CN1259135C - Solid acid catalyzer for producing glycol by hydrating ethylene oxide - Google Patents

Abstract

The present invention relates to a solid acid catalyst for producing glycol by hydrating epoxy ethane, which mainly solves the defects of high water ratio, large energy consumption and high production cost of the existing epoxy ethane non-catalytic hydration reaction or equipment corrosion, environmental pollution of a liquid acid catalyst for catalytic hydration and poor stability of a solid acid catalyst, or the stability and the activity of the solid acid catalyst can not simultaneously exist. The present invention provides a solid acid catalyst for producing glycol by hydrating epoxy ethane and has the technical scheme that oxide loaded with niobium on a carrier of the oxide is used as a main active component; VIB metal compounds are introduced, and metal of cerium, manganese or thorium or compounds of the elements are not forcefully introduced and used as a cocatalyst. The prepared catalyst is used for a reaction for producing glycol by hydrating epoxy ethane, has good activity and selectivity, and is suitable for low water ratio operation. Meanwhile, the catalyst has good stability. The energy consumption of energy sources is obviously reduced, and the production cost is greatly reduced. The present invention can be used in industrial production of glycol.

Description

Ethylene oxide hydration is produced the solid acid catalyst of ethylene glycol

Technical field

The present invention relates to a kind of ethylene oxide hydration reaction and produce the solid acid catalyst of ethylene glycol, particularly a kind of Niobic Acid agent that ethylene glycol is produced in reaction about ethylene oxide hydration.

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 contain two kinds of process routes: a kind of is direct hydration method, oxirane and water react generation ethylene glycol under certain condition, and 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 is the ethylene carbonate method, promptly oxirane under catalyst action, elder generation and CO ₂Reaction generates ethylene carbonate, and hydrolysis generates ethylene glycol then.

Industrial production ethylene glycol adopts the uncatalysed processes of hydration method at present, also is current method of producing unique use.This method is not used catalyst, the mol ratio of water and oxirane (hereinafter to be referred as water than) be 20～25: 1,150～200 ℃ of reaction temperatures, reaction pressure 0.8～2.0MPa, oxirane conversion ratio be near 100%, glycol selectivity 88～90%.This method disadvantage is that energy consumption is big, the evaporation and concentration long flow path, for example in refined product ethylene glycol step, when the feed water ratio is 20, evaporate and remove the no water that is approximately 19 times of ethylene glycol, need to consume and count 170 kilocalories heat energy, mean that producing 1 ton of ethylene glycol need consume about 5.5 tons of steam with every mole of ethylene glycol, make that this method equipment investment is big, the production cost height.Simultaneously in the presence of catalyst-free, hydration reaction speed is slow, the industrial need adopted bigger pipeline reactor, caused the increase of transmission and mass transfer energy, in addition, a high proportion of feed water is than the glycol product selectivity is improved significantly, and consumptions such as the accessory substance diethylene glycol that generates, triethylene glycol are little, and the ethylene glycol demand growth is very fast, thereby, develop a kind of preparing ethandiol by catalyzing epoxyethane hydration technology, improve this technology whole synthesis performance and seem particularly important.

Catalysis hydration is produced the method for ethylene glycol the earliest, once adopts inorganic acid as catalyst, makes catalyst as using sulfuric acid, and oxirane can all transform, and the ethylene glycol yield is 88～90%.But because liquid acid catalyst etching apparatus, contaminated environment, there are problems in product quality, need add alkali neutralization and separation circuit during post processing, and product selectivity is compared with the on-catalytic hydration and be there is no clear superiority and can say, therefore, traditional acid catalysis hydrating process is eliminated, and does not re-use.

For overcoming the shortcoming of inorganic acid catalysis hydration, people have carried out many-sided improvement research to the catalyst that is used for hydration of epoxy ethane to prepare ethandiol, and the research focus mainly adopts solid acid as catalyst such as ion exchange resin, quaternary alkylphosphonium salt.

