CN1566049A - Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration - Google Patents
Solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration Download PDFInfo
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Abstract
The invention relates to a solid acid catalyst for preparing ethylene glycol by ethylene oxide hydration, wherein the niobium oxide loaded on oxide carrying agent is used as the main active component, metallic compounds selected from IVA and antimony, phosphor, sulfur, ferrum or cobalt as catalyst promoters, the obtained catalyst can be used for preparing ethylene glycol by ethylene oxide catalytic hydration, which possesses not only good activity, selectivity, but also fine steadiness.
Description
Technical field
The present invention relates to a kind of solid acid catalyst that is used for ethylene oxide hydration prepared in reaction ethylene glycol, particularly about being used for a kind of Niobic Acid agent of ethylene oxide hydration prepared in reaction ethylene glycol.
Background technology
Ethylene glycol is important aliphatic dihydroxy alcohol, and is of many uses, and main application is to produce vibrin, comprises fiber, film and engineering plastics.Also can directly be used as refrigerant and frostproofer, also be simultaneously to produce the indispensable materials of product such as Synolac, softening agent, paint, tackiness agent, tensio-active agent, explosive and capacitor electrolyte.
With oxyethane is feedstock production ethylene glycol, mainly contain two kinds of operational paths: a kind of is direct hydration method, oxyethane and water react generation ethylene glycol under certain condition, and reaction does not need catalyzer just can carry out, and is divided into two kinds of technologies of catalytic hydration and on-catalytic hydration; Another kind is the ethylene carbonate method, promptly oxyethane 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 catalyzer, the mol ratio of water and oxyethane (hereinafter to be referred as water than) be 20～25: 1,150～200 ℃ of temperature of reaction, reaction pressure 0.8～2.0MPa, oxyethane transformation efficiency be near 100%, glycol selectivity 88～90%.This method disadvantage is that energy consumption is big, the evaporation 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 facility 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 by product 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.
Catalytic hydration is produced the method for ethylene glycol the earliest, once adopts inorganic acid as catalyst, makes catalyzer as using sulfuric acid, and oxyethane can all transform, and the ethylene glycol yield is 88～90%.But because liquid acid catalyst etching apparatus, contaminate environment, there are problems in quality product, need add alkali neutralization and separation circuit during aftertreatment, 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 mineral acid catalytic hydration, people have carried out many-sided improvement research to the catalyzer 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 anionite-exchange resin of quaternary ammonium group that has as the ethylene oxide hydration catalyzer.At 80～200 ℃ of temperature of reaction, reaction pressure 200～3000KPa, water is than 1～15: react under 1 the condition, the transformation efficiency of oxyethane is near 100%, the selectivity 95% of ethylene glycol.But the remarkable shortcoming of this catalyst system is that the resin catalyst resistance toheat is poor, and in the hydration reaction temperature range, the expansion situation of catalyzer is more serious, and it is very fast to cause the reactor bed pressure drop to be risen, and shortens catalyzer work-ing life.
JP82106631 discloses a kind of K
2MoO
4-KI catalyzer makes oxyethane and carbonic acid gas generate ethylene carbonate 160 ℃ of reactions, is catalyzer then with the aluminum oxide, 140 ℃ of temperature of reaction, under the pressure 2.25MPa condition, hydrolysis obtains the ethylene glycol product, oxyethane transformation efficiency 100%, glycol selectivity 99.8%.Use the distinguishing feature of above-mentioned catalyzer to be: when catalyzer was dissolvable in water water, oxyethane transformation efficiency and product selectivity were higher, but catalyzer easily runs off, and poor stability has brought unnecessary trouble to postprocessing working procedures; When catalyzer was water insoluble, the oxyethane transformation efficiency 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 organic silicon alkane ammonium salt in catalysis, oxyethane and water prepared in reaction ethylene glycol, the disclosed embodiment reaction result of document is: the reaction times is usually about 6 hours, glycol selectivity is 93～95%, but the oxyethane transformation efficiency 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 water-containing solvent, can effectively the oxirane 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 catalyzer.
