CN85109109A

CN85109109A - Ethylene oxide silver catalyst and preparation usage thereof

Info

Publication number: CN85109109A
Application number: CN85109109.1A
Authority: CN
Inventors: 田村文秀; 五月女稔
Original assignee: Nippon Shokubai Co Ltd
Current assignee: Nippon Shokubai Co Ltd
Priority date: 1984-04-13
Filing date: 1985-10-14
Publication date: 1987-04-15
Also published as: CN1008513B

Abstract

The present invention is used to silver catalyst that makes ethene and molecular oxygen produce oxirane by catalytic gas phase oxidation when the halogenation inhibitor exists and preparation method thereof.This catalyst contains silver and at least a accelerator that is selected from alkali metal and compound thereof, and they are deposited on and are shaped as on Ying Telaokesi (Inta-lox) shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr (Berl).

Description

Ethylene oxide silver catalyst and preparation usage thereof

This invention is to make ethene and molecular oxygen when the halogenation inhibitor exists about being used for silver catalyst, generates the silver catalyst of oxirane and the preparation method of this silver catalyst by catalytic gas phase oxidation.

Industrial ethene and the molecular oxygen of being used for produced the silver catalyst of oxirane by catalytic gas phase oxidation, and be minimum in the pressure loss that requires it to have high selectivity, high activity for a long time on the performance and to produce in catalytic bed.

In order to improve the performance of catalyst, dealing with various requirements has been done many-sided research so far, and many achievements are all at improving carrier, reaction accelerator and silver compound.Some trials that improve the deposition of silver method are existing open in following patent publication: Japanese patent application publication No. SHO 46(1971)-19,606, and United States Patent (USP) 3,702,259, Japanese patent application publication No. SHO 59(1984)-29,291, United States Patent (USP) 4,248,740,4,305,844, with 4,400, No. 308.

About reaction accelerator, known mainly is that alkali metal and thallium are all effective.Various suggestions are being proposed, aspect element kind, quantity and the adding method for example in following these patent specifications: United States Patent (USP) 3,962,136,4,039,561,4,207,210, Japan Patent SHO 50(1975)-95,213, United States Patent (USP) 3,962,136,4,033,903,4,248,740, UK Patent Application 2,043,481, Japan Patent SHO 56(1981)-5,471 and No. 4,389,338, United States Patent (USP).

Many reports have been proposed aspect carrier.These reports are published in United States Patent (USP) 3,207,700, Japanese patent application publication No. SHO 43(1968)-13,137, SHO 45(1970)-21,373, SHO 45(1970)-22,419, SHO 45(1970)-11,217, United States Patent (USP) 4,368,144,2,766,261,3,172,893 and 4,242, No. 235.Mostly in these reports relate to that pore size in the carrier distributes and specific area.

All these specifications are not all mentioned catalytic selectivity and the pressure of improving catalyst bed owing to the selection of support shapes, and these lay particular stress on the catalyst shape of employing so far on commercial production scale and only revealed pill, spheroid and Raschig ring.

United States Patent (USP) 4,389,338 disclose a kind of method for preparing silver catalyst, the step of this method be silver and a kind of as reaction accelerator alkali metal with (or) thallium is deposited on the porous, inorganic refractory support, place the mixture that generates inactive gas to carry out high-temperature process again, temperature rises in 550 ℃ to the 950 ℃ scopes, and the content of oxygen can not be greater than 3% volume ratio in the inactive gas.

At United States Patent (USP) 4,248, a kind of method of producing silver catalyst is disclosed in No. 740 the specification, this method is that the porous, inorganic refractory support is immersed in the silver compound solution that contains a kind of reducing compound, impregnated carrier is heat-treated so that silver restores, thereby argent is disperseed and is deposited on the surface of carrier and the inner surface of pore, then water and (or) the lower alcohol purging compound, the mixture that drying was washed, dried mixture be immersed in contain a kind of alkali metal and (or) in the solution of its compound, by the evaporation of liquid component, dry impregnated mixture.These are several examples of industrial production silver catalyst method, and these silver catalysts have the highest selectivity, the highest active and can keep high selectivity and the most highly active catalyst performance in over a long time concurrently.

Silver catalyst carrier about using in producing oxirane has many main points still need further specify, and many problems still need solve.For example, the mixing of carrier component, specific area, pore diameter, pore distribution, pore volume, porous, granular size and these physical propertys of support shapes and the chemical property that carrier material such as Alpha-alumina, carborundum, silica and zirconia had all have much room for improvement to reach optimization.

