CN1175932C - Method for preparing vinyl epoxide argentum catalyst - Google Patents
Method for preparing vinyl epoxide argentum catalyst Download PDFInfo
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- CN1175932C CN1175932C CNB021124396A CN02112439A CN1175932C CN 1175932 C CN1175932 C CN 1175932C CN B021124396 A CNB021124396 A CN B021124396A CN 02112439 A CN02112439 A CN 02112439A CN 1175932 C CN1175932 C CN 1175932C
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Abstract
The present invention relates to a method for preparing a vinyl epoxide argentum catalyst, which mainly solves the problem that the activity of a silver catalyst prepared by the prior art is not high enough. In the method of the present invention, an alpha-alumina carrier is processed by an alkaline substance, and the alkali processing comprises two modes of solution and gas; the amount of the alkaline substance is 0.01 to 500% measured by the weight percentage of the carrier, the processing temperature is 30 to 800 DEG C, and the processing time is 1 to 30 hours. The carrier processed by alkali is washed with water until the effluent liquid is neutral, and then the silver catalyst carrier is prepared by drying. The carrier is loaded with silver and at least one auxiliary agent selected from sulfur, rhenium, molybdenum, tungsten, nickel, alkali metals or alkaline earth metals; the loading amount of the silver is 5 to 40% of the weight of the catalyst measured by silver, and the loading amount of the auxiliary agent is 0.001 to 1% of the weight of the catalyst measured by the weight of elements. The silver catalyst prepared by the method of the present invention is used for producing epoxy ethane, and has the advantages of low reaction temperature and high reactivity. Simultaneously, the high selectivity of the catalyst is kept. The method can be used in the industrial production of the silver catalyst for producing the epoxy ethane.
Description
Technical field
The present invention relates to a kind of preparation method who is used for vinyl epoxide argentum catalyst.
Background technology
Silver catalyst is used for ethylene epoxidizing production oxirane extensively to be implemented at commercial plant, and high activity and high selectivity are two important performances of silver catalyst, and carrier property plays crucial effects to silver catalyst activity, selectivity.Silver catalyst is carrier usually with the Alpha-alumina,, adds minor amounts of promoters and prepares as main active constituent with silver.Obtain high activated catalyst, high silver granuel specific surface must be provided, require carrier to have enough big specific surface, but specific surface is excessive, can cause reaction system to remove the heat difficulty, the oxidation of aggravation reaction depth reduces product oxirane selectivity.How the active and relation optionally of hormany catalyt agent makes catalyst have high activity and high selectivity simultaneously, is the emphasis that people pay close attention to research for a long time always.In the prior art, many patents relate to the silver catalyst and the catalyst carrier of producing oxirane, though the silver catalyst and the carrier of design have carried out abundant improvement at present, have higher activity and selectivity, but consider the ethylene oxide production scale, catalyst activity or selectivity have raising slightly, all can bring very high economic benefit, therefore, still have the more demand of high activity, selectivity silver catalyst of developing in the prior art.
US4742034 has introduced a kind of silver catalyst preparation method of epoxidation of ethylene, alkali-metal alumina support is rich in use, add alkali metal and fluorine in the main body, alkali metal is mainly introduced with the form of fluoride or nitrate, this catalyst has selectivity and stability preferably, fluorine-containing catalyst selectivity reaches 81.2%, improves 2% than not fluorine-containing catalyst selectivity.
EP716884A
2Introduced a kind of silver catalyst preparation method, pre-preg alkali metal in carrier, through heat treatment, make it to load on the carrier, main body is flooded silver, rhenium, sulphur, alkali metal etc. then, and the pretreated purpose of carrier mainly improves the initial selectivity of catalyst and optionally stable, and the catalyst that so obtains is used for epoxidation of ethylene, selectivity reaches 82%, and has selectivity steady in a long-term.
