CN100413579C - Catalyst used for hydrating epoxy ethane to prepare ethandiol - Google Patents
Catalyst used for hydrating epoxy ethane to prepare ethandiol Download PDFInfo
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- CN100413579C CN100413579C CNB2004100666288A CN200410066628A CN100413579C CN 100413579 C CN100413579 C CN 100413579C CN B2004100666288 A CNB2004100666288 A CN B2004100666288A CN 200410066628 A CN200410066628 A CN 200410066628A CN 100413579 C CN100413579 C CN 100413579C
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Abstract
The present invention relates to a catalyst for preparing glycol by epoxy ethane hydration, which mainly solves the problems that the reaction water ratio of the existing epoxy ethane non-catalytic hydration is high, the energy consumption is large and the production cost is high, or a liquid acid catalyst used in catalytic hydration erodes equipment and pollutes the environment, the stability of a solid acid catalyst is poor, or the stability and the activity can not be kept simultaneously. The present invention solves the problems by adopting the technical scheme that the oxide of niobium, at least one kind of element or compounds selected from vanadium, molybdenum, tungsten, tin and lead, and at least one kind of element or compounds selected from lanthanum, praseodymium and neodymium are loaded on a carrier. The present invention can be used in industrial production of glycol.
Description
Technical field
The present invention relates to a kind of catalyst that is used for hydrating epoxy ethane to prepare ethandiol, particularly about being used for the columbium oxide catalyst 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 contains two kinds of research methods: a kind of is direct hydration method, and promptly oxirane and water react generation ethylene glycol under certain condition; Another kind is the ethylene carbonate method, promptly oxirane under catalyst action, elder generation and CO
2Reaction generates ethylene carbonate, and latter's hydrolysis generates ethylene glycol.
Industrial production ethylene glycol adopts on-catalytic hydration method at present.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.In the presence of catalyst-free, hydration reaction speed is slow simultaneously, and industrial the 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, 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 research to the catalyst that is used for hydration of epoxy ethane to prepare ethandiol, and the research focus mainly adopts anion exchange resin, quaternary alkylphosphonium salt etc. as the hydration reaction catalyst.
US 5874653 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: reaction was carried out 600 hours, catalyst has good selectivity and stability, glycol selectivity is 93～95%, but the oxirane conversion ratio is on the low side, and the highest have only 57.9%.
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, the existence of big water gaging is separated for aryl ethylene glycol and brings huge energy consumption, 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 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 that according to the study 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 exist oxirane on-catalytic hydration reaction water than higher in the document in the past, 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 problem that can not take into account simultaneously provide a kind of new catalyst that is used for hydrating epoxy ethane to prepare ethandiol.When this catalyst is used for ethylene oxide hydration prepared in reaction ethylene glycol, 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 catalyst that is used for hydrating epoxy ethane to prepare ethandiol, to be selected from least a in aluminium oxide, silica, titanium oxide, zirconia or the zeolite is carrier, weight in carrier is benchmark, and the active constituent that is stated from the carrier comprises following component:
A) oxide 1～30% of niobium;
B) at least a compound 0.01～8% that is selected from vanadium, molybdenum, tungsten, tin, lead;
C) at least a compound 0.001～2% that is selected from lanthanum, praseodymium, neodymium.
In the technique scheme, be benchmark in the weight of carrier, the oxide consumption preferable range of niobium is 2～20%; At least a consumption preferable range that is selected from the compound of vanadium, molybdenum, tungsten, tin, lead is 0.01～5%.
In the technique scheme, described oxide carrier can use separately, also can mix and use with arbitrary proportion, the carrier preferred version is selected from least a in aluminium oxide, silica, titanium oxide or the zirconia, wherein said aluminium oxide preferred version is an Alpha-alumina, and described zeolite preferred version is the ZSM-5 zeolite.
The weight that catalyst of the present invention also contains with carrier is that benchmark is counted 1～10% binding agent, 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, rare nitric acid.
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 blending method and infusion process, 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.Infusion process is to prepare the required carrier of catalyst earlier, then activity of such catalysts component and co-catalyst one or many is impregnated on the carrier, and drying, steps such as roasting are prepared from.Concrete preparation process is as follows:
1, niobium source:
Solid state powder form with commercially available niobium oxide, 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 that contains, 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, vanadium, molybdenum, tungsten, tin, plumbous source:
Introduce with oxide, nitrate, chloride or acetate solid state powder form, or be dissolved in the water and be mixed with salting liquid.In fact, as long as it can be mixed with the aqueous solution, there is no particular restriction on the method.
