CN1463960A - Process for preparing ethandiol by catalyzing epoxyethane hydration - Google Patents
Process for preparing ethandiol by catalyzing epoxyethane hydration Download PDFInfo
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- CN1463960A CN1463960A CN02112037A CN02112037A CN1463960A CN 1463960 A CN1463960 A CN 1463960A CN 02112037 A CN02112037 A CN 02112037A CN 02112037 A CN02112037 A CN 02112037A CN 1463960 A CN1463960 A CN 1463960A
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to process of catalytic hydration of ethylene epoxide to prepare glycol and aims at solving the problems of available corresponding process. The said process is especially suitable for low water ratio operation, and has the features of very low heat energy consumption and power consumption, high activity, selectivity and stability of catalyst, and low production cost. The said process may be used in industrial production of glycol.
Description
Technical field
The present invention relates to a kind of method of preparing ethandiol by catalyzing epoxyethane hydration, particularly make catalyzer, prepare the method for ethylene glycol about niobic acid with a kind of loading type.
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 be divided into two kinds of methods, a kind of is direct hydration method, i.e. direct under certain condition the and water reaction generation ethylene glycol of oxyethane, reaction does not need catalyzer just can carry out, and is divided into two kinds of methods of catalytic hydration and on-catalytic hydration; Another kind method is the ethylene carbonate method, and promptly oxyethane generates ethylene carbonate with the CO2 reaction earlier under catalyst action, and hydrolysis generates ethylene glycol then.
Present industrial preparation ethylene glycol adopts the on-catalytic hydrating process of direct hydration method, also claim the pressurization hydration, this method is not used catalyzer, the mol ratio of reaction feed water and oxyethane (hereinafter to be referred as the water ratio) is 20～25: 1,150～200 ℃ of temperature of reaction, reaction pressure 0.8～2.0MPa, oxyethane transformation efficiency be near 100%, glycol selectivity about 90%.In the reaction, because ethylene glycol and reacting ethylene oxide activity are higher than the reactive behavior of water and oxyethane, unconverted oxyethane continues and the glycol product reaction, generates by products such as glycol ether, triglycol, therefore the industrial water of often taking is big excessive way, improves glycol selectivity.The disadvantage of this method is that lot of energy is used for the moisture content of evaporation product more than 85% in producing.For example, in ethylene glycol product purification step, when the feed water ratio is 20, remove the no water that is approximately 19 times of ethylene glycol by evaporation, required heat is counted 170 kilocalories with every mole of ethylene glycol, mean that producing 1 ton of ethylene glycol need consume about 5.5 tons of steam, cause this method energy consumption huge, production cost is higher.Therefore, in order to reduce the reaction water ratio, cut down the consumption of energy, the investigator has competitively carried out the research of multiple catalyzing epoxyethane hydration reaction technology both at home and abroad.
The method of ethylene glycol is produced in Industrial Catalysis hydration the earliest, with mineral acid or alkali as a catalyst, as with sulfuric acid or phosphoric acid etc. during as catalyzer, oxyethane can all transform, the ethylene glycol yield is about 90%, but inorganic acid catalyst causes corrosion to equipment, contaminate environment; When using inorganic alkali as a catalyst, easily promote to produce some high-molecular weight by products, reduce product selectivity.Therefore, although acid, alkali has obvious catalysis to ethylene oxide hydration, traditional acid-base catalysis hydrating process is all eliminated, and does not re-use.
For overcoming the shortcoming of mineral acid and base catalysis hydration, people have carried out many-sided improvement research to the method and the catalyzer of catalyzing epoxyethane hydration.
Spent ion exchange resin is made catalyzer, and a class is to have-SO
3H ,-PO (OH)
2The storng-acid cation exchange resin of group, another kind of is the basic anion exchange resin that contains quaternary amine, and based on the anionite-exchange resin of metal oxygen-containing acid group katalysis.As US Patent 5,874,653 a kind of anionite-exchange resin that has quaternary ammonium group by vinylbenzene and divinyl benzene crosslinked is disclosed 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, even in lower temperature range (＜95 ℃), the expansion of catalyzer is still more serious, thereby it is very fast to cause the reactor bed pressure drop to be risen, catalyzer is changed frequent, and it is unfavorable to bring to industrial production.Although thereby above-mentioned research work obtained remarkable progress, but still limited its range of application.