Chinese patent 95196582.4 (CN1168644A) provides a kind of preparation method that ethylene oxy turns to silver catalyst for ethylene oxide that is used for, inert carrier is immersed in a kind of silver/amine aqueous solution, through after the roasting, introduce co-catalysts such as Cs, Re, S, in calcining in the inert atmosphere more than 100 ℃.By O
27% (V), 8%CO
2, 15%C
2H
4, 70%N
2The raw mix of forming is with 5500h
-1Air speed is by catalyst, and reaction pressure 21.69 is clung to, and when oxirane outflow concentration was 1.5% (volume), the reaction temperature that embodies catalyst activity was 228～259 ℃, and selectivity is 81～83.7%.
Chinese patent 00119774.6 has been introduced a kind of preparation method of silver catalyst carrier, in alumina raw material, add fluorochemical, high-temperature roasting, generate Alpha-alumina, then with additives kneading, moulding such as perforating agent, binding agents, make alpha-alumina supports through high-temperature roasting for the second time, silver catalyst with this preparing carriers, be used for ethylene epoxidizing and prepare reacting ethylene oxide, has higher selectivity, but the catalyst reaction activity was high not enough, reaction pressure 2.1MPa (gauge pressure), air speed 7000 hours
-1Under the condition, when the reactor outlet ethylene oxide concentration was 1.4 moles of %, the reaction temperature that embodies catalyst activity was 225～230 ℃.
Above-mentioned catalyst all has selectivity, activity and stable preferably, but the catalyst reaction activity is high not enough.
Summary of the invention
Technical problem to be solved by this invention is to overcome the high not enough defective of silver catalyst reactivity that existing document makes, a kind of preparation method of vinyl epoxide argentum catalyst is provided, the catalyst of this method preparation is used for epoxidation of ethylene and produces oxirane, have the advantage that reaction temperature is low, reactivity is high, keep the high selectivity of catalyst simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of vinyl epoxide argentum catalyst comprises the ethene step successively:
A) with the Alpha-alumina be carrier, the carrier consumption is 60～94% of a catalyst weight;
B) with alkaline matter carrier is carried out alkali treatment, comprise and use alkaline substance solution or two kinds of processing modes of gas, the alkaline matter consumption counts 0.01～500% with vehicle weight percentage, 30～800 ℃ of treatment temperatures, 1～30 hour processing time, carrier after the alkali treatment is washed with water to and flows out liquid for neutral, and drying obtains silver catalyst carrier;
C) load silver on the carrier that the b step makes, the load capacity of silver is counted 5～40% of catalyst weight with silver;
D) before load silver, load cocatalyst simultaneously or afterwards, co-catalyst is selected from a kind of in sulphur, rhenium, molybdenum, tungsten, nickel, alkali metal, the alkaline-earth metal or their mixture, and co-catalyst is 0.001～1% of a catalyst weight in the load capacity of element wt.
In the technique scheme, the preparation alpha-alumina supports is a raw material with hydrated alumina, transition aluminas or the mixture of the two, consider the cost of material problem, used alumina raw material is preferably selected hydrated alumina for use, hydrated alumina is a kind of in a water aluminium oxide, a false water aluminium oxide, gibbsite or the amorphous aluminium glue, or two or more mixture wherein, a preferred water aluminium oxide, gibbsite or the two mixture.
Because fluoride helps aluminium oxide and change into alpha-alumina crystal in roasting, eliminates unnecessary micropore, improve carrier as selection of catalysts.When the present invention prepares alpha-alumina supports, in alumina raw material, add binding agent, pore-foaming agent and water, simultaneously can a kind of fluorochemical of non-imposed adding, obtain mixed material; Wherein the addition of fluorochemical is counted 0.01～20% of alumina weight with fluorine, and the binding agent addition is 0.01～10% of an alumina weight, and the pore-foaming agent addition is 5～50% of an alumina weight; The fluorochemical that uses comprises alkali metal fluoride, alkali earth metal fluoride, NH
4F, (NH
4) HF
2, AlF
3Or HF or the like, preferably adopt ammonium fluoride, hydrogen fluoride or aluminum fluoride; The binding agent that uses comprises nitric acid, aluminium glue, inorganic clay, magnesium silicate, calcium silicates, barium silicate, barium aluminate, cellulose, methyl or ethyl or carboxyethyl cellulose, methyl stearate or ethyl ester, wax class, polyolefin epoxide etc.; Suitable pore-foaming agent comprises carbonaceous material, as coke, carbon dust, graphite; Powdered plastic such as polyethylene, polystyrene, Merlon, rosin; Cellulose and cellulose-based material; Wood chip and other vegetable material such as Powdered stone shell such as pecan shell, walnut shell, hazel shell etc.