So an object of the present invention is provides a kind of novel silver catalyst and preparation method thereof for producing oxirane, when the halogenation inhibitor existed, this catalyst is used for ethene and molecular oxygen is produced oxirane by catalytic gas phase oxidation.

Another object of the present invention provides a kind of silver catalyst and preparation method thereof, has high selectivity halogenation inhibitor when existing, and this catalyst can make ethene and molecular oxygen generate oxirane, and this bears the minimum pressure loss catalyst in catalytic bed.

A kind of in the presence of the halogenation inhibitor, the silver catalyst that can make ethene and molecular oxygen produce oxirane by catalytic gas phase oxidation can achieve the above object, this silver catalyst contains silver and at least a reaction accelerator that is selected from alkali metal and other compounds, and they are deposited on and are shaped as on Ying Telaokesi (Intalox) shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr (Berl).

Furtherly, can achieve the above object by a kind of method for preparing silver catalyst, this silver catalyst contains the tiny silver granuel that disperses and be deposited on porous, inorganic refractory support outer surface and pore inner surface, when the halogenation inhibitor exists, produce oxirane by the catalytic gas phase oxidation of ethene and molecular oxygen.The feature of this method is silver and at least a reaction accelerator that is selected from alkali metal and its compound, be deposited on and be shaped as on the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr, at last the mixture that generates is put into inactive gas, carry out high-temperature process under ascending temperature Celsius 550 ℃ to 950 ℃, oxygen content must not be greater than the 3%(volume in the gas).

Preparation method by a kind of silver catalyst can achieve the above object, this silver catalyst contains the tiny silver granuel that disperses and be deposited on porous, inorganic refractory support outer surface and pore inner surface, when the halogenation inhibitor exists, produce oxirane by the catalytic gas phase oxidation of ethene and molecular oxygen.The feature of this method is to contain in a kind of silver compound solution of reducing compound being shaped as the saddle-shaped porous, inorganic refractory support immersion of the Ying Telaokesi shape of a saddle or bohr, heat impregnated carrier to restore argent, thereby argent just disperses and is deposited on the outer surface of carrier and the inner surface of carrier pore, then with the mixture that is selected from least a liquid scrubbing generation in water or the lower alcohol, drying is washed the mixture that has wet, dried mixture is immersed the solution that contains a kind of alkali metal and its compound at least, then the mixture of dry wet is removed liquid component by evaporation.

Producing in the oxirane with silver catalyst, the support shapes that is suitable for using has been done research.Thereby find to have become effective on a kind of technology in commercial production scale be shaped as the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr and replace in the Catalyst Production the conventional Raschig ring carrier that uses the time, obtained a kind of high selectivity of reaching and on catalytic bed, only bear the catalyst that minimum pressure loses of also failing till now.This invention just is being based on this discovery.

When the halogenation inhibitor existed, ethene and molecular oxygen were produced oxirane by catalytic gas phase oxidation, used a kind of silver catalyst in it is produced.In fact the silver catalyst of this purpose that is useful on all is to support with itself carrier.As you know, employed carrier is the porous and granular refractory material.

Though they can be summarised as a term " porous and granular refractory support " simply, but difference is very big between them, as aspect the physical property, specific area, pore distribution, pore volume, size and support shapes, aspect chemical property, for the carrier that comprises Alpha-alumina, silica, carborundum, zirconia and clay, various materials have different chemical property.These physical propertys and chemical property have noticeable influence to catalyst performance.

So for the skilled person in the one's own profession technology, selecting a kind of special carrier in having many carriers of the characteristic that has nothing in common with each other is an important problem.Particularly the shape of carrier is very big to the performance impact of catalyst.In Preparation of Catalyst, concerning depositing silver, alkali metal and (or) these concrete steps of its compound, select a kind of support shapes of easy realization uniform deposition can cause producing the good catalyst of a kind of selectivity.And, when selecting support shapes, make in course of reaction, gas is unlikely on catalyst granules to cause stagnation, this is successfully to produce the key with the good catalyst of selectivity.In this respect, the long-pending ratio with apparent volume (all volumes (exclusive volume)) of the apparent surface of catalyst requires bigger.On industrial production, the majority carrier of Cai Yonging is sphere or Raschig ring shape so far.In spheric catalyst, obtain the increase of above-mentioned ratio by the diameter that reduces spheric granules.Yet if spherical particle diameters excessively reduces, spherolite will bear the very big pressure loss between the stage of reaction.So the result shows that the excessive minimizing of particle diameter is all unfavorable to equipment and economic benefit two aspects.In Raschig ring, it is effective that its wall thickness reduces increasing above-mentioned ratio.Yet the result shows that this reducing is disadvantageous, because it can make crushing strength reduce, and reduces the surface area of reaction tube inner catalyst per unit volume.