Mixture with heteropolyacid salt is made catalyzer, discloses a kind of K as JP82106631
2MoO
4-KI catalyzer makes oxyethane and carbonic acid gas generate ethylene carbonate, oxyethane transformation efficiency 99.9%, glycol selectivity 100% 160 ℃ of reactions; Be catalyzer then with the aluminum oxide, 140 ℃ of temperature of reaction, under the reaction 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 heteropolyacid salt catalyst to be: when catalyzer was dissolvable in water water, oxyethane transformation efficiency and product selectivity were higher, but catalyzer easily runs off, and had 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.
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, use this Niobic Acid agent effectively the oxirane ring in the aryl rings oxidative ethane partly to be added water decomposition, the yield of aryl ethylene glycol is more than 95%.But the shortcoming of this method be water than too high, the existence of big water gaging brings huge energy consumption for the ethylene glycol product separation.
Japanese patent laid-open 7-53219 has introduced a kind of columbic acid particle and preparation method thereof.Use the niobic acid of this method preparation can be under hydrothermal condition long-time stable existence.But the acidity of this Niobic Acid agent is strong excessively, is H more than 50%
0: the strong acid amount below-5.6 is not suitable for the catalyzing epoxyethane hydration reaction for preparing glycol.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past in the document, the on-catalytic hydration prepares the reaction water of ethylene glycol than higher, and be used to prepare the catalyst contamination environment of ethylene glycol, influence quality product, poor stability, catalyst reaction water is than higher, cause energy consumption huge, the defective that production cost is high provides a kind of method of preparing ethandiol by catalyzing epoxyethane hydration, and the catalyzer that this method is used had both had good activity, selectivity, has satisfactory stability again, be particularly suitable for low water than operation, reduce the required heat energy of processing reaction excessive water significantly, it is little to have an energy consumption, the characteristics that production cost is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing ethandiol by catalyzing epoxyethane hydration is a raw material with water and oxyethane, reacts under following reaction conditions:
1) raw water is contacted with catalyzer by fixed-bed reactor with oxyethane, 50～300 ℃ of temperature of reaction, reaction pressure 0～5.0MPa, the mol ratio 1～15: 1 of water and oxyethane, reaction velocity 1.0～3.0 hours
-1Prepared in reaction ethylene glycol under the condition;
2) used catalyzer is a carrier with a kind of or its mixture that is selected from aluminum oxide, silicon oxide, titanium oxide, zirconium white or the zeolite, the following active constituent of load on carrier, and the per-cent that accounts for vehicle weight is:
A) oxide compound of 0.1～30% niobium;
B) 0.01～10% be selected from least a in the metal oxide of IIB.
In the technique scheme, preferred 100～200 ℃ of described temperature of reaction, the preferred 0.5～3.0MPa of reaction pressure, the mol ratio of water and oxyethane preferred 1～10: 1, preferred 2.0～3.0 hours of reaction velocity
-1
In the technique scheme, described catalyzer is in vehicle weight per-cent, the oxide compound preferable range of niobium is 1～20%, best preferable range is 2～10%, the metal oxide preferable range that is selected from IIB is 0.01～5%, the preferred Alpha-alumina of described alumina catalyst support, the preferred HZSM-5 zeolite of described carrier zeolite, the metal of described IIB is preferably zinc or cadmium.
In the technique scheme, described catalyzer also contains counts 1～10% binding agent with vehicle weight per-cent, the binding agent that often uses as Preparation of Catalyst fields such as inorganic clay, methyl or ethyl or carboxyethyl cellulose, fibrous magnesium silicate element, polyvinyl alcohol, rare nitric acid.
The catalyzer raw material that preparation the inventive method is used is as follows:
Niobium source: commercially available niobic acid, niobium oxalate, acetic acid niobium or niobium ammonia complex.
Zinc, cadmium, mercury source: with its oxide compound, nitrate, muriate or acetate.