After above-mentioned mixed material fully mediated, make certain shape, support shapes can be spherical, block, ball shape, cylindric, Raschig ring shape, porous circular cylinder shape, clover shape etc.Above-mentioned article shaped in 60-200 ℃ of drying, is passed through high-temperature roasting again, promptly obtain the alpha-alumina supports of handling or handling without fluorine through fluorine.Described sintering temperature is 1000 ℃-1700 ℃, 1200 ℃-1600 ℃ of preferable range, and 1300 ℃-1500 ℃ of better preferable range, roasting time is 0.5-20 hour, preferable range 1-10 hour, better preferable range 1-6 hour.Sometimes, also can be by control the pore size distribution of carrier with the mixed method of varigrained alpha-alumina powder.
Aluminium oxide after fluorine is handled has the flat crystal configuration through high-temperature roasting, is the 0.1-30 micron by choosing the suitable initial oxidation aluminum feedstock and the fluorochemical content of adding, can controlling the flat crystal width, and preferable range is the 0.5-10 micron; Thickness is the 0.1-4 micron, and preferable range is the 0.1-2 micron.
The alpha-alumina supports (comprise through fluorine and handle or handle without fluorine) that makes is carried out alkali treatment with alkaline matter, the alkaline matter that uses comprises the gas that all can be mixed with the compound of alkaline solution and be alkalescence, inorganic alkaline compound for example, organic basic compound or their mixture, wherein inorganic alkaline compound can be selected from the oxide of alkali metal or alkaline-earth metal, hydroxide, be selected from the salt of weak acid of alkali metal or alkaline-earth metal, as carbonate, acetate, oxalates, carboxylate or their mixture, described alkali metal preferred lithium, sodium, potassium or caesium, alkaline-earth metal preferably magnesium or calcium; Inorganic alkaline compound also can be selected ammonia for use, and ammonia can adopt ammoniacal liquor and two kinds of states of matters of ammonia; Organic basic compound is selected from aminated compounds, pyridine compounds and their or their mixture, aminated compounds such as ethylenediamine, monoethanolamine, methylamine, ethamine, aniline or its mixture, preferred ethylenediamine, monoethanolamine or its mixture, pyridine compounds and their such as pyridine, trimethylpyridine etc.; The alkaline matter consumption counts 0.01～500% with vehicle weight percentage, and is preferred 0.05～300%, 30～800 ℃ of treatment temperatures, preferred 50～500 ℃, be more preferably 80～400 ℃, 1～30 hour processing time, preferred 2～20 hours, in general treatment temperature was high more, and the processing time is short more.
The alkali treatment mode can adopt alkaline substance solution or two kinds of states of matter modes of gas to handle, when handling with alkaline substance solution, the preparation of solution is that the alkaline matter that will count 0.01～500% with vehicle weight percentage is dissolved in water, methyl alcohol, ethanol, in acetone or the chloroform equal solvent, solvent is preferentially selected water or ethanol for use, make the liquor capacity of preparation can soak carrier at least, the volume ratio of solution and carrier can be 0.1～20: 1, preferred 1～5: 1, the concrete alkaline substance solution of use can be: lithium hydroxide aqueous solution, sodium hydrate methanol solution, potassium hydroxide aqueous solution, the cesium hydroxide ethanolic solution, ammoniacal liquor, aqueous sodium carbonate, ethylenediamine, monoethanolamine, pyridine or trimethylpyridine etc.; During with the alkaline matter gas treatment, used gas can be the gaseous mixture of ammonia, ammonia and Air mixing gas or ammonia and nitrogen, air (or nitrogen) wherein: the mol ratio of ammonia is 0～10: 1, make gas pass through the carrier bed with given pace, processing time is 1～30 hour, and alkali gas feeding amount counts 0.01～500% with vehicle weight percentage.
