaction pressure 2.25MPa condition, hydrolysis obtains the ethylene glycol product, oxirane conversion ratio 100%, glycol selectivity 99.8%.Use the distinguishing feature of above-mentioned heteropolyacid salt catalyst to be: when catalyst was dissolvable in water water, oxirane conversion ratio and product selectivity were higher, but catalyst easily runs off, and had brought unnecessary trouble to postprocessing working procedures; When catalyst was water insoluble, the oxirane conversion ratio obviously reduced, and the selectivity of ethylene glycol is relatively poor.
Japanese patent laid-open 06-179633 discloses a kind of manufacture method of aryl ethylene glycol, this patent is that the aryl rings oxidative ethane is handled with niobic acid in water and aqueous solvent, use this Niobic Acid agent effectively the epoxide ring in the aryl rings oxidative ethane partly to be added water decomposition, 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.
Japanese patent laid-open 7-53219 has introduced a kind of columbic acid particle and preparation method thereof.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.
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, and be used for the catalyst contamination environment that reacting ethylene oxide prepares ethylene glycol, influence product quality, poor catalyst stability, reaction water is than higher, cause energy consumption huge, the defective that production cost is high provides a kind of solid acid catalyst of hydrating epoxy ethane to prepare ethandiol, this catalyst is used for ethylene oxide hydration prepared in reaction ethylene glycol, both had good activity, selectivity has good stable again, is particularly suitable for low water than operation, can reduce energy consumption significantly, reduce production costs.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of solid acid catalyst of hydrating epoxy ethane to prepare ethandiol, to be selected from a kind of or its mixture in aluminium oxide, silica, titanium oxide, zirconia or the zeolite as carrier, the following active constituent of load on carrier, the percentage that accounts for vehicle weight is:
A) oxide of 0.1～30% niobium;
B) 0.01～10% be selected from least a in the metal oxide of IIB, the metal of wherein said IIB is zinc, cadmium or mercury.
In the technique scheme, in vehicle weight percentage, the oxide preferable range of niobium is 1～20%, and preferably preferable range is 2～10%; The metal oxide preferable range that is selected from IIB is 0.01～5%, the preferred zinc of the metal of described IIB, cadmium or its mixture, described catalyst also contains counts 1～10% binding agent with vehicle weight percentage, the binding agent that often uses as Preparation of Catalyst fields such as inorganic clay, methyl or ethyl or carboxyethyl cellulose, magnesium silicate fiber element, polyvinyl alcohol, rare nitric acid.
In the technique scheme, described oxide carrier can use separately, also can mix with arbitrary proportion and use, and carrier preferentially is selected from a kind of or its mixture in aluminium oxide, titanium oxide or the zirconia, the preferred Alpha-alumina of wherein said aluminium oxide, the preferred HZSM-5 zeolite of described zeolite.
The raw material for preparing catalyst use of the present invention is as follows:
Niobium source: commercially available niobic acid, niobium oxalate, acetic acid niobium or niobium ammino-complex.
Zinc, cadmium, mercury source: with its oxide, nitrate, chloride or acetate.
Catalyst of the present invention can use catalyst preparation method such as mixing method, infusion process or coprecipitation commonly used to make.This specification is that example describes the Preparation of catalysts method with the blending method, but is not limited to this method.Blending method is that carrier, active constituent niobic acid and co-catalyst are mixed, in order to be beneficial to the moulding of catalyst, improve catalyst strength, can add an amount of binding agent in the mixed process, be prepared from through steps such as kneading, moulding, drying and roastings then.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:
Solid state powder form with commercially available niobic acid, niobium oxalate, acetic acid niobium or niobium ammino-complex is introduced, and perhaps introduces with niobic acid solution form, and niobic acid solution is prepared as follows:
Take by weighing a certain amount of niobium compound, be generally commercially available niobic acid (Nb 2O 5NH 2O, n is 1-5), be dissolved in the acid solution, acid solution can be organic acid solns such as oxalic acid, acetic acid, tartaric acid, citric acid, malic acid, lactic acid, fumaric acid, the concentration of niobium compound in the acid solution is as long as below saturated concentration, no particular determination is generally 0.5～30% (weight), is preferably 1～20% (weight);
2, preparation zinc, cadmium or mercury salt solution
Take by weighing oxide, nitrate, chloride or the acetate of a certain amount of zinc, cadmium or mercury, be dissolved in 5～15% the dilute nitric acid solution, be mixed with salting liquid;
3, Preparation of Catalyst
Above-mentioned niobium source, solution 2, carrier and binding agent are fully mediated evenly in kneader, make certain shape, ℃ carry out drying in room temperature～200,100 ℃～200 ℃ of preferable range, 1～5 hour drying time, preferable range is 1～3 hour, can adopt vacuum drying or aeration-drying when dry; Carry out roasting then, 100～1000 ℃ of sintering temperatures, preferable range is 200～700 ℃, roasting time is 1～10 hour, preferable range is 1～5 hour, and calcination atmosphere can carry out in air, nitrogen, carbon dioxide or ammonia atmosphere, also can give roasting under vacuum, catalyst after the roasting cools off naturally, obtains the catalyst finished product.