The catalyzer that the inventive method is used can make by method for preparing catalyst such as hybrid system, pickling process or coprecipitation method commonly used.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 niobic acid and promotor are mixed, in order to be beneficial to the moulding of catalyzer, improve catalyst strength, can add an amount of binding agent in the mixing process, as inorganic clay, methyl or ethyl or carboxyethyl cellulose, fibrous magnesium silicate element or water, be prepared from through steps such as kneading, moulding, drying and roastings then.Catalyst shape can be made different shapes such as cylindric, spherical, disk, tubular, cellular or Raschig ring with ordinary method.Concrete preparation process is as follows:
1, niobium source:
Solid state powder form with commercially available niobic acid, niobium oxalate, acetic acid niobium or niobium ammonia complex is introduced, and perhaps introduces with niobic acid solution form, and niobic acid solution is prepared as follows:
Take by weighing a certain amount of niobium compound, be generally commercially available niobic acid (Nb
2O
5NH
2O, n is 1-5), be dissolved in the 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, preparation zinc, cadmium or mercury salt solution
Take by weighing oxide compound, nitrate, muriate or the acetate of a certain amount of zinc, cadmium or mercury, be dissolved in 5～15% the dilute nitric acid solution, be mixed with salts solution;
3, Preparation of Catalyst
Above-mentioned niobium source, solution 2, carrier and binding agent are fully mediated evenly in kneader, made definite shape, ℃ carry out drying in room temperature～200,100 ℃～200 ℃ of preferable range, 1～5 hour time of drying, preferable range 1～3 hour can adopt vacuum-drying or air seasoning when dry; Carry out roasting then, 100～1000 ℃ of maturing temperatures, preferable range is 200～700 ℃, roasting time 1～10 hour, preferable range is 1～5 hour, and calcination atmosphere can carry out in air, nitrogen, carbonic acid gas or ammonia atmosphere, also can give roasting under vacuum.
The method of the catalyzing epoxyethane hydration prepared in reaction ethylene glycol that the present invention proposes comprises:
Step 1: raw water and oxyethane mix, preheating;
Step 2: under catalyst action, water and ethylene oxide hydration prepared in reaction ethylene glycol;
Step 3: by underpressure distillation, separate the crude product that contains ethylene glycol, glycol ether and triglycol, obtain the ethylene glycol product.
The inventive method at first makes raw material 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 is housed, reactor is the stainless steel tube of 8 millimeters of internal diameters, 300 millimeters of length, 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.Then 50～300 ℃ of temperature of reaction, reaction pressure 0～5.0MPa, water is than 1～15: 1, reaction velocity 1.0～3.0 hours
-1Prepared in reaction ethylene glycol under the condition.The inventive method does not have particular requirement for raw water, can be the recirculated water in distilled water, deionized water, water coolant and this reaction process, but best metal ion not.The relatively good scope of reaction water is 10～1: 1, certainly, adopts and further improves reaction preference than higher water specific energy, but can consume more energy; Temperature of reaction is on the low side, and meeting reduces the treatment capacity of oxyethane, and operating mode is uneconomical, and reaction heat can not be in time removed in reaction under the high temperature, increases by product, reduce selectivity, so the better scope of temperature of reaction is 100～200 ℃; The better scope of reaction pressure is 0.5～3.0MPa, is in liquid phase state to guarantee reactant, improves the transformation efficiency of raw material oxyethane.The crude product of outflow reactor contains ethylene glycol, glycol ether and triglycol, obtains the ethylene glycol product through conventional decompression separation.
Solid acid catalyst of the present invention has good thermostability in water.The catalyst I of example 9 preparation for example was 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours
-1Under the condition, carry out hydrothermal test in 1000 hours, catalyzer after the hydrothermal test is without any manipulation of regeneration, adopt identical processing condition to investigate the reactive behavior of catalyzer hydrothermal test front and back, the evaluation processing condition are: reaction pressure 1.7MPa, 170 ℃ of temperature of reaction, water be than 10: 1, liquid air speed 2.0 hours
-1, reaction result is as follows:
Catalyst I oxyethane transformation efficiency % glycol selectivity %
Hydrothermal test preceding 100 88
After 1000 hours hydrothermal test 100 89
Through after 1000 hours hydrothermal test, trend 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.