US 5488184 discloses a kind of anion exchange resin of quaternary ammonium group that has 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, and in the hydration reaction temperature range, the expansion situation of catalyst is more serious, and it is very fast to cause the reactor bed pressure drop to be risen, and shortens catalyst service life.

JP82106631 discloses a kind of K ₂MoO ₄-KI catalyst makes oxirane and carbon dioxide generate ethylene carbonate 160 ℃ of reactions, is catalyst then with the aluminium oxide, 140 ℃ of reaction temperatures, under the 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 catalyst to be: when catalyst was dissolvable in water water, oxirane conversion ratio and product selectivity were higher, but catalyst easily runs off, and poor stability has 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.

US5874653 discloses a kind of method for preparing ethylene glycol, use the agent of poly-organosilicon alkane ammonium salt in catalysis, oxirane and water prepared in reaction ethylene glycol, the disclosed embodiment reaction result of document is: the reaction time is usually about 6 hours, glycol selectivity is 93～95%, but the oxirane conversion ratio is on the low side, and usually 40～50%, the highest have only 76%.

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, can effectively the epoxide ring in the aryl rings oxidative ethane partly be added water decomposition, the yield of aryl ethylene glycol is higher, the shortcoming of this method is that water is than too high, separation brings huge energy consumption to ethylene glycol in the existence of big water gaging, causes production cost higher; And document does not relate to the stability of catalyst.

Japanese patent laid-open 7-53219 has introduced a kind of columbic acid particle and preparation method thereof, and this columbic acid particle contains acidity H ₀: the acid amount A below-3.0 is 0.35 mM/more than the gram, wherein be H more than 50% ₀: the strong acid amount below-5.6, the document do not relate to and are used for the reaction that hydration prepares ethylene glycol, show according to the study, and the columbic acid particle of preparation is not suitable for the catalyzing epoxyethane hydration reaction for preparing glycol because acidity is strong excessively.

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 production cost height, or the liquid acid catalyst etching apparatus of catalysis hydration use, contaminated environment, solid acid catalyst poor stability or stability and the active defective that can not take into account simultaneously, the solid acid catalyst that provides a kind of ethylene oxide hydration to produce ethylene glycol, this catalyst are used for the ethylene oxide hydration reaction and produce ethylene glycol, not only have good activity, selectivity, be suitable for low water than operation, and have good stable simultaneously, and can significantly reduce energy energy consumption, 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 solid acid catalyst that is used for 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) metal of 5～40% niobiums or oxide;

B) 0.01～20% be selected from the metal of VIB or the oxide at least a;

C) 0～5.0% be selected from least a in the metal of cerium, manganese or thorium or the oxide.

In the technique scheme, in vehicle weight percentage, the metal of niobium or oxide consumption are preferred 5～20%, are more preferably 5～10%, it is preferred 0.1～10% to be selected from the metal of VIB or oxide consumption, is selected from the metal of cerium, manganese or thorium or the consumption preferred 0.01～2.0% of oxide.

In the technique scheme, described oxide carrier can use separately, also can mix with arbitrary proportion and use the preferred Alpha-alumina of wherein said aluminium oxide, the preferred ZSM-5 zeolite of described zeolite.

Catalyst of the present invention also contains counts 1～10% binding agent with vehicle weight percentage, the binding agent that often uses as catalyst field such as inorganic clay, methyl or ethyl or carboxyethyl cellulose, magnesium silicate fiber element, polyvinyl alcohol, polyvinylpyrrolidone, dextrin, rare nitric acid or water.

Catalyst of the present invention can use preparation method commonly used such as mixing method, infusion process or coprecipitation 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 niobium source and co-catalyst are mixed, and the moulding of catalyst for the benefit of improves catalyst strength, can add an amount of binding agent in the mixed process, mediate then, make shaping of catalyst after, be prepared from through steps such as super-dry, roastings.Concrete preparation process is as follows:

1, niobium source:

Solid state powder form with commercially available niobium compound-niobic acid, niobium oxalate, acetic acid niobium or niobium ammino-complex is introduced, and perhaps introduces with niobium compound solution form, and niobium compound 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, vib metal (chromium, molybdenum, tungsten), cerium, manganese or thorium source:

Introduce with oxide, nitrate, chloride, ammonium salt or acetate solid state powder form, or take by weighing the catalyst formulation requirement, be mixed with certain density salting liquid according to conventional method.