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, reactor 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 is than 1～10: 1, and 100～200 ℃ of reaction temperatures, reaction pressure 0.5～3.0MPa, the reactant liquor air speed is 1.0～3.0 hours -1, product obtains the ethylene glycol product through conventional partition method separation.
Solid acid catalyst of the present invention has good heat endurance in water.The catalyst H of example 8 preparation for example was 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours -1Under the condition, carry out hydrothermal test in 1000 hours, catalyst after the hydrothermal test is handled without any regeneration, adopt identical process conditions to investigate the reactivity of catalyst hydrothermal test front and back, the evaluation process conditions are: reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water be than 9: 1, liquid air speed 2.0 hours -1, reaction result is as follows:
Catalyst H oxirane conversion ratio % glycol selectivity %
Hydrothermal test preceding 100 90
After 1000 hours hydrothermal test 99.5 91
Through after 1000 hours hydrothermal test, 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.
Catalyst of the present invention is by the main active constituent of the conduct of load niobic acid on some oxide carriers, load is selected from IIB metal oxide or its mixture as co-catalyst, produce cooperative effect between each component, make the catalyst that makes have good reactivity worth, be used for the hydrating epoxy ethane to prepare ethandiol reaction, have following advantage:
1, activity of such catalysts height, the selectivity height, at reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water is than 1～10: 1, liquid air speed 1.0～3.0 hours -1Prepare ethylene glycol under the process conditions, the oxirane conversion ratio reaches more than 98%, glycol selectivity about 90%;
2, reaction water uses catalyst of the present invention can reduce the reaction water ratio significantly than low, and by 20～25 of prior art: 1 reduces to 1～10: 1, and reduced energy consumption significantly, thereby effectively reduced production costs.
3, catalyst stability of the present invention is good, and through the test of 1000 hours hydrothermal, trend does not fall in the acidity of catalyst, catalytic activity and selectivity as follows, does not fall trend as follows as the catalytic perfomance of solid acid.
4, solid acid catalyst of the present invention does not have corrosion to equipment, environmentally safe.
The present invention is further illustrated below by embodiment.
The specific embodiment
[embodiment 1]
Take by weighing the commercially available niobium oxalate of 12 grams and be dissolved in 40 ml waters, make niobium oxalate solution; Take by weighing 1.8 gram Zn (NO 3) 26H 2O is dissolved in 5 milliliter 10% the diluted nitric acid aqueous solution, makes zinc nitrate solution.Take by weighing Alpha-alumina 100 grams, join in the kneading machine, add the niobium oxalate and the zinc nitrate solution of above-mentioned preparation then, fully mediate with Alpha-alumina, form the bulk material, extruded moulding, in 150 ℃ of air dryings 2 hours, roasting was 4 hours in 600 ℃ of air, obtains catalyst A.The catalyst composition sees Table 1.
[embodiment 2]
Take by weighing 90 gram Alpha-aluminas, 10 gram titanium dioxide and the commercially available niobic acid of 12 grams respectively, join in the kneader and fully mix, obtain mixed material, take by weighing 8.1 gram Cd (NO 3) 26H 2O is dissolved in 40 milliliter 10% the diluted nitric acid aqueous solution, makes cadmium nitrate solution, join in the aforementioned mixed material, through mediate, after the extrusion, in 120 ℃ of vacuum drying 2 hours, roasting was 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst B.The catalyst composition sees Table 1.
