CN1218917C - Process for preparing ethylene glycol by ethylene oxide catalytic hydration - Google Patents
Process for preparing ethylene glycol by ethylene oxide catalytic hydration Download PDFInfo
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- CN1218917C CN1218917C CN 03141453 CN03141453A CN1218917C CN 1218917 C CN1218917 C CN 1218917C CN 03141453 CN03141453 CN 03141453 CN 03141453 A CN03141453 A CN 03141453A CN 1218917 C CN1218917 C CN 1218917C
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Abstract
The present invention relates to a method for preparing ethylene glycol by ethylene oxide catalytic hydration. The present invention mainly solves the defects that the water ratio in ethylene oxide non catalytic hydration is relatively high, or liquid acid catalysts used for catalytic hydration erode the equipment and pollute the environment, and solid acid catalysts are poor in stability, or the stability and activity of the solid acid catalysts can not reach the ideal state at the same time. The present invention provides a method for preparing ethylene glycol by ethylene oxide catalytic hydration. The solid acid catalysts used in the method take niobium compounds as major active constituents, and take at least one of germanium, tin, lead, antimony, phosphorus, sulfur, iron and cobalt as auxiliary agents; the reaction and preparation of ethylene glycol under the condition of low water ratio can greatly reduce the needed heat energy for processing the excessive water in the reaction; the catalysts used in the present invention have the advantages of favorable activity, selectivity and superior stability; the method has the characteristics of extension of running period of catalysts, small energy consumption and low production cost, and can be used for industrial production of preparing ethylene glycol.
Description
Technical field
The present invention relates to a kind of method that is used for preparing ethandiol by catalyzing epoxyethane hydration, particularly make catalyzer, by the method for preparing ethandiol by catalyzing epoxyethane hydration 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 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.Simultaneously in the presence of catalyst-free, hydration reaction speed is slow, the industrial need adopted bigger pipeline reactor, caused the increase of transmission and mass transfer energy, in addition, a high proportion of feed water is than the glycol product selectivity is improved significantly, and consumptions such as the by product Diethylene Glycol that generates, triethylene glycol are little, and the ethylene glycol demand growth is very fast, thereby, develop a kind of preparing ethandiol by catalyzing epoxyethane hydration technology, improve this technology whole synthesis performance and seem particularly important.
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 the 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, and a tree name studies show that 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, or the liquid acid catalyst etching apparatus of catalytic hydration use, contaminate environment, solid acid catalyst poor stability or stability and activity can not be taken into account simultaneously, cause this method energy consumption big, defect of high cost, a kind of method that is used for preparing ethandiol by catalyzing epoxyethane hydration is provided, and this method is suitable for low water than operation, reduces the required heat energy of processing reaction excessive water significantly, the catalyzer that uses not only has good activity, selectivity, have advantages of excellent stability simultaneously, 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 that is used for preparing ethandiol by catalyzing epoxyethane hydration is a raw material with water and oxyethane, under the following conditions reaction:
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) catalyzer of Shi Yonging to be being 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, and 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, preferred 100～200 ℃ of described temperature of reaction, the preferred 1.0～3.0MPa of reaction pressure, the mol ratio of water and oxyethane preferred 1～10: 1.
In the technique scheme, described catalyzer is in vehicle weight per-cent, and 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 germanium, tin, lead, antimony, iron or the cobalt of being selected from of described b component.
In the technique scheme, described oxide carrier can use separately, also can mix with arbitrary proportion and use the preferred Alpha-alumina of wherein said alumina catalyst support, the preferred HZSM-5 zeolite of described zeolite.
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 catalyst field such as inorganic clay, methyl or ethyl or carboxyethyl cellulose, fibrous magnesium silicate element, polyvinyl alcohol, rare nitric acid.
The method that is used for 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 solid Niobic Acid agent effect, 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 through 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.Make raw material 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 1～10: 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 1.0～3.0MPa, 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.
The solid Niobic Acid agent that the inventive method is used can make with catalyzer preparation method such as hybrid system, pickling process or coprecipitation method commonly used.This specification sheets is that example describes Preparation of catalysts 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.
Solid acid catalyst of the present invention has good hydrothermal stability.With catalyzer 300 ℃ of temperature, pressure 3.0MPa, liquid air speed 50 hours
-1Under the condition, carry out water-fast thermal test in 1000 hours, transformation efficiency after evaluate catalysts hydrothermal treatment consists under the same process condition and selectivity, find out by experimental data, catalyzer is after 1000 hours hydrothermal treatment consists, trend (embodiment 11) does not fall in its transformation efficiency 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, 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 produces synergistic effect as auxiliary agent between each component, make catalyzer 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 the 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.By vehicle weight per-cent, catalyst A is formed:
5.0％Nb
2O
5-0.5％GeO
2/α-Al
2O
3。
[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 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.By vehicle weight per-cent, catalyst B is formed: 10%Nb
2O
5-2.4%SnO
2/ 60%Al
2O
3+ 40%SiO
2
[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.By vehicle weight per-cent, catalyzer C forms: 15%Nb
2O
5-1.0%PbO
2/ ZrO
2
[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.By vehicle weight per-cent, catalyzer D forms: 20%Nb
2O
5-0.5%PbO
2-0.05%Fe
2O
3/ 90%TiO
2+ 10%HZSM-5.