3, Preparation of Catalyst

With above-mentioned niobium source, vib metal (chromium, molybdenum, tungsten), cerium, manganese or thorium source, after carrier and binding agent are fully mediated, make certain shape, catalyst shape can be made different shapes such as cylindric, spherical, disk, tubular, cellular or Raschig ring with conventional method.℃ carry out drying in room temperature～200, preferred 100 ℃～200 ℃, 1～5 hour drying time, preferred 1～3 hour, can adopt vacuum drying or aeration-drying when dry; Carry out roasting then, 100～1000 ℃ of sintering temperatures, preferred 200～700 ℃, roasting time 1～10 hour, preferred 1～5 hour, calcination atmosphere can carry out in air, nitrogen, carbon dioxide, ammonia atmosphere or in the mixed atmosphere of above-mentioned several gases, also can give roasting under vacuum, catalyst after the roasting cools off naturally, promptly obtains the catalyst finished product.

Catalyst of the present invention is mainly used in ethylene oxide hydration reaction, useful ethylene glycol product on the manufacture.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 1～15: 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 hydrothermal stability.With catalyst liquid air speed 50 hours ^-1Pressure 3.0MPa, carry out water-fast heat test in 1000 hours under 300 ℃, conversion ratio and selectivity under the same process condition before and after the evaluate catalysts hydrothermal treatment consists, find out by experimental data, trend (embodiment 11) 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, the compound that load is selected from vib metal compound or its mixture and is selected from cerium, manganese, thorium is as co-catalyst, produce cooperative effect between each component, make the catalyst that makes have good reactivity worth, be used for ethylene oxide hydration and produce ethylene glycol, have the following advantages:

1, activity of such catalysts is good, the selectivity height, and 150 ℃ of reaction temperatures, reaction pressure 1.5MPa, water is than 1～10: 1, liquid air speed 1.0～3.0 hours ^-1Produce ethylene glycol under the process conditions, the oxirane conversion ratio reaches more than 98%, glycol selectivity about 90%;

2, operation 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, reduced energy consumption significantly, and significantly reduce production costs.

3, catalyst reaction good stability, the life-span is long.The catalyst successive reaction is more than 1500 hours, and catalytic activity is not seen reduction, and the selectivity of ethylene glycol remains unchanged substantially, prolongs the catalyst runs cycle, reduces production costs.

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]

With 10 gram niobic acids, 100 gram α-Al ₂O ₃Powder joins in the kneading machine and fully mixes, chromic nitrate (III) aqueous solution that adds 4.4 ml concns 0.03% (weight), and rare nitric acid of 55 milliliter 10% (weight), fully mediate, form the bulk material, extruded moulding was in 150 ℃ of dryings 2 hours, roasting is 4 hours in 200 ℃ of air, obtains catalyst A.The catalyst composition sees Table 1.

[embodiment 2]

60 gram aluminium oxide and 40 gram silica are fully mixed, add 60 milliliters in rare nitric acid of 10% (weight) then, fully mediate in kneading machine, form the bulk material, extruded moulding in 150 ℃ of dryings 2 hours, in 1400 ℃ of roastings 4 hours, obtains the bar shaped carrier.Carrier is pulverized, with a certain amount of concentration be 125 mMs/liter ammonium molybdate aqueous solution at room temperature flood above-mentioned carrier, the maceration extract solid volume was flooded 2 hours than 2: 1, elimination solution was in 120 ℃ of vacuum drying 2 hours; Use the niobium ammonium complex solution (NH of a certain amount of weight concentration 15% then ₄[NbO (C ₂O ₄) ₂(H ₂O) ₂] (H ₂O) _n) at room temperature continuing the carrier after the above-mentioned processing of dipping, the maceration extract solid volume is than 2: 1, dip time 2 hours, elimination solution in 120 ℃ of vacuum drying 2 hours, so carries out three times and floods; The polyvinylpyrrolidonesolution solution that then adds 80 ml concns 10% (weight), after kneading, extrusion, in 120 ℃ of vacuum drying 2 hours, roasting was 4 hours in 300 ℃ of carbon dioxide atmospheres, obtains catalyst B.The catalyst composition sees Table 1.