[embodiment 3]
Method by embodiment 2 prepares catalyst C, and different is niobium amine complex consumption 7.6 grams in the preparation process, titanium dioxide 100 grams, Cd (NO 3) 26H 2O2.7 gram is dissolved in 40 ml waters, and in 100 ℃ of air dryings 3 hours, roasting was 4 hours in 200 ℃ of air.The catalyst composition sees Table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyst D, and different is niobic acid consumption 2.4 grams in the preparation process, is dissolved in the hot oxalic acid aqueous solution (this oxalic acid solution is dissolved in the 40ml water by 7g oxalic acid and makes) Zn (NO 3) 26H 2O 0.18 gram is dissolved in 20 ml waters, HZSM-5 molecular sieve carrier 100 grams, and in 110 ℃ of air dryings 2 hours, roasting was 4 hours in 300 ℃ of air.The catalyst composition sees Table 1.
[embodiment 5]
Method by embodiment 2 prepares catalyst E, different is niobic acid consumption 5 grams, and mercuric nitrate 0.015 gram, silica 1 00 gram, binding agent polyvinyl alcohol 10 grams are dissolved in 40 milliliters of hot water, 120 ℃ of air dryings 2 hours, roasting is 4 hours in 200 ℃ of air.The catalyst composition sees Table 1.
[embodiment 6]
Method by embodiment 2 prepares catalyst F, different is niobic acid consumption 18 grams, and a certain amount of cadmium nitrate, carrier is made up of 15 gram Alpha-aluminas and 85 gram silica, 120 ℃ of vacuum drying 2 hours, 500 ℃ of vacuum bakings 4 hours.The catalyst composition sees Table 1.
[embodiment 7]
Method by embodiment 1 prepares catalyst G, and different is consumption 24 grams of preparation process mesoxalic acid niobium, Zn (NO 3) 26H 2Consumption 18 grams of O, binding agent inorganic clay 5 grams, carrier is made up of 20 gram Alpha-aluminas and HZSM-5 molecular sieve 80 grams, and in 120 ℃ of vacuum drying 2 hours, roasting was 4 hours in 700 ℃ of air.The catalyst composition sees Table 1.
[embodiment 8]
Method by embodiment 2 prepares catalyst H, and that different is Cd (NO in the preparation process 3) 26H 2Consumption 0.8 gram of O, Zn (NO 3) 26H 2Consumption 0.7 gram of O, a certain amount of niobic acid, binding agent carboxyethyl cellulose 8 grams, carrier is made up of 60 gram zirconia carriers and 40 gram silica, 120 ℃ of vacuum drying of catalyst 2 hours, roasting is 3 hours in 400 ℃ of air.The catalyst composition sees Table 1.
[embodiment 9]
Method by embodiment 1 prepares catalyst I, and different is consumption 10 grams of niobic acid in the preparation process, Zn (NO 3) 26H 2Consumption 1.0 gram of O, Alpha-alumina 80 grams and zirconia 20 restrain, 120 ℃ of vacuum drying 2 hours, roasting is 4 hours in 500 ℃ of air.The catalyst composition sees Table 1.
[embodiment 10]
Get each 10 milliliters of the catalyst A～I of embodiment 1～9 preparation, filling in internal diameter one by one is 8 millimeters, and 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 1.0～3.0 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]
Get the catalyst H10 milliliter of embodiment 8 preparation, being loaded into internal diameter is 8 millimeters, in long 300 millimeters the stainless steel fixed bed reactors, and at reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water is than 9: 1, liquid air speed 2.0 hours -1Under the condition, carry out the catalyst activity evaluation; Change into then and in reactor, feed water vapour, 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours -1Under the condition, carry out the test of 1000 hours hydrothermal, after the hydrothermal test, catalyst is handled without any regeneration, adopts the process conditions identical with activity rating, and investigation is through the activity of such catalysts after 1000 hours hydrothermal test.Reaction result is as follows:
Catalyst H oxirane conversion ratio % glycol selectivity %
Hydrothermal test preceding 100 90
After 1000 hours hydrothermal test 99.5 91
Through after 1000 hours hydrothermal test, trend does not fall in the conversion ratio of catalyst and selectivity as follows, shows that catalyst of the present invention has advantages of excellent stability.