[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, 120 ℃ of dryings 2 hours, roasting is 4 hours in 200 ℃ of air, obtains catalyzer E.By vehicle weight per-cent, catalyzer E forms:
8.0％Nb
2O
5-0.01％SnO
2-3.0％S/SiO
2。
[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.By vehicle weight per-cent, catalyzer F forms:
18％Nb
2O
5-0.2％GeO
2-1.2％P
2O
5/20％Al
2O
3+80％SiO
2。
[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.By vehicle weight per-cent, catalyzer G forms: 20%Nb
2O
5-5%PbO
2-0.2%Sb
2O
3/ 30%
3ZrO
2+ 70%HZSM-5.
[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.By vehicle weight per-cent, catalyzer H forms:
10％Nb
2O
5-0.16％SnO
2-0.3％CoO/TiO
2。
[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, make 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.By vehicle weight per-cent, catalyst I is formed:
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。
[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, with raw water and oxyethane in molar ratio 1～15: 1 by the volume pump charging, 100～200 ℃ of temperature of reaction, reaction pressure 1.0.～3.0MPa, 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.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, being loaded into internal diameter was 8 millimeters, in long 300 millimeters the stainless steel fixed-bed reactor, heats up, and feeds water vapor in reactor, 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 evaluation 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, to the catalyst A of example 1 preparation and example 9 preparations catalyst I carry out water-fast heat stability test, 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 10 milliliters of the catalyzer H of embodiment 8 preparation, filling in internal diameter is 8 millimeters, and 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 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 1.
[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 1.
Table 1
| Embodiment | 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 | 98.5 | 90 |
| B | 180 | 1.2 | 5∶1 | 2.0 | 100 | 82 |
| C | 150 | 2.0 | 7∶1 | 3.0 | 100 | 88 |
| D | 120 | 2.2 | 2∶1 | 1.0 | 100 | 84 |
| E | 100 | 1.0 | 10∶1 | 2.0 | 89 | 94 |
| F | 140 | 1.8 | 8∶1 | 3.0 | 100 | 92.5 |
| G | 200 | 3.0 | 15∶1 | 3.0 | 100 | 87 |
| H | 160 | 1.6 | 9∶1 | 2.0 | 100 | 91 |
| I | 170 | 1.7 | 10∶1 | 2.0 | 100 | 91 |
| Compare 1 | 150 | 1.5 | 10∶1 | 2.0 | 92 | 75 |
| Compare 2 | 150 | 1.5 | 22∶1 | 2.0 | 100 | 90 |
Claims (9)
1, a kind of method that is used for preparing ethandiol by catalyzing epoxyethane hydration is a raw material with water and oxyethane, under the following conditions reaction:
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) catalyzer of Shi Yonging to be being 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, and 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, according to the described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that 100～200 ℃ of described temperature of reaction, reaction pressure 1.0～3.0MPa.
3, according to the described method that is used for 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.
4, according to the described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described catalyzer in vehicle weight per-cent, the metal of niobium or oxide compound consumption are 1～20%.
5, according to the described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 4, it is characterized in that described catalyzer in vehicle weight per-cent, the metal of niobium or oxide compound consumption are 2～10%.
6, according to the described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described catalyzer 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%.
7,, 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 described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 1.
8, according to the described method that is used for preparing ethandiol by catalyzing epoxyethane hydration of claim 1, it is characterized in that described alumina catalyst support is an Alpha-alumina, described zeolite is the HZSM-5 zeolite.
9, according to the described method that is used for 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141453 CN1218917C (en) | 2003-07-09 | 2003-07-09 | Process for preparing ethylene glycol by ethylene oxide catalytic hydration |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03141453 CN1218917C (en) | 2003-07-09 | 2003-07-09 | Process for preparing ethylene glycol by ethylene oxide catalytic hydration |
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| CN1566050A CN1566050A (en) | 2005-01-19 |
| CN1218917C true CN1218917C (en) | 2005-09-14 |
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| CN 03141453 Expired - Lifetime CN1218917C (en) | 2003-07-09 | 2003-07-09 | Process for preparing ethylene glycol by ethylene oxide catalytic hydration |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100469745C (en) * | 2005-12-29 | 2009-03-18 | 中国石油化工股份有限公司 | Hydration process for preparing ethylene glycol by epoxy ethane |
| CN101723802B (en) * | 2008-10-24 | 2013-06-19 | 中国科学院大连化学物理研究所 | Method for preparing ethylene glycol from cellulose |
| CN101870638A (en) * | 2009-04-21 | 2010-10-27 | 北京金骄生物质化工有限公司 | Method for preparing ethylene alcohol by plant straws |
| CN104014227B (en) * | 2014-06-05 | 2016-03-09 | 万华化学集团股份有限公司 | A kind of purification method containing expoxy propane or oxirane organic exhaust gas |
| 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 |
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