The inventive method principal character has been to use a kind of novel solid Niobic Acid agent, this catalyzer does not have corrosion to equipment, environmentally safe, oxide compound by load niobium on some oxide carriers and be selected from metal oxide or its mixture of IIB, produce synergy between each component, make catalyzer have good activity, selectivity, have satisfactory stability simultaneously; The another one of the inventive method is characterised in that reaction water is than low, 20-25 by prior art: 1 reduces to 1～10: 1, reduced energy consumption of reaction significantly, simultaneously because catalyzer hydrothermally stable performance is good, prolong the replacement cycle of catalyzer, significantly reduced production cost.The catalyzer F of the inventive method embodiment 6 preparation for example, 140 ℃ of temperature of reaction, reaction pressure 1.8MPa, water be than 8: 1, liquid air speed 3.0 hours
-1Under the processing condition, the oxyethane transformation efficiency reaches 100%, and glycol selectivity 91.5% has obtained better effects.
Embodiment
[embodiment 1]
Take by weighing the commercially available niobium oxalate of 12 grams and be dissolved in 40 ml waters, make niobium oxalate solution; Take by weighing 1.8 gram Zn (NO
3)
26H
2O is dissolved in 5 milliliter 10% the diluted nitric acid aqueous solution, makes zinc nitrate solution.Take by weighing Alpha-alumina 100 grams, join in the kneading machine, add the niobium oxalate and the zinc nitrate solution of above-mentioned preparation then, fully mediate with Alpha-alumina, form the bulk material, extruded moulding, in 150 ℃ of air dryings 2 hours, roasting was 4 hours in 600 ℃ of air, obtains catalyst A.The catalyzer composition sees Table 1.
[embodiment 2]
Take by weighing 90 gram Alpha-aluminas, 10 gram titanium dioxide and the commercially available niobic acid of 12 grams respectively, it is even to join in the kneader thorough mixing, obtains mixture, takes by weighing 8.1 gram Cd (NO
3)
26H
2O is dissolved in 40 milliliter 10% the diluted nitric acid aqueous solution, makes cadmium nitrate solution, join in the aforementioned mixture, through mediate, after the extrusion, in 120 ℃ of vacuum-dryings 2 hours, roasting was 4 hours in 500 ℃ of ammonia atmospheres, obtains catalyst B.The catalyzer composition sees Table 1.
[embodiment 3]
Method by embodiment 2 prepares catalyzer C, and different is niobium amine complex consumption 7.6 grams in the preparation process, titanium dioxide 100 grams, Cd (NO
3)
26H
2O2.7 gram is dissolved in 40 ml waters, and in 100 ℃ of air dryings 3 hours, roasting was 4 hours in 200 ℃ of air.The catalyzer composition sees Table 1.
[embodiment 4]
Method by embodiment 1 prepares catalyzer D, and different is niobic acid consumption 2.4 grams in the preparation process, is dissolved in the hot oxalic acid aqueous solution (this oxalic acid solution is dissolved in the 40ml water by 7g oxalic acid and makes) Zn (NO
3)
26H
2O 0.18 gram is dissolved in 20 ml waters, HZSM-5 molecular sieve carrier 100 grams, and in 110 ℃ of air dryings 2 hours, roasting was 4 hours in 300 ℃ of air.The catalyzer composition sees Table 1.
[embodiment 5]
Method by embodiment 2 prepares catalyzer E, different is niobic acid consumption 5 grams, and Mercury pernitrate 0.015 gram, silica 1 00 gram, binding agent polyvinyl alcohol 10 grams are dissolved in 40 milliliters of hot water, 120 ℃ of air dryings 2 hours, roasting is 4 hours in 200 ℃ of air.The catalyzer composition sees Table 1.
[embodiment 6]
Method by embodiment 2 prepares catalyzer F, different is niobic acid consumption 18 grams, and a certain amount of cadmium nitrate, carrier is made up of 15 gram Alpha-aluminas and 85 gram silicon-dioxide, 120 ℃ of vacuum-drying 2 hours, 500 ℃ of vacuum bakings 4 hours.The catalyzer composition sees Table 1.