3, lanthanum, praseodymium, neodymium source
Introduce with oxide, nitrate, chloride, carbonate or acetate solid state powder form, or be dissolved in the water and be mixed with salting liquid.In fact, as long as it can be mixed with the aqueous solution, there is no particular restriction on the method.
4, Preparation of Catalyst
With above-mentioned niobium source, vanadium, molybdenum, tungsten, tin, plumbous source, lanthanum, praseodymium, neodymium source, carrier and binding agent are fully mediated evenly in kneader, and 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 at least a atmosphere in air, nitrogen, carbon dioxide, hydrogen or ammonia, 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 1～10: 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.
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 under 300 ℃, and acid amount, the acid strength of 1000 hours inner catalysts are not seen obvious decline.The catalyst of example for example of the present invention 7～9 preparations after carrying out 1000 hours hydrothermal treatment consists under the above-mentioned process conditions, is loaded into once more and carries out performance evaluation in the fixed bed reactors, estimate process conditions: reaction pressure 1.5MPa, 120 ℃ of reaction temperatures, water be than 10, liquid air speed 2.0 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.
Catalyst of the present invention is by the main active constituent of the conduct of load niobium oxide on some oxide carriers, the compound that load is selected from vanadium, molybdenum, tungsten, tin, plumbous compound or its mixture and is selected from lanthanum, praseodymium, neodymium is 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 120 ℃ 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%, and glycol selectivity about 90% reaches as high as 95%;
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 reduced energy consumption significantly, thereby significantly reduced 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.
4, 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]
With former powder 113 grams of aluminium hydroxide, 5 gram graphite, 5 gram sesbania powder fully mix, 60 milliliters in the rare nitric acid that adds 4% (weight) then, in kneading machine, fully mediate, form the bulk material, extruded moulding, drying is 24 hours under the room temperature, 150 ℃ of dryings 2 hours, 1200 ℃ of roastings 4 hours obtain bar shaped α-Al
2O
3Carrier.The oxalic acid solutions that will contain 6.25 gram niobic acids impregnated on the Manufactured carrier, 120 ℃ of dryings 2 hours; Then ammonium metavanadate is dissolved in 5% (weight) hydrogen peroxide, is impregnated into once more on the catalyst, 120 ℃ of dryings 2 hours; At last the lanthanum trichloride aqueous solution is impregnated on the catalyst 120 ℃ of dryings 2 hours.The roasting 4 hours in 700 ℃ of air of above-mentioned catalyst precarsor obtains catalyst A.The catalyst composition sees Table 1.
[embodiment 2]
67.6 gram aluminium hydroxides, 40 gram silica, 8 gram graphite, 4 gram cyclodextrin are fully mixed, 60 milliliters in the rare nitric acid that adds 4% (weight) then, in kneading machine, fully mediate, form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours,, obtain the bar shaped carrier in 1400 ℃ of roastings 4 hours.With a certain amount of concentration be 125 mMs/liter ammonium molybdate 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; Be that the cerous chlorate and the concentration of 0.2800 mol is the LaCl of 200.64 grams per liters then with a certain amount of concentration
3Mixed solution at room temperature floods above-mentioned catalyst precarsor, and the maceration extract solid volume was flooded 2 hours than 2: 1, elimination solution, and in 120 ℃ of vacuum drying 2 hours, roasting was 4 hours in 300 ℃ of ammonia atmospheres, obtains catalyst B.The catalyst composition sees Table 1.
[embodiment 3]
With commercially available niobium oxalate 40.5 grams, 15 gram polyvinyl alcohol, 8 gram sedimentation sulphur, required ammonium tungstate and 100 gram titanium dioxide fully mix, and obtain a kind of mixture, then add suitable quantity of water, in kneading machine, fully mediate, form the bulk material, extruded moulding was in 200 ℃ of dryings 3 hours, the praseodymium trichloride solution impregnation that then with concentration is 0.12 mol is in above-mentioned catalyst, and in 150 ℃ of dryings 2 hours, roasting was 4 hours in 400 ℃ of carbon dioxide atmosphere, 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), in kneading machine, fully mediate, form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, 800 ℃ of roastings 4 hours obtained the stripe shape carrier, carrier is pulverized, with concentration is the neodymium chloride aqueous solution impregnated carrier 2 hours at room temperature of 39.88 grams per liters, liquid-solid volume ratio 2.5: 1, elimination solution, in 120 ℃ of vacuum drying 2 hours, obtain carrier 1; Continue vacuum impregnation carrier 1 with the stannous chloride aqueous solution, liquid-solid volume ratio 2.0: 1, elimination solution in 120 ℃ of vacuum drying 2 hours, gets carrier 2.Then with required niobium oxalate solution impregnation to carrier 2, liquid-solid volume ratio 1.5: 1,120 ℃ of down dehydrations, roasting is 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst D.The catalyst composition sees Table 1.