Carrier water repeated multiple times washing after the alkali treatment, water can be distilled water or deionized water, shows neutrality until the scrub stream fluid, and is dry under 80～200 ℃, promptly obtains producing the silver catalyst carrier of oxirane.By the carrier that said method obtains, its specific area is generally 0.2-1.5 rice
2/ gram, water absorption rate is generally 0.2-0.8 milliliter/gram, and bulk density is generally the 0.4-1.0 grams per milliliter.
In the Preparation of Catalyst of the present invention, method on the carrier of alkali treatment that silver is loaded on has multiple, can use the silver nitrate aqueous solution impregnated carrier, with hydrogen, hydrazine or formaldehyde silver ion reduction is become argent then; The ammonia spirit impregnated carrier of also available silver oxalate or silver carbonate, drying makes silver ion reduction become argent through heating.The best way be mixture with a kind of silver salt-organic solvent/reducing agent-water as silver-colored maceration extract, behind the impregnated carrier, make silver ion reduction become argent through heat treatment, this method can make argent be carried on the carrier with the fine particulate of high degree of dispersion.
Mixture as the silver salt-organic solvent/reducing agent-water of silver-colored maceration extract, silver salt wherein comprises inorganic salts and organic salt, as silver nitrate, silver carbonate, silver sulfate, silver chlorate, silver oxalate, silver acetate, actol, succinic acid silver, glycolic silver, preferred silver oxalate.Organic solvent/reducing agent both can be used as the solvent of silver salt, can under the situation of heating, be reduced into the silver of ionic state the silver of metallic state simultaneously again, can adopt organic amine, especially alkanolamine, Alkylenediamine are as the mixture of ethylenediamine, propane diamine, monoethanolamine, Propanolamine, butanolamine and their mixture or they and ammonia.Silver maceration extract compound method commonly used has two kinds, can illustrate by following two examples.An example is that the mixture of silver oxide and ethylenediamine and oxalic acid is reacted, generate a kind of mixture of silver oxalate-ethylenediamine that contains as silver-colored maceration extract, note avoiding a silver oxide directly to join ethylenediamine, because the silver of Sheng Chenging-ethylenediamine solution instability thus sets off an explosion easily.Another example is: liquor argenti nitratis ophthalmicus and ammonium oxalate solution are mixed, generation silver oxalate precipitation, the precipitation of cyclic washing gained is with flush away nitrate anion wherein, with ethylenediamine solution dissolving silver oxalate precipitation, the mixture of the silver oxalate-ethylenediamine of gained can be used as silver-colored maceration extract then.
Carrier is taken out from silver-colored maceration extract, dry, heat-treat, hot gas flows through wet carrier, removes organic solvent and water in the carrier that dries, and silver is deposited on the carrier with the metal fine shape, the load capacity of silver is 5～40% of a catalyst weight, preferred 10～20%.Heat treatment atmosphere can be air, nitrogen, oxygen, hydrogen, carbon dioxide, steam or their mixture.Heat treatment temperature can be selected 80～700 ℃ for use, preferred 150～500 ℃.Heat treatment time can be selected for use 1 minute～10 hours, was preferably 2～30 minutes.
Co-catalyst can improve the catalytic performance of silver catalyst effectively, as performances such as selectivity, activity, stability.The co-catalyst that the inventive method is selected for use is selected from a kind of in sulphur, rhenium, molybdenum, tungsten, nickel, alkali metal, the alkaline-earth metal or their mixture, preferred sulphur, rhenium, alkali metal or their mixture, co-catalyst is 0.001～1% of a catalyst weight in the load capacity of element wt, preferred 0.003～0.1%; Wherein alkali metal is the most frequently used co-catalyst of a class, with the caesium is best, the example of the alkali metal catalyst raw material that is suitable for has, alkali-metal nitrate, hydroxide, carbonate, oxalates, carboxylate, alkoxide or their mixture, instantiation has cesium carbonate, rubidium nitrate, potassium hydroxide, sodium acetate, lithium oxalate.Co-catalyst can be before silver impregnated in carrier, simultaneously or be applied on the carrier afterwards.