The argument of ratio that the increase of catalyst selectivity is proportional to carrier apparent area and apparent volume is forever correct.This ratio can not infinitely increase, but its upper limit is arranged.

Find behind our the difform after deliberation carrier, use the catalyst of the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr to have high selectivity, on catalytic bed, only bear the minimum pressure loss.

For fixing particle size and wall thickness, compare with Raschig ring, be shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr and have lower packed density.This surface area that is equivalent to per unit volume in the reaction tube reduces to some extent.This is an astonishing fact, this catalyst, and let it be, and shape is unfavorable significantly, but demonstrates satisfied selectivity, bears the low pressure loss on catalytic bed.Even when the apparent surface of the catalyst that is shaped as sphere or Raschig ring carrier long-pending with the ratio of apparent volume when corresponding ratio in the catalyst that is shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr equates, the former does not reach the such high selectivity of the latter and such low pressure loss.In addition, when the catalyst of spherical or cured uncommon ball carrier equated with the packed density of the catalyst of the Ying Telaokesi shape of a saddle or bohr shape of a saddle porous, inorganic refractory support, the former did not reach the high like that selectivity of the latter and such low pressure loss.

Fig. 1 is the perspective view of a Ying Telaokesi (Intalox) shape of a saddle carrier.

Fig. 2 is the front view of this Ying Telaokesi shape of a saddle carrier.

Fig. 3 is the side view of this Ying Telaokesi shape of a saddle carrier.

Fig. 4 is the perspective view of a bohr (Berl) shape of a saddle carrier.

Fig. 5 is the front view of this bohr shape of a saddle carrier.

Fig. 6 is the side view of this bohr shape of a saddle carrier.

Fig. 7 is the perspective view of a Raschig ring (Rasing ring) carrier.

Fig. 8 is the front view of this Raschig ring carrier.

Fig. 9 is the side view of this Raschig ring carrier.

Figure 10 is the perspective view of a Raschig ring carrier.

Figure 11 is the front view of this Raschig ring carrier.

Figure 12 is the side view of this Raschig ring carrier.

In this invention, be shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr and really have specific area in 0.01 to the 10 meters squared per gram scope, preferably have the specific area between 0.1 to 5 meters squared per gram. If specific area is less than 0.01 meters squared per gram, the packed density that then is shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr is too low, so that the surface area of unit volume is quite little in the reaction tube, and the result shows that this carrier is unfavorable to activity. If specific area surpasses 10 meters squared per gram, the pore diameter in the carrier is too little, and during reaction, reactant gas and product gas will certainly be stuck in the catalyst particles intragranular. That uses in the present invention is shaped as Ying Telaokesi saddle or bohr shape of a saddle porous, inorganic refractory support, and the long-pending ratio with apparent volume of its apparent surface is in 0.1 to 10/ millimeter scope, is preferably between 0.5 to 5/ millimeter. If the long-pending ratio with apparent volume of apparent surface is less than 0.1/ millimeter, then to the elective reduction of oxirane. If the long-pending ratio with apparent volume of apparent surface surpasses 10/ millimeter, then the saddle-shaped thickness of the Ying Telaokesi shape of a saddle or bohr is too little, so that can not keep the necessary intensity of any industrial catalyst.

Requirement is shaped as the saddle-shaped porous, inorganic refractory support of Ying Telaokesi and has following physical property, apparent porosity drops in 20% to 80% scope, be preferably between 30% to 70%, drop in 0.06 to the 1.0 cubic centimetre/gram scope than pore volume, be preferably between 0.1 to the 0.8 cubic centimetre/gram, peripheral long (A) drops in 3 to 70 millimeters scopes, be preferably between 3.5 to 30 millimeters, interior girth (C) drops in 1.5 to 68 millimeters scopes, be preferably between 1.8 to 28 millimeters, thickness (W) drops in 0.1 to 4 millimeter scope, be preferably between 0.8 to 3 millimeter, external diameter (D) drops in 0.5 to 20 millimeter scope, is preferably between 3 to 15 millimeters, length (E) drops in 0.5 to 65 millimeter scope, is preferably between 3 to 20 millimeters.