[embodiment 5]
With 100 gram silica, 2 gram lanthanas, 18.75 gram niobic acids fully mix, and with tablet press machine it are pressed into sheet (pressure 200 kg/cm
2), and 200 ℃ of dryings 4 hours.Be that the butter of tin solution room temperature of 0.8930 mol is flooded above-mentioned catalyst then with concentration, liquid-solid volume ratio 2: 1, dip time 2 hours filters, and in 150 ℃ 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, 0.02 gram praseodymium oxide, 5 gram potassic feldspars and 75 gram silica are fully mixed, the rare nitric acid that adds 50 ml concns 2% (weight), in kneading machine, fully mediate, form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, 900 ℃ of roastings 4 hours obtained the bar shaped carrier.Earlier at room temperature flood above-mentioned carrier with a certain amount of lead nitrate solution, the maceration extract solid volume was flooded 2 hours than 2: 1, and elimination solution in 120 ℃ of vacuum drying 2 hours, gets carrier 1; Then use a certain amount of acetic acid niobium solution, flood above-mentioned carrier, the maceration extract solid volume was flooded 2 hours than 1.5: 1, elimination solution, and in 120 ℃ of dryings 2 hours, 400 ℃ of vacuum bakings 4 hours obtained catalyst F.The catalyst composition sees Table 1.
[embodiment 7]
With 85 gram aluminium oxide, 15 gram ZSM-5 (SiO
2/ Al
2O
3Mol ratio 150), 0.02 gram vanadic anhydride, 0.001 gram neodymia and 25 gram niobic acids mix, and 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 2 hours in 400 ℃ of air.Then be the above-mentioned catalyst of stannous sulfate solution impregnation of 0.5759 mol with concentration, the maceration extract solid volume was flooded 2 hours than 2.5: 1, elimination solution, and in 120 ℃ of dryings 2 hours, roasting 2 hours once more obtained catalyst G in 400 ℃ of air.The catalyst composition sees Table 1.
[embodiment 8]
Method according to embodiment 1 prepares α-Al
2O
3Carrier, difference are to add 0.01% praseodymium oxide in raw material, then are the Ce (NO of 0.453 mol with concentration
3)
3, concentration is that the butter of tin of 0.8930 mol successively is impregnated on the carrier, the maceration extract solid volume was flooded 2 hours than 2.5: 1, elimination solution, 120 ℃ of dryings 2 hours.Then with tartaric acid niobium solution impregnation to catalyst, 120 ℃ of drying and dehydratings; The last required stannous chloride solution of equivalent impregnation, 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, 15 gram niobium pentaoxides, 0.004 gram neodymium carbonate, the ammonium ceric nitrate of aequum and 10 gram inorganic claies fully mix, add suitable quantity of water, fully mediate, form the bulk material, extruded moulding, in 120 ℃ of vacuum drying 2 hours, roasting was 2 hours in 500 ℃ of air.The butter of tin that then with concentration is 0.8930 mol is impregnated on the carrier, and the maceration extract solid volume was flooded 2 hours than 2.5: 1, elimination solution, 120 ℃ of dryings 2 hours.Be the LaCl of 200.64 grams per liters at last with concentration
3Solution at room temperature floods above-mentioned catalyst precarsor, and the maceration extract solid volume was flooded 2 hours than 2: 1, elimination solution, and in 120 ℃ of vacuum drying 2 hours, roasting 2 hours once more obtained catalyst I 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, 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 120 ℃ 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, 120 ℃ of reaction temperatures, water is than 10: 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 95
After 1000 hours hydrothermal test 100 94.9
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, 120 ℃ 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 92.5%.