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 mmole/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, oxyethane on-catalytic hydration reaction water is than higher, energy consumption is big, the production cost height, or the liquid acid catalyst etching apparatus of catalytic hydration use, contaminate 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 of hydrating epoxy ethane to prepare ethandiol is provided, and this catalyzer is used for ethylene oxide hydration prepared in reaction ethylene glycol, not only has good activity, selectivity, be suitable for low water than operation, and have satisfactory stability 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 aluminum oxide, silicon oxide, titanium oxide, zirconium white or the zeolite as carrier, the following active constituent of load on carrier, the per-cent that accounts for vehicle weight is:
A) metal of niobium or oxide compound 0.1～40%;
B) at least a element or the oxide compound 0.0001～10% that is selected from germanium, tin, lead, antimony, phosphorus, sulphur, iron or cobalt.
In the technique scheme, in vehicle weight per-cent, the metal of niobium or oxide compound preferable range are 1～20%, and preferably preferable range is 2～10%; At least a element or the oxide compound preferable range that is selected from germanium, tin, lead, antimony, phosphorus, sulphur, iron or cobalt is 0.01～5%, at least a element in the preferred germanium of described b component, tin, lead, antimony, iron or the cobalt.
In the technique scheme, described oxide carrier can use separately, also can mix and use with arbitrary proportion, carrier preferentially is selected from a kind of or its mixture in aluminum oxide, silicon oxide, titanium oxide or the zirconium white, the preferred Alpha-alumina of wherein said aluminum oxide, the preferred HZSM-5 zeolite of described zeolite.
Catalyzer of the present invention also contains counts 1～10% binding agent with vehicle weight per-cent, the binding agent that often uses as catalyst field such as inorganic clay, methyl or ethyl or carboxyethyl cellulose, fibrous magnesium silicate element, polyvinyl alcohol, rare nitric acid.Catalyzer of the present invention can use preparation method commonly used such as hybrid system, pickling process or coprecipitation method to make.This specification sheets 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 promotor are mixed, and the moulding of catalyzer for the benefit of improves catalyst strength, can add an amount of binding agent in the mixing 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 niobic acid, niobium oxalate, acetic acid niobium or niobium ammonia 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 acidic solution, acidic solution can be organic acid solns such as oxalic acid, acetic acid, tartrate, citric acid, oxysuccinic acid, lactic acid, fumaric acid, the concentration of niobium compound in the acidic solution is as long as below saturation concentration, no particular determination is generally 0.5～30% (weight), is preferably 1～20% (weight);
2, germanium, tin, lead, antimony, iron or cobalt source:
Introduce with oxide compound, nitrate, muriate or acetate solid state powder form, or be dissolved in the rare nitric acid or dilute hydrochloric acid solution of 5～15% (weight), be mixed with salts solution; In fact, as long as it can be mixed with the aqueous solution, there is no particular restriction on the method.
3, phosphorus or sulphur source: with its simple substance, corresponding oxygen acid or oxysalt.
4, Preparation of Catalyst
With above-mentioned niobium source, germanium, tin, lead, antimony, iron or cobalt source, phosphorus or sulphur source, carrier and binding agent are fully mediated evenly in kneader, make certain shape, and catalyst shape can be made different shapes such as cylindric, spherical, disk, tubular, cellular or Raschig ring with ordinary method.℃ carry out drying in room temperature～200, preferred 100 ℃～200 ℃, 1～5 hour time of drying, preferred 1～3 hour, can adopt vacuum-drying or air seasoning when dry; Carry out roasting then, 100～1000 ℃ of maturing temperatures, preferred 200～700 ℃, roasting time 1～10 hour, preferred 1～5 hour, calcination atmosphere can carry out in air, nitrogen, carbonic acid gas or ammonia atmosphere, also can give roasting under vacuum, catalyzer naturally cooling after the roasting promptly obtains the catalyzer finished product.
