CN1255216C - Solid acid catalyzer for preparing glycol by hydrating ethylene oxide - Google Patents
Solid acid catalyzer for preparing glycol by hydrating ethylene oxide Download PDFInfo
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- CN1255216C CN1255216C CN 03141451 CN03141451A CN1255216C CN 1255216 C CN1255216 C CN 1255216C CN 03141451 CN03141451 CN 03141451 CN 03141451 A CN03141451 A CN 03141451A CN 1255216 C CN1255216 C CN 1255216C
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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 preparing ethylene glycol by hydrating epoxy ethane, which has the technical scheme that oxide loaded with niobium on a carrier of the oxide is used as a main active component, and at least one auxiliary agent selected from IVB metal compounds and metal compounds of vanadium or tantalum non-forcefully added. 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
Technical field
The present invention relates to a kind of solid acid catalyst, particularly about a kind of Niobic Acid agent by ethylene oxide hydration prepared in reaction ethylene glycol by 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 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 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, a kind of solid acid catalyst by hydrating epoxy ethane to prepare ethandiol is provided, this solid acid catalyst is used for ethylene oxide hydration prepared in reaction ethylene glycol, not only has good activity, selectivity is suitable for low water than operation, and has good stable simultaneously, 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 by hydrating epoxy ethane to prepare ethandiol, to be selected from a kind of or its mixture in aluminium oxide, silica 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 IVB or the oxide at least a;
C) 0~10% be selected from the metal of vanadium or tantalum or the oxide at least a.
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 IVB or oxide consumption, is selected from the metal or the oxide consumption preferred 0.1~5% of vanadium or tantalum.
In the technique scheme, described oxide carrier can use separately, also can mix with certain proportion and use the preferred Alpha-alumina of wherein said aluminium oxide, the preferred β 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, dextrin, rare nitric acid or water.
Catalyst of the present invention can use method for preparing catalyst 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, fully 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 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, IVB metal (titanium, zirconium, hafnium), vanadium or tantalum source:
Introduce with metal, oxide, nitrate, chloride, acetate or organic matter, during obtain solution, preferred version:
Titanium source: titanium sulfate, tetrabutyl titanate (TEOS) or other titanium sources;
Zirconium source: zirconyl nitrate, tetrachloro oxygen zirconium, zirconium chloride;
Vanadium source: ammonium metavanadate.
Take by weighing a certain amount of above-mentioned substance, make solution or be hydrolyzed according to corresponding conventional method and make colloidal sol.
3, Preparation of Catalyst
With above-mentioned niobium source, after titanium, zirconium, hafnium, vanadium or tantalum source, carrier unit's powder and binding agent are fully mediated in kneader, 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 or ammonia atmosphere, 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 the ethylene oxide hydration reaction, prepares industrial useful ethylene glycol product.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, reactant liquor air speed 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
-1, pressure 3.0MPa carries out water-fast heat test in 1000 hours under 300 ℃ of conditions of temperature, conversion ratio and selectivity under the same process condition before and after the evaluate catalysts hydrothermal treatment consists.Find out by experimental data, catalyst is through after 1000 hours hydrothermal treatment consists, trend (embodiment 11) does not fall in conversion ratio and selectivity as follows, show that catalyst of the present invention is specially adapted to the inefficient high temperature aqueous reaction of general solid acid system, and have 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 be selected from IVB metallic compound or its mixture and be selected from vanadium or the compound of tantalum 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 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
-1Prepare 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 make reaction water than reduction significantly than low, and by the 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.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, 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, 0.5 gram titanium dioxide and 100 gram α-Al
2O
3Fully mixed in kneading machine, add 60 milliliters in rare nitric acid of weight concentration 5% then, mediate and form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, roasting was 4 hours in 400 ℃ of air, obtains catalyst A.The catalyst composition sees Table 1.
[embodiment 2]
60 gram aluminium oxide and 40 gram silica are joined in the kneading machine, mix, 60 milliliters in the rare nitric acid that adds concentration 1% (weight) then, mediate and form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, the bar shaped carrier is made in 1400 ℃ of roastings 4 hours, and carrier is pulverized, carrier after weighing 12.5 gram niobic acids and 1.0 restrain zirconium dioxides and pulverize fully mixes, add 70 milliliters of binding agent poly-vinyl alcohol solutions, and after mediate, after the extrusion, in 120 ℃ of vacuum drying 2 hours, roasting is 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst B.The catalyst composition sees Table 1.