The catalyst of the inventive method preparation is used for ethene and oxirane is produced in the molecular oxygen reaction.The process conditions of being put down in writing in process conditions that adopted and the common document are close.The process conditions that silver catalyst of the present invention can adopt are: reaction temperature is preferably in 200～280 ℃ at 150～300 ℃; Reaction pressure is preferably in 15～30 kilograms/square centimeter at 10～40 kilograms/square centimeter; Gas compartment speed was at 1000～30000 hours
-1, better at 3000～15000 hours
-1The volume of unstripped gas is formed can be 0.5～40% ethene, 3～10% oxygen; 5～30% carbon dioxide, a spot of inhibitor, all the other are inactive gas, as nitrogen, argon gas, water vapour or rudimentary hydrocarbon, as methane, ethane.Inhibitor in the unstripped gas can be regulated the reactivity worth of catalyst within the specific limits, usually adopt halide or nitrogen-containing compound, halide can be chloride, bromide, fluoride or iodide, for example dichloroethanes, chloroethanes, dichloroethylene, vinyl chloride, monochlor-benzene, dichlorobenzene.Nitrogen-containing compound such as nitropropane.The inhibitor that contains 0.1～20 part of volume in the unstripped gas of per 1,000,000 parts of volumes.
Activity is the important performance of silver catalyst.Activity is meant under the situation of fixing other reaction condition (as temperature, pressure, air speed etc.), the height of reactor exit ethylene oxide concentration, that is to say that if it is low more to reach the needed temperature of a certain definite ethylene oxide concentration, activity of such catalysts is just high more; Reaction temperature is high more, illustrates that then activity of such catalysts is low more.Activity of such catalysts is represented with the height of reaction temperature.
The key of the inventive method is alpha-alumina supports to be carried out alkali treatment under certain condition with the alkaline matter of liquid state or gaseous state, contained alkaline matter such as cation and the OH such as alkali metal, alkaline-earth metal of carrier after the alkali treatment
-Do not stay in the carrier Deng anion, by repeatedly washing it is removed from carrier, main micro adjusting carrier surface of the purpose of alkali treatment and internal microcellular structure make carrier surface produce a large amount of high energy site, effectively improve the reactivity worth of Alpha-alumina as silver catalyst carrier.Load silver and some auxiliary agents on the alkali treatment carrier, the load capacity of silver is 5～40% of a catalyst weight, auxiliary agent can be S, Re, Mo, W, Ni, alkali metal, alkaline-earth metal or their mixture, auxiliary agent is 0.001～1% of a catalyst weight in the load capacity of element wt, makes vinyl epoxide argentum catalyst of the present invention.
The silver catalyst of the inventive method preparation, by carrier process alkali treatment with catalyst, make carrier surface be rich in a large amount of high energy site, make the silver and the co-catalyst ratio that load on these high energy sites manifest higher reactivity usually, this catalyst is used for epoxidation of ethylene and produces oxirane, under the situation of fixed reactor outlet ethylene oxide concentration, the reaction temperature of catalyst reduces by 10～20 ℃ than prior art, activity of such catalysts is significantly improved, and keeps the high selectivity of catalyst simultaneously.In addition, the present invention adds fluorochemical in the alpha-alumina supports preparation, the catalyst selectivity of handling preparing carriers through fluorine increases than the catalyst selectivity of handling preparing carriers without fluorine, thereby has improved the reactivity worth of whole catalyst, has obtained better effects.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
1, preparation carrier A:
Get a water alumina powder 500 grams and place kneading machine, add graphite 125 grams, calcium silicates 3 grams, water 160 grams are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1500 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Get alpha-alumina supports 100 grams, add potassium hydroxide aqueous solution (0.05 gram potassium hydroxide is dissolved in 100 ml waters), handled 10 hours in 300 ℃.After the cooling, be neutral with deionized water cyclic washing carrier to flowing out liquid, in 120 ℃ of dryings.