[embodiment 7]
Method by embodiment 1 prepares catalyzer G, and different is consumption 24 grams of preparation process mesoxalic acid niobium, Zn (NO
3)
26H
2Consumption 18 grams of O, binding agent inorganic clay 5 grams, carrier is made up of 20 gram Alpha-aluminas and HZSM-5 molecular sieve 80 grams, and in 120 ℃ of vacuum-dryings 2 hours, roasting was 4 hours in 700 ℃ of air.The catalyzer composition sees Table 1.
[embodiment 8]
Method by embodiment 2 prepares catalyzer H, and that different is Cd (NO in the preparation process
3)
26H
2Consumption 0.8 gram of O, Zn (NO
3)
26H
2Consumption 0.7 gram of O, a certain amount of niobic acid, binding agent carboxyethyl cellulose 8 grams, carrier is made up of 60 gram zirconia carriers and 40 gram silicon-dioxide, 120 ℃ of vacuum-dryings of catalyzer 2 hours, roasting is 3 hours in 400 ℃ of air.The catalyzer composition sees Table 1.
[embodiment 9]
Method by embodiment 1 prepares catalyst I, and different is consumption 10 grams of niobic acid in the preparation process, Zn (NO
3)
26H
2Consumption 1.0 gram of O, Alpha-alumina 80 grams and zirconium white 20 restrain, 120 ℃ of vacuum-drying 2 hours, roasting is 4 hours in 500 ℃ of air.The catalyzer composition sees Table 1.
Table 1
| Embodiment | The catalyzer numbering | Catalyzer is formed |
| ????1 | ????A | ?6.1％Nb 2O 5-0.5％ZnO/α-Al 2O 3 |
| ????2 | ????B | ?10％Nb 2O 5-3％CdO/90％α-Al 2O 3+10％TiO 2 |
| ????3 | ????C | ?5％Nb 2O 5-1.0％CdO/TiO 2 |
| ????4 | ????D | ?2％Nb 2O 5-0.05％ZnO/HZSM-5 |
| ????5 | ????E | ?4.2％Nb 2O 5-0.01%HgO-10% binding agent/SiO 2 |
| ????6 | ????F | ?15％Nb 2O 5-0.2％CdO/15％α-Al 2O 3+85％SiO 2 |
| ????7 | ????G | ?20％Nb 2O 5-5%ZnO-5% binding agent/20% α-Al 2O 3+80％HZSM-5 |
| ????8 | ????H | ?10％Nb 2O 5-0.2%ZnO+O.3%CdO-10% binding agent/60%ZrO 2+40％SiO 2 |
| ????9 | ????I | ?8.3％Nb 2O 5-0.3％ZnO/80％α-Al 2O 3+20％ZrO 2 |
[embodiment 10]
Get each 10 milliliters of the catalyst A～I of embodiment 1～9 preparation, filling in internal diameter one by one is 8 millimeters, in long 300 millimeters the stainless steel fixed-bed reactor, the filler of packing into up and down, use metering pump massage that than 1～10: 1 charging raw water and oxyethane, at reaction pressure 0.5～3.0MPa, 100～200 ℃ of temperature of reaction, air speed 1.0～3.0 hours
-1Prepared in reaction ethylene glycol under the condition carries out qualitative, quantitative analysis with the HP5890 gas-chromatography to product, ring oxidative ethane transformation efficiency, glycol selectivity.Reaction result is listed in table 2.