Catalyzer 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 oxyethane, and raw water is not had particular requirement, can be the recirculated water in distilled water, deionized water, water coolant and this reaction process.Make raw water and oxyethane enter mixing tank according to a certain percentage by volume pump, enter preheater behind the thorough mixing, raw material after the preheating enters in the fixed-bed reactor that catalyzer 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 thermopairs are equipped with control and measurement heating and temperature of reaction in the outside.Reaction process condition: water is than 1～15: 1, and 100～200 ℃ of temperature of reaction, reaction pressure 0.5～3.0MPa, the reaction solution air speed is 1.0～3.0 hours
-1, reaction product obtains the ethylene glycol product through conventional partition method separation.
Solid acid catalyst of the present invention has good hydrothermal stability.With catalyzer liquid air speed 50 hours
-1Pressure 3.0MPa, carry out water-fast thermal test in 1000 hours under 300 ℃, transformation efficiency and selectivity under the same process condition before and after the evaluate catalysts hydrothermal treatment consists, find out by testing data, trend (embodiment 11) does not fall in the transformation efficiency of catalyzer and selectivity as follows, shows that catalyzer 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.
Catalyzer 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 IVA metallic compound or its mixture and is selected from Fe, Co, Sb, P or S is as promotor, produce synergistic effect between each component, make the catalyzer 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 temperature of reaction, reaction pressure 1.5MPa, water is than 1～10: 1, liquid air speed 1.0～3.0 hours
-1Prepare ethylene glycol under the processing condition, the oxyethane transformation efficiency reaches more than 98%, glycol selectivity about 90%;
2, operation water uses catalyzer 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, reduced production 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.
Embodiment
[embodiment 1]
With 6.3 the gram commercially available niobic acid be dissolved in heat oxalic acid solution in (by 70 the gram oxalic acid be dissolved in 500 ml waters make), make niobic acid solution; Prepare 50 milliliters of 10% (weight) diluted nitric acid aqueous solutions according to a conventional method.Take by weighing α-Al
2O
3Carrier unit powder 100 grams and 0.5 gram germanium dioxide join in the kneading machine, add the niobic acid and the salpeter solution of above-mentioned preparation then, fully mediate in kneading machine with carrier, form the bulk material, extruded moulding, in 150 ℃ of dryings 2 hours, roasting was 4 hours in 600 ℃ of air, obtains catalyst A.The catalyzer composition sees Table 1.
[embodiment 2]
The commercially available acetic acid niobium of 20 grams is dissolved in 40 milliliters of fumaric acid solutions, makes niobic acid solution; With 3.6 gram SnCl
22H
2O is dissolved in 15 milliliters of dilute hydrochloric acid solutions of concentration 10% (weight), makes stannous chloride solution.Take by weighing Al
2O
3Powder 60 gram and SiO
2Powder 40 gram, thorough mixing is even, earlier with above-mentioned niobic acid solution impregnation 2 hours, elimination solution in 120 ℃ of vacuum-dryings 2 hours, flooded 2 hours with stannous chloride solution then, filter,, then add 70 gram polyvinyl alcohol solutions in 120 ℃ of vacuum-dryings 2 hours, fully mediate in kneading machine with carrier, form the bulk material, extruded moulding was in 120 ℃ of vacuum-dryings 2 hours, roasting is 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst B.The catalyzer composition sees Table 1.
[embodiment 3]
With 18.8 gram niobic acids, 100 gram ZrO
2It is even that carrier joins in the kneader thorough mixing, adds rare nitric acid binding agent of a certain amount of lead nitrate aqueous solution and 40 ml concns 2% (weight) then, fully mediates, form the bulk material, extruded moulding, 100 ℃ of dryings 3 hours, roasting is 4 hours in 200 ℃ of air, obtains catalyzer C.The catalyzer composition sees Table 1.
[embodiment 4]
With 25 gram niobic acids, 90 gram TiO
2Reach 10 gram HZSM-5 (SiO
2/ Al
2O
3Mol ratio 80) carrier joins in the kneader and mixes, and a certain amount of lead nitrate and iron trichloride are made the aqueous solution respectively, joins in the kneading machine, fully mediate, form the bulk material, extruded moulding, 110 ℃ of dryings 2 hours, roasting is 4 hours in 300 ℃ of nitrogen, obtains catalyzer D.The catalyzer composition sees Table 1.