2, preparation catalyst A:
Taking by weighing silver nitrate 59.1 grams is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters.Add cesium carbonate 0.115 gram, add water again, make silver-colored amine complex liquid.The silver-colored amine complex liquid that carrier A excessive dipping under vacuum is above-mentioned is pulled wet feed out and is drained, and puts into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, catalyst A.Catalyst A contains 13.0% silver by weight, the caesium of 326ppm.
3, the reactivity worth of catalyst A test:
Adopt 10 milliliters of minisize reaction evaluation systems, catalyst breakage to 10～20 orders, get 10 milliliters of internal diameters of packing into and be in 8 millimeters the stainless steel reactor, carry out the epoxidation of ethylene performance test in the minisize reaction evaluation system, relevant reaction condition is as follows:
The unstripped gas mole is formed:
C
2H
4: 28% O
2: 6.4% CO
2: 5% inhibitor: micro-N
2: all the other
Pressure: 2.1MPa (gauge pressure)
Air speed: 7000 hours
-1
Outlet ethylene oxide concentration: 1.4 moles of %
The epoxidation of ethylene of catalyst A the results are shown in Table 1.
The catalyst performance method of testing of following examples 2～7, comparative example 1～2 preparation is identical with the performance test methods of embodiment 1, and reaction result sees Table 1.
[comparative example 1]
1, preparation carrier A
1:
Get a water alumina powder 500 grams and place kneading machine, add graphite 125 grams, calcium silicates 3 grams, water 160 grams are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1500 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports A
1
2, preparation catalyst A
1:
Carrier A
1Need not any alkaline matter for processing, prepare catalyst A according to the method identical with embodiment 1
1, different is the consumption that changes caesium, catalyst A
1Contain 13.0% silver by weight, the caesium of 290ppm.
[embodiment 2]
1, preparation carrier B:
Get alpha-alumina supports 100 grams of embodiment 1, add aqueous sodium carbonate (50 gram sodium carbonate are dissolved in 500 ml waters), handled 10 hours down in 300 ℃.The cooling, with deionized water cyclic washing carrier to flow out liquid be neutrality, drying.
2, preparation catalyst B:
Method by embodiment 1 prepares catalyst B, and different is to replace carrier A with carrier B, the consumption of silver and caesium in the change catalyst, and the catalyst B that makes contains 20% silver by weight, the caesium of 250ppm.
[embodiment 3]
1, preparation support C:
Get a water alumina powder 900 grams and place kneading machine, add graphite 225 grams, calcium silicates 4.5 grams, ammonium fluoride 0.5 gram, water 290 grams are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1400 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Getting alpha-alumina supports 100 gram, add cesium hydroxide ethanolic solution (10 gram cesium hydroxides are dissolved in 500 milliliters of ethanol), handled 2 hours down in 500 ℃, cooling, is neutrality with deionized water cyclic washing carrier to flowing out liquid, 120 ℃ of dryings.
2, preparation catalyst C:
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.With of the ethylenediamine solution dissolving of silver oxalate filter cake with 32.8 milliliters of ethylenediamines and 32.8 ml waters.Add concentration and be 1.5 milliliters of the perrhenic acid solution of 0.0627 grams per milliliter, ammonium sulfate 0.0495 gram, cesium carbonate 0.143 gram adds water again, makes silver-colored amine complex liquid.The silver-colored amine complex liquid that support C excessive dipping under vacuum is above-mentioned is pulled wet feed out and is drained, and puts into thermal decomposer, with 260 ℃ of warm air blowoff 8 minutes, take out, catalyst C.Catalyst C contains 13.0% silver by weight, the rhenium of 243ppm, the sulphur of 41.7ppm, the caesium of 405ppm.
[comparative example 2]
1, preparation support C
1:
Get Alpha-alumina powder 900 grams and place kneading machine, add graphite 225 grams, calcium silicates 4.5 grams, ammonium fluoride 0.5 gram, water 290 grams are fully kneaded, and are squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1400 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports C
1
2, preparation catalyst C
1:
Support C
1Need not any alkaline matter for processing, according to preparing catalyst C with embodiment 3 same procedure
1, different is the consumption that changes rhenium, sulphur, caesium, catalyst C
1Contain 13.0% silver by weight, the rhenium of 215ppm, the sulphur of 50.0ppm, the caesium of 445ppm.