[embodiment 11]
Get 10 milliliters of the catalyst I of embodiment 9 preparation, being loaded into internal diameter is 8 millimeters, in long 300 millimeters the stainless steel fixed-bed reactor, and at reaction pressure 1.7MPa, 170 ℃ of temperature of reaction, water is than 10: 1, liquid air speed 2.0 hours
-1Under the condition, carry out the catalyst activity evaluation; Change into then and in reactor, feed water vapor, 300 ℃ of temperature, pressure 3.0MPa, air speed 50 hours
-1Under the condition, carry out the test of 1000 hours hydrothermal, after the hydrothermal test, catalyzer adopts the processing condition identical with above-mentioned activity rating without any manipulation of regeneration, and investigation is through the activity of such catalysts after 1000 hours hydrothermal test.Reaction result is as follows:
Catalyst I oxyethane transformation efficiency % glycol selectivity %
Hydrothermal test preceding 100 88
After 1000 hours hydrothermal test 100 89
Through after 1000 hours hydrothermal test, trend does not fall in the transformation efficiency of catalyzer and selectivity as follows, shows that catalyzer of the present invention has advantages of excellent stability.
[comparative example 1]
With granularity is that to fill in internal diameter be 8 millimeters to 10 milliliters on 20-40 purpose porcelain ring, 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 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 2.
[comparative example 2]
Method by comparative example 1 prepares ethylene glycol, difference: raw material feed water ratio is 22: 1.Reaction result is listed in table 2.
Table 2
| The catalyzer numbering | Temperature of reaction ℃ | Reaction pressure MPa | Water is than (mole) | Air speed hour -1 | Oxyethane transformation efficiency % | Glycol selectivity % |
| ????A | ????150 | ????1.5 | ????10∶1 | ????2.0 | ????98 | ????87 |
| ????B | ????180 | ????1.2 | ????5∶1 | ????3.0 | ????100 | ????82 |
| ????C | ????150 | ????2.0 | ????7∶1 | ????2.0 | ????96 | ????85 |
| ????D | ????120 | ????2.2 | ????2∶1 | ????1.0 | ????96 | ????84 |
| ????E | ????100 | ????1.0 | ????10∶1 | ????2.0 | ????89 | ????92 |
| ????F | ????140 | ????1.8 | ????8∶1 | ????3.0 | ????100 | ????91.5 |
| ????G | ????200 | ????3.0 | ????15∶1 | ????3.0 | ????100 | ????87 |
| ????H | ????160 | ????1.6 | ????9∶1 | ????2.0 | ????100 | ????90 |
| ????I | ????170 | ????1.7 | ????10∶1 | ????2.0 | ????100 | ????88 |
| Compare 1 | ????150 | ????1.5 | ????10∶1 | ????2.0 | ????92 | ????75 |
| Compare 2 | ????150 | ????1.5 | ????22∶1 | ????2.0 | ????100 | ????90 |
Claims (10)
1, a kind of method of preparing ethandiol by catalyzing epoxyethane hydration is a raw material with water and oxyethane, reacts under following reaction conditions:
1) raw water is contacted with catalyzer by fixed-bed reactor with oxyethane, 50～300 ℃ of temperature of reaction, reaction pressure 0～5.0MPa, the mol ratio 1～15: 1 of water and oxyethane, reaction velocity 1.0～3.0 hours
-1Prepared in reaction ethylene glycol under the condition;
2) used catalyzer is a carrier with a kind of or its mixture that is selected from aluminum oxide, silicon oxide, titanium oxide, zirconium white or the zeolite, the following active constituent of load on carrier, and the per-cent that accounts for vehicle weight is:
A) oxide compound of 0.1～30% niobium;
B) 0.01～10% be selected from least a in the metal oxide of IIB.
2,, it is characterized in that described temperature of reaction is 100～200 ℃ according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1.
3,, it is characterized in that described reaction pressure is 0.5～3.0MPa according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1.
4, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1, the mol ratio that it is characterized in that described water and oxyethane is 1～10: 1.
5,, it is characterized in that described reaction velocity is 2.0～3.0 hours according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1
-1
6, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described catalyzer in vehicle weight per-cent, the oxide compound consumption of niobium is 1～20%, the metal oxide consumption that is selected from IIB is 0.01～5%.
7, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described catalyzer in vehicle weight per-cent, the oxide compound consumption of niobium is 2～10%.
8, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described alumina catalyst support is an Alpha-alumina, described carrier zeolite is the HZSM-5 zeolite.
9, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration of claim 1, the metal that it is characterized in that described IIB is zinc or cadmium.