[embodiment 3]

48.5 gram niobium oxalates and 100 gram titanium dioxide are fully mixed, obtain a kind of mixture, with a certain amount of concentration 25 mMs/liter ammonium tungstate solution in room temperature, vacuum condition this mixture of dipping down, liquid-solid volume ratio 2: 1, flooded 2 hours, then add 5 gram dextrin and suitable quantity of water, in kneading machine, fully mediate, form the bulk material, extruded moulding, in 100 ℃ of dryings 3 hours, roasting was 4 hours in 400 ℃ of nitrogen atmospheres, obtains catalyst C.The catalyst composition sees Table 1.

[embodiment 4]

With 30 gram zirconium dioxides and 70 gram ZSM-5 zeolite (SiO ₂/ Al ₂O ₃Mol ratio 60, the ammonium type) fully mix, 65 milliliters in rare nitric acid of adding 10% (weight) is fully mediated in kneading machine, form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, 800 ℃ of roastings 4 hours, obtain the stripe shape carrier, carrier is pulverized, with chromic nitrate (III) aqueous solution impregnated carrier 2 hours at room temperature, liquid-solid volume ratio 1.5: 1, elimination solution, in 120 ℃ of vacuum drying 2 hours, obtain carrier 1, continue vacuum impregnation carrier 1 with the cerous nitrate aqueous solution, liquid-solid volume ratio 1.5: 1, elimination solution in 120 ℃ of vacuum drying 2 hours, gets carrier 2.Then 18.8 gram niobic acids, 80 milliliter of 5% (weight) polyvinyl alcohol (technical grade) are fully mediated in kneading machine with above-mentioned carrier 2, formed the bulk material, extruded moulding, in 110 ℃ of dryings 2 hours, roasting was 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst D.The catalyst composition sees Table 1.

[embodiment 5]

Manganese nitrate (III) solution room temperature dipping 100 gram silica supports with a certain amount of concentration 1% (weight), liquid-solid volume ratio 2: 1, dip time 2 hours, filter, in 150 ℃ of dryings 2 hours, will flood above-mentioned carrier, the 22.5 gram niobic acid and the blend of a certain amount of sodium tungstate aqueous solution of manganese, and add 40 grams and (contain 40% weight SiO ₂) silica sol binder, in kneading machine, fully mediate, form the bulk material, extruded moulding, in 120 ℃ of dryings 2 hours, roasting was 4 hours in 600 ℃ of oxygen atmospheres, obtains catalyst E.The catalyst composition sees Table 1.

[embodiment 6]

25 gram aluminium oxide and 75 gram silica are fully mixed, add rare nitric acid of 50 ml concns 2% (weight), in kneading machine, fully mediate, form the bulk material, extruded moulding was in 150 ℃ of dryings 2 hours, in 900 ℃ of roastings 4 hours, obtain the bar shaped carrier, above-mentioned carrier is pulverized, at room temperature use earlier the above-mentioned carrier of a certain amount of thorium nitrate (IV) solution impregnation, the maceration extract solid volume was flooded elimination solution 2 hours than 2: 1, in 120 ℃ of vacuum drying 2 hours, get carrier 1; Then use a certain amount of ammonium molybdate solution room temperature vacuum impregnation carrier 1, the maceration extract solid volume is than 2: 1, dip time 2 hours, elimination solution, in 120 ℃ of vacuum drying 2 hours, carrier 2; With 33 gram acetic acid niobiums, 7 gram carboxyethyl celluloses and carrier 2 join in the kneader, add suitable quantity of water and fully mediate, and form the bulk material, extruded moulding, and 120 ℃ of vacuum drying 2 hours, 700 ℃ of vacuum bakings 4 hours obtain catalyst F.The catalyst composition sees Table 1.