[embodiment 5]
With 23.6 gram niobium ammonia complex (NH
4[NbO (C
2O
4)
2(H
2O)
2] (H
2O)
n), 8 gram inorganic claies, a certain amount of sublimed sulphurs, and 100 gram SiO
2Carrier joins in the kneader and mixes, and tin protochloride is made the aqueous solution (compound method is with embodiment 2), joins in the kneading machine, mediate evenly, form the bulk material, extruded moulding, in 120 ℃ of dryings 2 hours, roasting was 4 hours in 200 ℃ of air, obtains catalyzer E.The catalyzer composition sees Table 1.
[embodiment 6]
The commercially available niobic acid of 22.5 grams is dissolved in 50 milliliters of tartrate, makes niobic acid solution, 85% (weight) strong phosphoric acid is joined in the niobic acid solution for 2 milliliters, make solution 1; With 20 gram Al
2O
3Reach 80 gram SiO
2The carrier thorough mixing is used solution 1 impregnated carrier 2 hours, filters, and in 100 ℃ of oven dry, obtains mixture 1; With plain 12 grams of binding agent fibrous magnesium silicate and 0.2 gram germanium dioxide and mixture 1 continuation thorough mixing, make mixture 2, in mixture 2, add 4% (weight) dilute nitric acid solution, in kneading machine, fully mediate, form the bulk material, extruded moulding, and 120 ℃ of vacuum-dryings 2 hours, 500 ℃ of vacuum bakings 4 hours obtain catalyzer F.The catalyzer composition sees Table 1.
[embodiment 7]
With a certain amount of commercially available niobic acid, plumbic oxide, antimonous oxide, 30 gram ZrO
2With 70 gram HZSM-5 (SiO
2/ Al
2O
3Mol ratio 122) carrier thorough mixing in kneading machine adds rare nitric acid of 60 milliliter 10% (weight), and mediate and form the bulk material, extruded moulding, 120 ℃ of vacuum-drying 2 hours, roasting is 4 hours in 700 ℃ of carbon dioxide atmospheres, obtains catalyzer G.The catalyzer composition sees Table 1.
[embodiment 8]
With commercially available niobium oxalate and 100 gram titania support thorough mixing, make mixture, saturated Xiao Suangu (II) solution and 55 milliliter 10% (weight) rare nitric acid binding agent are mixed, then join in the aforementioned mixture, in kneading machine, fully mediate, form the bulk material, extruded moulding, 120 ℃ of air dryings 2 hours, roasting is 2 hours in 400 ℃ of air, obtains catalyst precursor 1.With tin protochloride (compound method is with embodiment 2) solution for vacuum equivalent impregnation to catalyst precursor 1,120 ℃ of vacuum-drying 2 hours, roasting is 2 hours in 400 ℃ of ammonia atmospheres, obtains catalyzer H.The catalyzer composition sees Table 1.
[embodiment 9]
With a certain amount of commercially available niobic acid, plumbic oxide, antimonous oxide, sedimentation sulphur and 80 gram aluminum oxide and 20 gram zirconium dioxide thorough mixing, make mixture, tin protochloride is dissolved in (weight) in 30% hydrochloric acid soln, makes saturated solution, join jointly in the aforementioned mixture with 50 milliliter of 5% (weight) rare nitric acid, in kneading machine, 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 catalyzer 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 reactor, the filler of packing into up and down carries out the catalyst activity evaluation.With raw water and oxyethane in molar ratio 1～10: 1 ratio by the volume pump charging, 150 ℃ of temperature of reaction, reaction pressure 1.5MPa, the liquid air speed is 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 transformation efficiency, glycol selectivity.Concrete reaction conditions and reaction result are listed in table 1.
[embodiment 11]
The test of catalyst tolerates hydrothermal stability.