10, according to the method for the described preparing ethandiol by catalyzing epoxyethane hydration 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 |
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| CN1318364C (en) * | 2004-10-29 | 2007-05-30 | 中国石油化工股份有限公司<Del/> | Aliphatic dihydroxy alcohol preparation method |
| CN100335173C (en) * | 2004-09-24 | 2007-09-05 | 中国石油化工股份有限公司 | Method for preparing catalyst for hydration of epoxy ethane to produce ethandiol |
| CN100413580C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Method for preparing catalyst for hydration of epoxy ethane to prepare ethandiol |
| CN100413579C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Catalyst used for hydrating epoxy ethane to prepare ethandiol |
| CN100413578C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Columbium oxide catalyst for hydrating epoxy ethane to prepare ethandiol |
| WO2010017681A1 (en) | 2008-08-14 | 2010-02-18 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, its preparation method and its use in obtaining ethylene glycol by cellulose |
| WO2010045766A1 (en) | 2008-10-24 | 2010-04-29 | 中国科学院大连化学物理研究所 | A process for preparing ethylene glycol using cellulose |
| WO2011113281A1 (en) | 2010-03-17 | 2011-09-22 | 中国科学院大连化学物理研究所 | Process for preparing ethylene glycol from polyhydric compounds |
| CN103391929A (en) * | 2011-01-24 | 2013-11-13 | 国际壳牌研究有限公司 | Process for the production of ethylene oxide |
| US8969602B2 (en) | 2011-01-24 | 2015-03-03 | Shell Oil Company | Process for the production of ethylene oxide |
| CN104926610A (en) * | 2015-05-27 | 2015-09-23 | 广西梧松林化集团有限公司 | Preparation method of dihydromyrcenol |
| US10654781B2 (en) | 2015-11-12 | 2020-05-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method of catalytic conversion of carbohydrates to low-carbon diols by using alloy catalysts |
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2002
- 2002-06-12 CN CNB021120374A patent/CN1204103C/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335173C (en) * | 2004-09-24 | 2007-09-05 | 中国石油化工股份有限公司 | Method for preparing catalyst for hydration of epoxy ethane to produce ethandiol |
| CN100413580C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Method for preparing catalyst for hydration of epoxy ethane to prepare ethandiol |
| CN100413579C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Catalyst used for hydrating epoxy ethane to prepare ethandiol |
| CN100413578C (en) * | 2004-09-24 | 2008-08-27 | 中国石油化工股份有限公司 | Columbium oxide catalyst for hydrating epoxy ethane to prepare ethandiol |
| CN1318364C (en) * | 2004-10-29 | 2007-05-30 | 中国石油化工股份有限公司<Del/> | Aliphatic dihydroxy alcohol preparation method |
| WO2010017681A1 (en) | 2008-08-14 | 2010-02-18 | 中国科学院大连化学物理研究所 | Tungsten carbide catalyst, its preparation method and its use in obtaining ethylene glycol by cellulose |
| WO2010045766A1 (en) | 2008-10-24 | 2010-04-29 | 中国科学院大连化学物理研究所 | A process for preparing ethylene glycol using cellulose |
| WO2011113281A1 (en) | 2010-03-17 | 2011-09-22 | 中国科学院大连化学物理研究所 | Process for preparing ethylene glycol from polyhydric compounds |
| CN103391929A (en) * | 2011-01-24 | 2013-11-13 | 国际壳牌研究有限公司 | Process for the production of ethylene oxide |
| US8969602B2 (en) | 2011-01-24 | 2015-03-03 | Shell Oil Company | Process for the production of ethylene oxide |
| US9067901B2 (en) | 2011-01-24 | 2015-06-30 | Shell Oil Company | Process for the production of ethylene oxide |
| US9260366B2 (en) | 2011-01-24 | 2016-02-16 | Shell Oil Company | Process for the production of ethylene oxide |
| CN104926610A (en) * | 2015-05-27 | 2015-09-23 | 广西梧松林化集团有限公司 | Preparation method of dihydromyrcenol |
| US10654781B2 (en) | 2015-11-12 | 2020-05-19 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method of catalytic conversion of carbohydrates to low-carbon diols by using alloy catalysts |
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