Requirement is shaped as the saddle-shaped porous, inorganic refractory support of bohr and has following physical property, apparent porosity drops in 20% to 80% scope, be preferably between 30% to 70%, drop in 0.06 to the 1.0 cubic centimetre/gram scope than pore volume, be preferably between 0.1 to the 0.8 cubic centimetre/gram, outer perimeter (A) drops in 3 to 70 millimeters scopes, be preferably between 3.5 to 30 millimeters, interior girth (C) drops in 1.5 to 68 millimeters scopes, be preferably between 1.8 to 28 millimeters, thickness (W) drops in 0.1 to 4 millimeter scope, be preferably between 0.8 to 3 millimeter, external diameter (D) drops in 0.5 to 20 millimeter scope, is preferably between 3 to 15 millimeters, length (E) drops in 0.5 to 65 millimeter scope, is preferably between 3 to 20 millimeters.

The material that is suitable for doing carrier has Alpha-alumina, carborundum, silica, zirconia and clay. In the material of quoting, select Alpha-alumina optimum in the above. In addition, except key component, require to sneak into that the amount of the component of carrier adopts usually close to general technology Amount.

The example that has shown in the accompanying drawings the carrier that this invention is used. Fig. 1-3 has described one and has been shaped as the saddle-shaped porous, inorganic refractory support of Ying Telaokesi. Fig. 4-6 has described one and has been shaped as bohr shape of a saddle porous, inorganic refractory support.

For the preparation of carrier, the preparation method of any routine can use. In general, the method for employing is that carrier is immersed in a kind of decomposable silver salt solution or the organic solvent, the aqueous solution of silver nitrate for example, the ammonia solution of organic acid or inorganic acid silver salt, the organic amide solution of silver salt or the aqueous solution of actol. Alkali metal and (or) its compound can the method for choosing any one kind of them be deposited on the carrier, can deposit in advance, can be added in the silver salt solution, be deposited on simultaneously on the carrier with silver, perhaps also can be by decomposition and the reduction of silver salt, then dissolve and remove resultant product silver is deposited on the carrier earlier, and then alkali metal and (or) its Compound deposition is on carrier. After this, can adopt to comprise that the impregnated carrier of heating can decompose silver salt with decomposition and reduction, remove catabolite with the gas of heat then, perhaps water or organic solvent are removed the method for catabolite and are prepared catalyst.

In this invention, use the silver catalyst of the porous, inorganic refractory support that is shaped as the Ying Telaokesi shape of a saddle or bohr saddle, for example when existing, the halogenation inhibitor produces the silver catalyst that in oxirane use by catalytic gas phase oxidation with ethene and molecular oxygen, its preparation method comprises following a few step, to be immersed in the solution (for example amine aqueous solution of the amine aqueous solution of silver salt or organic acid silver salt) that can decompose silver salt inner being shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr, in being 100 ℃ to 300 ℃ scopes, temperature heats then impregnated carrier, thereby reduction or thermal decomposition silver salt, then reusable heat gas dissolves and removes the catabolite of generation, or removes catabolite with solvent.

Other examples that are used for preparing silver catalyst are as follows.

(1) preparation method for the production of the deposition of silver catalyst of oxirane comprises following a few step, Immerse in a kind of mixed solution being shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr, this mixed liquor contain silver nitrate, at least a in a molecular cell, have one to three alcoholic extract hydroxyl group, two rudimentary aliphatic alcohols to six carbon atom, water and have at least a kind ofly contain one to the rudimentary acid amide of four carbon atom, thereby heat then impregnated carrier argent is deposited on the carrier, further the mixture of heating generation is to remove organic substance wherein.

(2) preparation method for the production of the silver catalyst of oxirane comprises following a few step: silver and alkali metal with (or) a kind of alkali metal compound is deposited on and is shaped as on the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr, at last the mixture that generates is put in the inactive gas, stand high-temperature process under in 550 ° to 950 ℃ scopes, heating up gradually, in the inactive gas, the volume ratio of oxygen content can not be greater than 3%.

(3) preparation method for the production of the silver catalyst of oxirane comprises following a few step: be immersed in the silver compound solution that contains a kind of reduzate being shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr, impregnated carrier carries out thermal reduction to be processed, thereby cause the silver dispersion and be deposited on the outer surface of carrier and the inner surface of pore, water and (or) mixture that generates of lower alcohol washing, the mixture of dry wet, then the mixture of drying is immersed in contain a kind of alkali metal and (or) in the solution of its compound, dry impregnated mixture, thus remove liquid component by evaporation.