[embodiment 7]

With 85 gram aluminium oxide, 15 gram HZSM-5 (SiO ₂/ Al ₂O ₃Mol ratio 150), 6.3 gram niobic acids, a certain amount of chromic nitrate (III), thorium nitrate (IV) mix, add 2 gram 5% (weight) polyvinyl alcohol, in kneading machine, fully mediate, form the bulk material, extruded moulding, 120 ℃ of vacuum drying 2 hours, roasting is 4 hours in 400 ℃ of air, obtains catalyst G.The catalyst composition sees Table 1.

[embodiment 8]

80 gram zirconium dioxides and 20 gram silica are fully mixed, add rare nitric acid of 50 ml concns 1% (weight), in kneading machine, fully mediate, form the bulk material, extruded moulding was in 150 ℃ of dryings 2 hours, in 700 ℃ of roastings 4 hours, obtain the bar shaped carrier, above-mentioned carrier is pulverized, with the above-mentioned carrier of a certain amount of ammonium tungstate solution vacuum impregnation under room temperature, liquid-solid volume ratio 2: 1, dip time 1 hour filtered, in 120 ℃ of dryings 2 hours; The chromic nitrate (III) of 12.5 gram niobic acids, requirements, cerous nitrate are mixed with carrier after the above-mentioned impregnation process, the rare nitric acid that adds 40 ml concns 3% (weight), fully mediate, form the bulk material, extruded moulding, in 120 ℃ of vacuum drying 2 hours, roasting was 3 hours in 400 ℃ of air, obtains catalyst H.The catalyst composition sees Table 1.

[embodiment 9]

With 80 gram aluminium oxide, 20 gram zirconium dioxides, 10 gram niobic acids, a certain amount of ammonium molybdate, manganese nitrate (III), thorium nitrate (IV) and 10 gram inorganic claies, fully mix, add suitable quantity of water, fully mediate, form the bulk material, extruded moulding was in 120 ℃ of vacuum drying 2 hours, roasting is 4 hours in 500 ℃ of air, obtains catalyst I.The catalyst composition sees Table 1.

[embodiment 10]

Get each 10 milliliters of the catalyst A～I of embodiment 1～9 preparation, fill in 8 millimeters of internal diameters one by one, in long 300 millimeters the stainless steel fixed bed reactors, the filler of packing into up and down carries out the catalyst activity evaluation.By measuring pump 1～10: 1 charging in molar ratio, is 1.5MPa at reaction bed pressure with raw water and oxirane, and 150 ℃ of reaction temperatures, liquid air speed are 1.0～3.0 hours ^-1Ethylene glycol is produced in reaction under the condition, with the HP5890 gas-chromatography product is carried out qualitative, quantitative analysis, ring oxidative ethane conversion ratio, glycol selectivity.Reaction result is listed in table 1.

[embodiment 11]

The test of catalyst tolerates hydrothermal stability.

Get 10 milliliters of the catalyst H of embodiment 8 preparation, be loaded into 8 millimeters of internal diameters, in long 300 millimeters the stainless steel fixed bed reactors, heat up, in reactor, feed water vapour, 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours ^-1Under the condition, carry out hydrothermal test in 1000 hours, after the hydrothermal test, catalyst is handled without any regeneration, adopts identical activity rating process conditions, investigates through the catalyst activity after the above-mentioned hydrothermal treatment consists.At reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water is than 9: 1, liquid air speed 2 hours ^-1Under the condition, carry out the catalyst activity evaluation; Reaction result is as follows:

Catalyst H oxirane conversion ratio % glycol selectivity %

Hydrothermal test preceding 100 94

After 1000 hours hydrothermal test 100 93.8

Through after 1000 hours hydrothermal test, trend does not fall in the conversion ratio of catalyst H and selectivity as follows.

By above-mentioned same method, carry out the catalyst A of example 1 preparation and the water-fast heat stabilization test of catalyst E of example 5 preparations, the conversion ratio and the selectivity of catalyst there is no downward trend, show that catalyst of the present invention has good hydrothermal stability.