[embodiment 4]
1, preparation carrier D:
Getting alpha-alumina supports 100 gram of embodiment 3, add weight concentration and be 200 milliliters of 25% concentrated ammonia liquors, handled 25 hours down in 50 ℃, cooling, is neutrality with deionized water cyclic washing carrier to flowing out liquid, 120 ℃ of dryings.
2, preparation catalyst D:
Method by embodiment 3 prepares catalyst D, and different is to replace support C with carrier D, changes the consumption of silver, rhenium, sulphur, caesium in the catalyst, and the catalyst D that makes contains 15.0% silver by weight, the rhenium of 306ppm, the sulphur of 81ppm, the caesium of 600ppm.
[embodiment 5]
1, preparation carrier E:
Get a water alumina powder 400 gram and gibbsite powder 200 grams place kneading machine, add graphite 90 grams, calcium silicates 3 grams, ammonium fluoride 6 grams, water 190 restrains, and fully kneads, and is squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.100 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Get alpha-alumina supports 100 grams, add ethylenediamine 300 grams, handled 20 hours down at 100 ℃.After the cooling, be neutral with distilled water cyclic washing carrier to flowing out liquid, in 150 ℃ of dryings.
2, preparation catalyst E:
Method by embodiment 3 prepares catalyst E, and different is to replace support C with carrier E, replaces ammonium sulfate with ammonium molybdate, change the consumption of silver, rhenium, caesium in the catalyst, the catalyst E that makes contains 10.0% silver by weight, the rhenium of 280ppm, the molybdenum of 65ppm, the caesium of 283ppm.
[embodiment 6]
1, preparation carrier F:
Get a water alumina powder 600 gram and gibbsite powder 600 grams place kneading machine, add graphite 300 grams, 6 gram calcium silicates, 24 gram amine fluorides, water 380 restrains, and fully kneads, and is squeezed into 8 millimeters of external diameters, 4 millimeters of internal diameters, high 6.4 millimeters Raschig ring.120 ℃ of oven dry, 1460 ℃ of roastings 4 hours obtain Raschig ring shape alpha-alumina supports.
Get 100 gram alpha-alumina supports, feed ammonia and Air mixing gas down in 200 ℃, air: ammonia (mole) is than being 5: 1, and 18 liters/hour of air speeds kept 10 hours.After the cooling, be neutral with distilled water cyclic washing carrier to flowing out liquid, in 150 ℃ of dryings.
2, preparation catalyst F:
Getting 59.1 gram silver nitrates is dissolved in 200 ml waters.Other gets ammonium oxalate 26.8 grams and is dissolved in 364 ml waters.Above-mentioned two solution carry out precipitation reaction under 40 ℃, with the silver oxalate precipitate with deionized water washing that obtains, filter.The silver oxalate filter cake with the dissolving of the ethylenediamine solution of 32.8 milliliters of ethylenediamines and 32.8 ml waters, is added concentration and be 1.8 milliliters of the perrhenic acid of 0.0627 grams per milliliter, and wolframic acid 0.180 gram adds cesium carbonate 0.185 gram again, adds water again, makes silver-colored amine complex liquid.Get 100 gram carrier F excessive dippings under vacuum above-mentioned silver-colored amine complex liquids, pull wet feed out and drain, put into thermal decomposer,, take out, under nitrogen atmosphere, handled 4 hours for 400 ℃ with 260 ℃ of warm air blowoff 8 minutes, must catalyst F.Catalyst F contains 13.0% silver by weight, the rhenium of 291ppm, the tungsten of 460ppm, the caesium of 525ppm.
[embodiment 7]
1, preparation carrier G:
Get alpha-alumina supports 100 grams of embodiment 6, add pyridine 200 grams, handled 5 hours down in 400 ℃.After the cooling, be neutral with distilled water cyclic washing carrier to flowing out liquid, in 150 ℃ of dryings.