Be deposited on the silver amount of the surfaces externally and internally of carrier with fine-grained form, take the weight of catalyst as benchmark, 5% to 30%, preferably between 5% to 25%. Alkali metal or its compound join in the silver salt solution with the form of the aqueous solution or alcoholic solution, be deposited on simultaneously on the carrier with silver, to make a kg catalyst as benchmark, add the amount of alkali metal compound 0.0001 to 0.05 gram equivalent of scope, preferably be no less than 0.001 gram equivalent, be not more than 0.03 gram equivalent. At carrier deposition alkali metal or its compound, can be before deposition of silver, also can be after deposition of silver, the alternatively.

The result shows that to the preparation of silver catalyst among the present invention, method 2 and method 3 meet the requirements especially.

In the method 2 of preparation catalyst of the present invention, preparation process can be with any is implemented in known so far most of processes up to this step of high-temperature process.The example of a technical process comprises following a few step: be immersed in the aqueous solution of organic or inorganic silver salt or the organic solution (aqueous solution of actol for example being shaped as the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr, the organic amine solution of organic acid silver salt) and a kind of alkali metal and (or) in a kind of aqueous solution or organic solvent of alkali metal compound (for example the cesium nitrate aqueous solution, the alcoholic solution of cesium carbonate aqueous solution or cesium carbonate); Dry impregnated carrier; Thereby the carrier behind the heat drying decomposes and the reduction silver salt, make argent and a kind of alkali metal and (or) a kind of alkali metal compound is deposited on the carrier; In order to activate, promptly, further heat product again for the thermal decomposition and the excessive organic or inorganic component of overflowing, just made catalyst.The example of another technical process comprises following a few step, being shaped as the aqueous solution or the organic solution that the saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr is immersed in the organic or inorganic silver salt, for example in the organic amine solution of the actol aqueous solution or acylate, dry impregnated carrier, thereby the carrier of heat drying decomposes and the reduction silver salt, argent is deposited on the carrier, then will produce thing and stand so-called activation, be water or organic solvent washing or boil product to remove excessive organic or inorganic component, then product be immersed in a kind of alkali metal and (or) a kind of aqueous solution or organic solution of alkali metal compound, the aqueous solution of cesium nitrate for example, or in the alcoholic solution of the aqueous solution of cesium carbonate or cesium carbonate, dry impregnated mixture, thus catalyst made.As used silver salt solution in above-mentioned two routine technologies, in fact, any in the one's own profession technology in all known silver salt solutions all can adopt.Use easily that the example of several silver salt solutions is the aqueous solution of silver nitrate and actol, the ethylene glycol solution of silver oxalate, silver acetate and silver carbonate and amine aqueous solution and silver nitrate.Like this, be benchmark with the catalyst weight, silver can be with 5% to 30%, and 5% to 25% content preferably is deposited on the surfaces externally and internally of carrier with the form of particulate.

Can from the metal of potassium, rubidium, caesium and compound thereof, pick out alkali metal or its compound, the preferably caesium that one or several member uses as the preparation silver catalyst.Wherein using easily, compound has nitrate, sulfate, hydroxide, oxide and acetate.Form with the aqueous solution or methanol solution or ethanolic solution or other similar alcoholic solutions is used this compound.Alkali metal or its compound can be added in the silver salt solution, be deposited on simultaneously on the carrier with silver then, and be benchmark to make a kg catalyst, its consumption preferably is no less than 0.003 gram equivalent 0.001 to 0.05 gram equivalent of scope, is not more than 0.03 gram equivalent.Alkali metal or its compound can be deposited on before deposition of silver on the carrier, also can be deposited on the carrier either-or behind the deposition of silver.

The activation processing that relates among the present invention can be implemented with the conventional method that adopts in this technology.For example, even employed silver salt and solvent species are different, activation can be implemented by thermal decomposition in air or inactive gas in about 150 ° to 400 ℃ temperature ranges.The thermal decomposition of the actol aqueous solution or organic acid silver salt amine aqueous solution can be used as an example and quotes.In other cases, when using silver nitrate aqueous solution, available hydrogen air-flow reducing process is carried out.Specific process by water or pure purging compound is implemented special activation.This method and other similar methods can adopt in the present invention.When using the sedimental activation method of washing, should be noted that the deposition that to carry out alkali metal or its compound at washing step later on again.

After following above-mentioned activation, the silver catalyst that contains alkali metal or its compound will carry out high-temperature process at 550 ° under the intensification of 950 ℃ of scopes in inactive gas, in the inactive gas, the volume ratio of oxygen content is not more than 3%, requires to be not more than 1%, preferably is not more than 0.1%.