[embodiment 3]
With 80 gram aluminium oxide and 20 gram-zeolite (SiO
2/ Al
2O
3Mol ratio 12) joins in the kneading machine, mix, 55 milliliters in the rare nitric acid that adds concentration 1.5% (weight) then, mediate to form the bulk material, extruded moulding was in 150 ℃ of dryings 2 hours, in 1200 ℃ of roastings 4 hours, make the bar shaped carrier, carrier is pulverized, mix with 3 gram titanium dioxide and obtain mixture.The commercially available acetic acid niobium of 16.5 grams is dissolved in 110 milliliters of citric acids, makes niobic acid solution; 0.26 gram ammonium metavanadate is dissolved in 50 milliliter of 5% (weight) hydrogen peroxide solution, makes ammonium metavanadate solution; At room temperature use earlier niobic acid solution impregnation said mixture, the maceration extract solid volume is than 2: 1, dip time 2 hours, elimination solution, in 120 ℃ of vacuum drying 2 hours, at room temperature continued incipient impregnation 2 hours then,, then add 70 milliliters of 10% (weight) polyvinylpyrrolidonesolution solution in 120 ℃ of vacuum drying 2 hours with ammonium metavanadate solution, after kneading, extrusion, in 100 ℃ of dryings 3 hours, roasting was 4 hours in 200 ℃ of air, obtains catalyst C.The catalyst composition sees Table 1.
[embodiment 4]
With niobium ammonium complex compound (NH
4[NbO (C
2O
4)
2(H
2O)
2] (H
2O)
n), tantalic acid and 100 gram silica supports fully mix according to a certain percentage, obtain solid mixture; Under 50 ℃, tetrabutyl titanate (TEOS) slowly is added to the water, being stirred to its complete hydrolysis becomes glue to make colloidal tio 2, colloidal tio 2 and Macrogol 6000 solution are added in the above-mentioned solid mixture for 30 milliliters, mediate and form the bulk material, extruded moulding, in 110 ℃ of dryings 2 hours, roasting was 4 hours in 300 ℃ of nitrogen atmospheres, obtains catalyst D.The catalyst composition sees Table 1.
[embodiment 5]
Take by weighing 15 gram aluminium oxide and 85 gram silica supports join in the kneading machine, add 50 milliliters in rare nitric acid of concentration 8% (weight), mediate and form the bulk material, extruded moulding in 150 ℃ of dryings 2 hours, in 1000 ℃ of roastings 4 hours, is made the bar shaped carrier.Carrier is pulverized, and the tetrabutyl titanate (TEOS) with the catalyst formulation requirement under 60 ℃ slowly is added to the water, and is stirred to its complete hydrolysis and becomes glue, makes the metatitanic acid colloid; The zirconyl nitrate of requirement is dissolved in 10 ml waters, makes zirconium salt solution.A certain amount of niobium oxalate, above-mentioned carrier, metatitanic acid colloid and zirconium salt solution are fully mediated in kneading machine, formed the bulk material, extruded moulding, 120 ℃ of dryings 2 hours, roasting is 4 hours in 600 ℃ of air, obtains catalyst E.The catalyst composition sees Table 1.
[embodiment 6]
A certain amount of niobic acid and hafnium oxide, 8 gram inorganic claies and 100 gram silica supports are joined in the kneading machine, mix, 65 milliliters in the rare nitric acid that adds concentration 1% (weight) then, mediate and form the bulk material, extruded moulding, 120 ℃ of vacuum drying 2 hours, 500 ℃ of vacuum bakings 4 hours.Obtain catalyst F.The catalyst composition sees Table 1.
[embodiment 7]
A certain amount of zirconyl chloride is dissolved in 100 ml waters makes zirconium salt solution, ammonium metavanadate is dissolved in 55 milliliter of 5% (weight) hydrogen peroxide, with niobic acid, 100 gram alumina supports fully mix, obtain solid mixture, earlier at room temperature flood above-mentioned solid mixture with above-mentioned zirconium salt solution, the maceration extract solid volume was than 1.5: 1, dip time 2 hours, elimination solution, in 120 ℃ of vacuum drying 2 hours, at room temperature continued equivalent impregnation 2 hours then,, then add 70 milliliters of 10% (weight) polyvinylpyrrolidonesolution solution in 120 ℃ of vacuum drying 2 hours with above-mentioned ammonium metavanadate solution, through mediating, behind the extruded moulding, in 120 ℃ of vacuum drying 2 hours, roasting was 4 hours in 700 ℃ of carbon dioxide atmospheres, obtains catalyst G.The catalyst composition sees Table 1.
[embodiment 8]
100 gram silica supports are joined in the kneading machine, add 60 milliliters in rare nitric acid of concentration 4% (weight), mediate and form the bulk material, extruded moulding in 150 ℃ of dryings 2 hours, in 800 ℃ of roastings 4 hours, is made the bar shaped carrier.Carrier is pulverized, join in the kneader, add a certain amount of niobic acid, tantalic acid then, mix, add 60 milliliters of the dilute nitric acid solutions of the zirconyl nitrate aqueous solution of concentration requirement and concentration 2% (weight) again, mediate and 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]
The tetrabutyl titanate (TEOS) of prescription requirement is slowly joined the niobium ammonium complex compound (NH of concentration 15% (weight) under 40 ℃
4[NbO (C
2O
4)
2(H
2O)
2] (H
2O)
n) in the aqueous solution, form a kind of mixed solution, 100 gram alumina supports are joined in the kneader, add above-mentioned mixed solution then, fully mediate, form the bulk material, extruded moulding, 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 evaluation of catalyst.Use metering pump massage that than 1~10: 1 charging raw water and oxirane, reaction bed pressure is 1.5MPa, and 150 ℃ of reaction temperatures, liquid air speed are 2.0~3.0 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]
The test of catalyst tolerates hydrothermal stability.