Get the catalyzer F10 milliliter of embodiment 6 preparation, be loaded into 8 millimeters of internal diameters, in long 300 millimeters the stainless steel fixed-bed reactor, heat up, in reactor, feed water vapor, 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours
-1Under the condition, carry out hydrothermal test in 1000 hours, after the hydrothermal test, catalyzer adopts and the preceding identical activity rating processing condition of hydrothermal treatment consists without any manipulation of regeneration, investigates through the catalyst activity after the above-mentioned hydrothermal treatment consists.At reaction pressure 1.5MPa, 150 ℃ of temperature of reaction, water is than 8: 1, liquid air speed 3.0 hours
-1Under the condition, carry out the catalyst activity evaluation; Reaction result is as follows:
Catalyzer F oxyethane transformation efficiency % glycol selectivity %
Hydrothermal test preceding 100 93
After 1000 hours hydrothermal test 99.5 93
Through after 1000 hours hydrothermal test, trend does not fall in the transformation efficiency of catalyzer and selectivity as follows.
By above-mentioned same method, carry out the catalyst A of example 1 preparation and example 9 preparations the water-fast heat stability test of catalyst I, the transformation efficiency and the selectivity of catalyzer there is no downtrending, show that catalyzer of the present invention has good hydrothermal stability.
[embodiment 12]
The catalyst reaction stability test.
Get the catalyzer H10 milliliter of embodiment 8 preparations, fill in 8 millimeters of internal diameters, in long 300 millimeters the stainless steel fixed-bed reactor, 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 oxyethane by the volume pump charging, 150 ℃ of temperature of reaction, 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 transformation efficiency, glycol selectivity.Reaction was carried out 1500 hours continuously.Initial reaction stage (48 hours), oxyethane transformation efficiency 99%, glycol selectivity 93%, after reaction is carried out 1500 hours, oxyethane transformation efficiency 99%, glycol selectivity 94%.
Use catalyzer 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 20-40 purpose porcelain ring fills in 8 millimeters of internal diameters for 10 milliliters, in long 300 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane your ratio of metering pump massage charging in 10: 1, at reaction pressure 1.5MPa, 150 ℃ of temperature of reaction, 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 transformation efficiency, 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
| Catalyzer | Catalyzer is formed | Water is than (mole) | Air speed hour -1 | Oxyethane transformation efficiency % | Glycol selectivity % |
| ??A | ?5.0％Nb 2O 5-0.5％GeO 2/α-Al 2O 3 | ????10∶1 | ????2.0 | ??98.5 | ??90 |
| ??B | ?10％Nb 2O 5-2.4％SnO 2/60％Al 2O 3+40％SiO 2 | ????5∶1 | ????2.0 | ??100 | ??86 |
| ??C | ?15％Nb 2O 5-1.0％PbO 2/ZrO 2 | ????7∶1 | ????3.0 | ??100 | ??87.5 |
| ??D | ?20％Nb 2O 5-0.5％PbO 2- ?0.05％Fe 2O 3/90％TiO 2+10％HZSM-5 | ????2∶1 | ????3.0 | ??100 | ??83 |
| ??E | ?8.0％Nb 2O 5-0.01％SnO 2-3.0％S/SiO 2 | ????10∶1 | ????2.0 | ??99 | ??91 |
| ??F | ?18％Nb 2O 5-0.2％GeO 2-1.2％P 2O 5/20％Al 2O 3+80％S ?iO 2 | ????8∶1 | ????3.0 | ??100 | ??93 |
| ??G | ?20％Nb 2O 5-5％PbO 2-0.2％Sb 2O 3/30％ZrO 2+ ?70％HZSM-5 | ????10∶1 | ????3.0 | ??95 | ??96 |
| ??H | ?10％Nb 2O 5-0.16％SnO 2-0.3％CoO/TiO 2 | ????9∶1 | ????2.0 | ??99 | ??93 |
| ??I | ?8.3％Nb 2O 5-0.16％SnO 2-5％PbO 2-0.1％S ?-0.03％Sb 2O 3/80％Al 2O 3+20％ZrO 2 | ????7∶1 | ????2.0 | ??99 | ??94 |
| Compare 1 | ?/ | ????10∶1 | ????2.0 | ??92 | ??75 |
| Compare 2 | ?/ | ????22∶1 | ????2.0 | ??100 | ??90 |
Claims (9)
1, a kind of solid acid catalyst that is used for hydrating epoxy ethane to prepare ethandiol, to be selected from a kind of or its mixture in aluminum oxide, silicon oxide, titanium oxide, zirconium white or the zeolite as carrier, the following active constituent of load on carrier, the per-cent that accounts for vehicle weight is:
A) metal of niobium or oxide compound 0.1～40%;
B) at least a element or the oxide compound 0.0001～10% that is selected from germanium, tin, lead, antimony, phosphorus, sulphur, iron or cobalt.