[embodiment 12]

The catalyst reaction stability test.

Get 10 milliliters of the catalyst of embodiment 6 preparation, fill in 8 millimeters of internal diameters, in long 300 millimeters the stainless steel fixed bed reactors, the filler of packing into up and down carries out the catalyst stability test.With raw water and 8: 1 in molar ratio ratios of oxirane by the measuring pump charging, 150 ℃ of reaction temperatures, reaction pressure 1.5MPa, liquid air speed 3.0 hours ^-1Ethylene glycol is produced in reaction under the condition, and reaction was carried out 1500 hours continuously.With the HP5890 gas chromatograph product is carried out qualitative, quantitative analysis, ring oxidative ethane conversion ratio, glycol selectivity.Initial reaction stage (reacting 48 hours), oxirane conversion ratio 98%, glycol selectivity 92% is reacted after 1500 hours oxirane conversion ratio 99%, glycol selectivity 91.6%.

Use catalyst of the present invention, trend does not fall in successive reaction 1500 hours, activity of such catalysts, selectivity as follows.

[comparative example 1]

Granularity 20-40 purpose porcelain ring is filled in 8 millimeters of internal diameters for 10 milliliters, 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

Catalyst	Catalyst is formed	Water is than (mole)	Air speed hour -1	Oxirane conversion ratio %	Glycol selectivity %
						A	8％Nb 2O 5-0.2％Cr 2O 3/α-Al 2O 3	5∶1	2.0	100	86
B	10％Nb 2O 5-3％MoO 3/60％Al 2O 3+40％SiO 2	10∶1	3.0	100	91
						C	12％Nb 2O 5-5％WO 3/TiO 2	7∶1	2.0	100	89
D	15％Nb 2O 5-0.8％Cr 2O 3-0.02％Ce 2O 3/30％ ZrO 2+70％ZSM-5	2∶1	3.0	100	84
						E	18％Nb 2O 5-0.7％WO 3-0.01％Mn 2O 3/SiO 2	10∶1	2.0	100	93
F	20％Nb 2O 5-0.03％MoO 3-0.2％ThO 2/25％Al 2O 3+75％ SiO 2	8∶1	3.0	98	92
						G	5％Nb 2O 5-0.02％Cr 2O 3-2.0％ThO 2/85％ Al 2O 3+15％HZSM-5	10∶1	3.0	99	94
H	10％Nb 2O 510％Cr 2O 3-0.1％WO 3+0.3％Ce 2O 3/80％ ZrO 2+20％SiO 2	9∶1	2.0	100	94
						I	8％Nb 2O 5-4％MoO 3-0.5％Mn 2O 3-0.004％ThO 2/80％ Al 2O 3+20％ZrO 2	10∶1	2.0	100	94
Compare 1	/	10∶1	2.0	92	75
						Compare 2	/	22∶1	2.0	100	90

Claims (8)

1, a kind of ethylene oxide hydration is produced the solid acid catalyst of ethylene glycol, 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) metal of 5～40% niobiums or oxide;

B) 0.01～20% be selected from the metal of VIB or the oxide at least a;

C) 0～5.0% be selected from the metal of cerium, manganese or thorium or the oxide at least a.

2, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 1, it is characterized in that in vehicle weight percentage the metal of niobium or oxide consumption are 5～20%.

3, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 2, it is characterized in that in vehicle weight percentage the metal of niobium or oxide consumption are 5～10%.

4, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 1, it is characterized in that in vehicle weight percentage the metal or the oxide consumption that are selected from VIB are 0.1～10%.

5, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 1, it is characterized in that in vehicle weight percentage being selected from the metal of cerium, manganese or thorium or the consumption of oxide is 0.01～2.0%.

6, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 1, it is characterized in that described aluminium oxide is an Alpha-alumina.

7, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration of claim 1, it is characterized in that described zeolite is the ZSM-5 zeolite.

8, produce the solid acid catalyst of ethylene glycol according to the described ethylene oxide hydration 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%.