Get 10 milliliters of the catalyst I of embodiment 9 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 and the preceding identical activity rating process conditions of hydrothermal treatment consists, investigates through the catalyst activity after the above-mentioned hydrothermal treatment consists.At reaction pressure 1.5MPa, 150 ℃ of reaction temperatures, water is than 10: 1, liquid air speed 2.0 hours
-1Under the condition, carry out the catalyst activity evaluation; Reaction result is as follows:
Catalyst rings oxidative ethane conversion ratio % glycol selectivity %
Hydrothermal test preceding 10 94
After 1000 hours hydrothermal test 100 93.6
Through after 1000 hours hydrothermal test, trend does not fall in the conversion ratio of catalyst and selectivity as follows.
By above-mentioned same method, carry out the catalyst A of example 1 preparation and example 2 preparations the water-fast heat stabilization test of catalyst B, 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 8 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 9: 1 in molar ratio ratios of oxirane by the measuring pump charging, 150 ℃ of reaction temperatures, reaction pressure 1.5MPa, 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 was carried out 1500 hours continuously.Initial reaction stage, oxirane conversion ratio 100%, glycol selectivity 94% is reacted after 1500 hours oxirane conversion ratio 100%, glycol selectivity 93.5%.
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]
With granularity is that to fill in internal diameter be 8 millimeters to 20-40 purpose porcelain ring 10ml, 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 | 8%Nb 2O 5-0.5%TiO 2/α-Al 2O 3 | 10 | 2.0 | 100 | 92 |
B | 10%Nb 2O 5-1%ZrO 2/60%Al 2O 3+40%SiO 2 | 5 | 3.0 | 100 | 87 |
C | 5%Nb 2O 5-3.0%TiO 2-0.2%V 2O 5/80%Al 2O 3+ 20%-zeolite | 7 | 2.0 | 100 | 89 |
D | 20%Nb 2O 5-0.4%TiO 2-5.0%Ta 2O 5/SiO 2 | 2 | 3.0 | 100 | 82 |
E | 13%Nb 2O 5-10%TiO 2-0.01%ZrO 2/15%Al 2O 3 +85%SiO 2 | 10 | 2.0 | 99 | 93 |
F | 15%Nb 2O 5-0.1%HfO 2/SiO 2 | 8 | 3.0 | 100 | 92 |
G | 20%Nb 2O 5-0.04%ZrO 2-0.2%- 2O 5/Al 2O 3 | 12 | 3.0 | 97 | 92 |
H | 18%Nb 2O 5-1.0%ZrO 2+0.3%Ta 2O 5/SiO 2 | 9 | 2.0 | 100 | 94 |
I | 8%Nb 2O 5-0.001%TiO 2/Al 2O 3 | 10 | 2.0 | 100 | 94 |
Compare 1 | / | 10 | 2.0 | 92 | 75 |
Compare 2 | / | 22 | 2.0 | 100 | 90 |
Claims (9)
1, a kind of solid acid catalyst by hydrating epoxy ethane to prepare ethandiol, being selected from a kind of or its mixture in aluminium oxide, silica 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 IVB or the oxide at least a;
C) 0~10% be selected from the metal of vanadium or tantalum or the oxide at least a.
According to the described solid acid catalyst of claim 1, it is characterized in that 2, the metal of niobium or oxide consumption are 5~20% in vehicle weight percentage by hydrating epoxy ethane to prepare ethandiol.
According to the described solid acid catalyst of claim 2, it is characterized in that 3, the metal of niobium or oxide consumption are 5~10% in vehicle weight percentage by hydrating epoxy ethane to prepare ethandiol.
According to the described solid acid catalyst of claim 1, it is characterized in that 4, the metal or the oxide consumption that are selected from IVB are 0.1~10% in vehicle weight percentage by hydrating epoxy ethane to prepare ethandiol.
According to the described solid acid catalyst of claim 1, it is characterized in that 5, the metal or the oxide consumption that are selected from vanadium or tantalum are 0.1~5% in vehicle weight percentage by hydrating epoxy ethane to prepare ethandiol.
6,, it is characterized in that described aluminium oxide is an Alpha-alumina according to the described solid acid catalyst of claim 1 by hydrating epoxy ethane to prepare ethandiol.
7,, it is characterized in that described zeolite is a beta-zeolite according to the described solid acid catalyst of claim 1 by hydrating epoxy ethane to prepare ethandiol.
8, according to the described solid acid catalyst by hydrating epoxy ethane to prepare ethandiol of claim 1, the metal that it is characterized in that described IVB is titanium or zirconium.
9, according to the described solid acid catalyst of claim 1 by hydrating epoxy ethane to prepare ethandiol, it is characterized in that described catalyst also contains binding agent, in vehicle weight percentage, the consumption of binding agent is 1~10%.
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