2,, it is characterized in that in vehicle weight per-cent the metal of niobium or oxide compound consumption are 1～20% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
3,, it is characterized in that in vehicle weight per-cent the metal of niobium or oxide compound consumption are 2～10% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 2.
4,, it is characterized in that in vehicle weight per-cent at least a element or the oxide compound consumption that is selected from germanium, tin, lead, antimony, phosphorus, sulphur, iron or cobalt is 0.01～5% according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
5,, it is characterized in that at least a germanium, tin, lead, antimony, iron or the cobalt of being selected from of described b component according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
6,, it is characterized in that described carrier is a kind of or its mixture in aluminum oxide, silicon oxide, titanium oxide or the zirconium white according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
7,, it is characterized in that described aluminum oxide is an Alpha-alumina according to the solid acid catalyst of claim 1 or 6 described hydrating epoxy ethane to prepare ethandiol.
8,, it is characterized in that described zeolite is the HZSM-5 zeolite according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1.
9, according to the solid acid catalyst of the described hydrating epoxy ethane to prepare ethandiol of claim 1, it is characterized in that described catalyzer also contains binding agent, in vehicle weight per-cent, the consumption of binding agent is 1～10%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147860B (en) * | 2006-09-20 | 2010-10-27 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from methanol |
| CN101190878B (en) * | 2006-11-21 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing propylene glycol ether |
| CN101148397B (en) * | 2006-09-20 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing dimethyl 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 |
| CN103638955A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN109867587A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of 3 chloro- 1,2- propylene glycol |
| CN114950535A (en) * | 2022-05-18 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of solid acid catalyst and application of solid acid catalyst in unsaturated ketone synthesis |
-
2003
- 2003-07-09 CN CNB031414524A patent/CN1218915C/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101147860B (en) * | 2006-09-20 | 2010-10-27 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from methanol |
| CN101148397B (en) * | 2006-09-20 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing dimethyl ether |
| CN101190878B (en) * | 2006-11-21 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing propylene 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 |
| CN103638955A (en) * | 2013-12-17 | 2014-03-19 | 中国科学院长春应用化学研究所 | Solid acid catalyst and preparation method thereof, and preparation method of diolefin compounds |
| CN103638955B (en) * | 2013-12-17 | 2016-06-01 | 中国科学院长春应用化学研究所 | The preparation method of a kind of solid acid catalyst, its preparation method and double olefin compound |
| CN109867587A (en) * | 2017-12-01 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of preparation method of 3 chloro- 1,2- propylene glycol |
| CN109867587B (en) * | 2017-12-01 | 2021-11-30 | 中国科学院大连化学物理研究所 | Preparation method of 3-chloro-1,2-propanediol |
| CN114950535A (en) * | 2022-05-18 | 2022-08-30 | 万华化学集团股份有限公司 | Preparation method of solid acid catalyst and application of solid acid catalyst in unsaturated ketone synthesis |
| CN114950535B (en) * | 2022-05-18 | 2023-12-19 | 万华化学集团股份有限公司 | Preparation method of solid acid catalyst and application of solid acid catalyst in unsaturated ketone synthesis |
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