[comparative example 1]
With granularity is that to be loaded into internal diameter be 8 millimeters to 10 milliliters on 20-40 purpose porcelain ring, 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 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]
Method by comparative example 1 prepares ethylene glycol, difference: 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 6.1％Nb 2O 5-0.5％ZnO/α-Al 2O 3 10∶1 2.0 98 87
B 10％Nb 2O 5-3％CdO/90％α-Al 2O 3+10％TiO 2 5∶1 3.0 100 84
C 5％Nb 2O 5-1.0％CdO/TiO 2 7∶1 2.0 96 85
D 2％Nb 2O 5-0.05％ZnO/HZSM-5 2∶1 1.0 97 80
E 4.2％Nb 2O 5-0.01%HgO-10% binding agent/SiO 2 10∶1 2.0 93 89
F 15％Nb 2O 5-0.2％CdO/15％α-Al 2O 3+85％SiO 2 8∶1 3.0 100 91
G 20％Nb 2O 5-5%ZnO-5% binding agent/20% α-Al 2O 3+80％HZSM-5 15∶1 3.0 100 92
H 10％Nb 2O 5-0.2%ZnO-0.3%CdO-10% binding agent/60%ZrO 2+40％SiO 2 9∶1 2.0 100 90
I 8.3％Nb 2O 5-0.3％ZnO/80％α-Al 2O 3+20％ ZrO 2 10∶1 2.0 99 90
Compare 1 / 10∶1 2.0 92 75
Compare 2 / 22∶1 2.0 100 90

Claims (9)

1, a kind of solid acid catalyst of hydrating epoxy ethane to prepare ethandiol, to be selected from a kind of or its mixture in aluminium oxide, silica, titanium oxide, zirconia or the zeolite as carrier, the following active constituent of load on carrier, the percentage that accounts for vehicle weight is:
A) oxide of 0.1～30% niobium;
B) 0.01～10% be selected from least a in the metal oxide of IIB, the metal of wherein said IIB is zinc, cadmium or mercury.
2,, it is characterized in that in vehicle weight percentage the oxide consumption of niobium is 1～20% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
3,, it is characterized in that in vehicle weight percentage the oxide consumption of niobium is 2～10% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
4,, it is characterized in that in vehicle weight percentage the metal oxide consumption that is selected from IIB is 0.01～5% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
5,, it is characterized in that described carrier is a kind of or its mixture in aluminium oxide, titanium oxide or the zirconia according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
6,, it is characterized in that described aluminium oxide is an Alpha-alumina according to the solid acid catalyst of claim 1 or 5 described hydrating epoxy ethane to prepare ethandiol.
7,, it is characterized in that described zeolite is the HZSM-5 zeolite according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
8, according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, the metal that it is characterized in that described IIB is zinc or cadmium.
9, according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that described catalyst also contains binding agent, in vehicle weight percentage, the consumption of binding agent is 1～10%.
CNB021120382A 2002-06-12 2002-06-12 Solid acid catalyst for preparing ethandiol by epoxyethane hydration Expired - Lifetime CN1181913C (en)

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CN100413578C (en) * 2004-09-24 2008-08-27 中国石油化工股份有限公司 Columbium oxide catalyst for hydrating epoxy ethane to prepare ethandiol
CN100413579C (en) * 2004-09-24 2008-08-27 中国石油化工股份有限公司 Catalyst used for hydrating epoxy ethane to prepare ethandiol
CN100413580C (en) * 2004-09-24 2008-08-27 中国石油化工股份有限公司 Method for preparing catalyst for hydration of epoxy ethane to prepare ethandiol
CN1318364C (en) * 2004-10-29 2007-05-30 中国石油化工股份有限公司<Del/> Aliphatic dihydroxy alcohol preparation method

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