2, preparation catalyst G:
Method by embodiment 6 prepares catalyst G, different is to replace carrier F with carrier G, replace wolframic acid with ammonium molybdate, ammonium sulfate, change the consumption of silver, rhenium, caesium in the catalyst, the catalyst G that makes contains 14.0% silver by weight, the rhenium of 410ppm, the molybdenum of 92.0ppm, 32.0ppm sulphur, the caesium of 700ppm.
The epoxidation of ethylene result of table 1 catalyst
| Catalyst | Selectivity % | Reaction temperature ℃ | |
| Embodiment 1 | A | 82.3 | 215 |
| Comparative example 1 | A 1 | 82.3 | 225 |
| Embodiment 2 | B | 86.4 | 216 |
| Embodiment 3 | C | 86.3 | 221 |
| Comparative example 2 | C 1 | 86.1 | 235 |
| Embodiment 4 | D | 86.2 | 225 |
| Embodiment 5 | E | 86.3 | 218 |
| Embodiment 6 | F | 86.1 | 215 |
| Embodiment 7 | G | 86.2 | 223 |
Claims (9)
1, a kind of preparation method of vinyl epoxide argentum catalyst may further comprise the steps successively:
A) with the Alpha-alumina be carrier, the carrier consumption is 60～94% of a catalyst weight;
B) with alkaline matter carrier is carried out alkali treatment, comprise and use alkaline substance solution or two kinds of processing modes of gas, the alkaline matter consumption counts 0.01～500% with vehicle weight percentage, 30～800 ℃ of treatment temperatures, 1～30 hour processing time, carrier after the alkali treatment is washed with water to and flows out liquid for neutral, and drying obtains silver catalyst carrier;
C) load silver on the carrier that the b step makes, the load capacity of silver is counted 5～40% of catalyst weight with silver;
D) before load silver, load cocatalyst simultaneously or afterwards, co-catalyst is selected from a kind of in sulphur, rhenium, molybdenum, tungsten, nickel, alkali metal, the alkaline-earth metal or their mixture, and co-catalyst is 0.001～1% of a catalyst weight in the load capacity of element wt.
2,, it is characterized in that alkaline matter comprises inorganic alkaline compound, organic basic compound or their mixture according to the preparation method of the described vinyl epoxide argentum catalyst of claim 1.
3,, it is characterized in that inorganic alkaline compound is oxide, hydroxide, salt of weak acid or their mixture of alkali metal or alkaline-earth metal according to the preparation method of the described vinyl epoxide argentum catalyst of claim 2.
4, according to the preparation method of the described vinyl epoxide argentum catalyst of claim 2, it is characterized in that inorganic alkaline compound is an ammonia, be the gaseous mixture of ammoniacal liquor, ammonia, ammonia and Air mixing gas or ammonia and nitrogen.
5,, it is characterized in that organic basic compound is aminated compounds, pyridine compounds and their or their mixture according to the preparation method of the described vinyl epoxide argentum catalyst of claim 2.
6,, it is characterized in that the alkaline matter consumption counts 0.05～300% with vehicle weight percentage according to the preparation method of the described vinyl epoxide argentum catalyst of claim 2.
7, according to the preparation method of the described vinyl epoxide argentum catalyst of claim 3, it is characterized in that treatment temperature is 50～500 ℃, the processing time is 2～20 hours.
8, according to the preparation method of the described vinyl epoxide argentum catalyst of claim 1, it is characterized in that alkali metal is lithium, sodium, potassium or caesium, alkaline-earth metal is magnesium or calcium.
9, according to the preparation method of the described vinyl epoxide argentum catalyst of claim 1, it is characterized in that the preparation of a step, also add fluorochemical in raw material, the addition of fluorochemical is counted 0.01～20% of alumina weight with fluorine, kneading then, moulding, roasting.
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| CNB021124396A CN1175932C (en) | 2002-07-10 | 2002-07-10 | Method for preparing vinyl epoxide argentum catalyst |
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| CNB021124396A CN1175932C (en) | 2002-07-10 | 2002-07-10 | Method for preparing vinyl epoxide argentum catalyst |
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| CN1175932C true CN1175932C (en) | 2004-11-17 |
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