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]
Granularity 20～40 purpose porcelain rings are 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, 120 ℃ 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 | 5％Nb 2O 5-0.2％V 2O 5-0.01％LaCl 3/α-Al 2O 3 | 2∶1 | 2.0 | 98 | 86 |
| B | 8％Nb 2O 5-3％MoO 3-0.005％LaCl 3-0.025％Ce Cl 3/60％Al 2O 3+40％SiO 2 | 5∶1 | 3.0 | 100 | 89.5 |
| C | 10％Nb 2O 5-8％WO 3-0.001％PrCl 3/TiO 2 | 7∶1 | 2.0 | 100 | 91 |
| D | 12％Nb 2O 5-0.01％SnCl 2-0.08％NdCl 3/ 30％ZrO 2+70％ZSM-5 | 10∶1 | 3.0 | 100 | 92.5 |
| E | 15％Nb 2O 5-0.7％SnCl 4-2.0％La 2O 3/SiO 2 | 10∶1 | 2.0 | 98 | 93 |
| F | 18％Nb 2O 5-0.01％PbO 2-0.02％Pr 2O 3/25％Al 2 O 3+75％SiO 2 | 8∶1 | 3.0 | 99 | 92.5 |
| G | 20％Nb 2O 5-0.02％V 2O 5-2.0％SnSO 4-0.001％ Nd 2O 3/85％Al 2O 3+15％ZSM-5 | 10∶1 | 3.0 | 100 | 94 |
| H | 12％Nb 2O 5-2％SnCl 2-1％SnCl 4-0.01％Pr 2O 3 -0.29％Ce 2O 3/α-Al 2O 3 | 10∶1 | 2.0 | 100 | 95 |
| I | 15％Nb 2O 5-5％SnCl 4-0.1％LaCl 3-0.4％Ce 2O 3- 0.004％Nd 2(CO 3) 3/80％Al 2O 3+20％ZrO 2 | 10∶1 | 2.0 | 100 | 94.5 |
| Compare 1 | / | 10∶1 | 2.0 | 61 | 84 |
| Compare 2 | / | 22∶1 | 2.0 | 82 | 93 |
Claims (7)
1. catalyst that is used for hydrating epoxy ethane to prepare ethandiol is a carrier to be selected from least a in aluminium oxide, silica, titanium oxide, zirconia or the zeolite, is benchmark in the weight of carrier, and the active constituent that is stated from the carrier comprises following component:
A) oxide 1～30% of niobium;
B) at least a compound 0.01～8% that is selected from vanadium, molybdenum, tungsten, tin, lead;
C) at least a compound 0.001～2% that is selected from lanthanum, praseodymium, neodymium.
2. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that the weight in carrier is benchmark, the oxide consumption of niobium is 2～20%.
3. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that the weight in carrier is benchmark, at least a consumption that is selected from the compound of vanadium, molybdenum, tungsten, tin, lead is 0.01～5%.
4. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that carrier is selected from least a in aluminium oxide, silica, titanium oxide or the zirconia.
5. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 4, it is characterized in that aluminium oxide is an Alpha-alumina.
6. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that zeolite is the ZSM-5 zeolite.
7. according to the described catalyst that is used for hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that catalyst also contains binding agent, is benchmark in the weight of carrier, and the consumption of binding agent is 1～10%.
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| CNB2004100666288A CN100413579C (en) | 2004-09-24 | 2004-09-24 | Catalyst used for hydrating epoxy ethane to prepare ethandiol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020024923A1 (en) | 2018-07-31 | 2020-02-06 | 中国石油化工股份有限公司 | Nanocaged catalyst, preparation method, and application |
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| CN101190876B (en) * | 2006-11-21 | 2010-05-12 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol ether |
| CN101601995B (en) * | 2008-06-12 | 2013-04-03 | 中国石油化工股份有限公司 | Aluminum oxide catalyst used for preparing dimethyl ether by gas-phase dehydration of methanol and preparation method thereof |
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| JPS5673035A (en) * | 1979-11-19 | 1981-06-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of alkylene glycol |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5673035A (en) * | 1979-11-19 | 1981-06-17 | Nippon Shokubai Kagaku Kogyo Co Ltd | Preparation of alkylene glycol |
| 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 |
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| Selective catalytic hydration of ethylene oxide overniobiumoxide supported on α-alumina.. Yingcheng Li, et al.Applied catalysis A :General,Vol.272 No.1-2. 2004 |
| Selective catalytic hydration of ethylene oxide overniobiumoxide supported on α-alumina.. Yingcheng Li, et al.Applied catalysis A :General,Vol.272 No.1-2. 2004 * |
| 环氧乙烷催化水合制乙二醇研究进展. 李应成等.工业催化，第10卷第2期. 2002 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020024923A1 (en) | 2018-07-31 | 2020-02-06 | 中国石油化工股份有限公司 | Nanocaged catalyst, preparation method, and application |
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