Several examples of the inactive gas that is easy to use in high-temperature process comprise nitrogen, helium, argon gas, carbon dioxide and neon.The intensification scope of carrying out high-temperature process drops on 550 ℃ and spends to 950 ℃, preferably between 550 ° to 800 ℃.

The duration of high-temperature process is three minutes at least, the most handy 20 minutes.Temperature rises and does not calculate within the described duration fall time.

A kind of saying " finally " of using is in the present invention looked like and is meant the time that is between activation processing is finished and catalyst begins to degenerate, activation processing is exactly in 150 ℃ to 400 ℃ temperature ranges, the heat treatment of in air or oxygen-containing gas, carrying out, thereby its objective is and decompose and effusion organic component and unnecessary inorganic component activation silver compound and reaction accelerator, for example prepare used a kind of alkali metal or its compound in the silver catalyst with known method; " finally " or be meant with washing and remove unnecessary organic or inorganic component with after activation silver compound this step, follow water or lower alcohol solubilizing reaction accelerator, as alkali metal or its compound, then with the solution impregnation mixture that generates, dry used time of impregnated mixture.

As the employed silver compound solution that contains a kind of reduzate of method among the present invention (3), any of all solution known so far in the present technique can both use.For this purpose and effectively the solution that uses comprises: contain the liquor argenti nitratis ophthalmicus of rudimentary acid amide as single ethylene glycol of reduction components, in alkanolamine and other amine, be dissolved with different silver compound and contain the solution that different alkanolamines is made reduzate, and contain the silver nitrate aqueous solution of formalin as reduction components.

The several exemplary that are used as the low-grade amine of reducing agent comprise formamide, acetamide, propionic acid amine, ethanol acid amide and dimethyl formamide.That the exemplary of alkanolamine and other amine comprises is single-, two one and triethanolamine, list-, two-and tripropanol amine, list-, two-and triisopropanolamine, n-butanol amine and isobutyl hydramine.These reduzates all demonstrate reproducibility in common room temperature to 200 ℃ scope, the silver compound of dissolving is reduced into argent.

As the silver compound that raw material is used, any inorganic silver salt and organic silver salts that can form complex salt with rudimentary acid amide reaction can both use.The exemplary of silver compound comprises silver nitrate, silver carbonate, silver sulfate, acetate, actol, succinic acid silver and grape saccharic acid silver.

In catalyst, silver can be deposited on the surfaces externally and internally of carrier with the form of particulate, is benchmark with the catalyst weight that generates, and the content of depositing silver drops in 5% to 30% scope, preferably between 5% to 25%.

Optional a kind of one to three alcoholic extract hydroxyl group, two the aliphatic compounds of in molecular cell, containing of the solvent that uses to six carbon atom.The exemplary of lower aliphatic compound easy to use, be used as under the occasion of reducing agent at rudimentary acid amide especially, comprise ethylene glycol, diethylene glycol (DEG), triethylene glycol, propane diols, dipropylene glycol, methyl cellosolvo, ethyl cellosolvo, methyl carbitol, ethyl carbitol and glycerine.Other solvents easy to use have alkanolamine and water.

To alkali metal or its compound, can select the metal and the compound thereof of potassium, rubidium and caesium for use, the most handy caesium.Typical example has nitrate, sulfate, hydroxide, oxide and acetate.Alkali metal or its compound use with the form of the aqueous solution, or use with the solution form of methyl alcohol, ethanol, propyl alcohol or other lower alcohols.The amount of using is benchmark with one kilogram of catalyst of making, requires to drop on 0.0001 to 0.03 gram equivalent of scope, preferably between 0.0008 to 0.02 gram equivalent.

Now, to specifically describe the method for using rudimentary acid amide to prepare a kind of silver catalyst as reducing agent below.

Silver nitrate is dissolved in a kind of solvent (for example ethylene glycol), and the consumption of solvent is 1 to 20 times of silver nitrate weight, preferably 1 to 10 times.Add a kind of reduzate (for example formamide) in the solution that generates, addition is 0.5 to 5 times of mole number of silver components in the solution, preferably 1 to 3 times, fully stirs it.The saddle-shaped porous, inorganic refractory support of the Ying Telaokesi shape of a saddle or bohr that is shaped as of ormal weight is immersed mixed solution.The carrier that will soak heated 1 to 10 hour in 100 ℃ to 150 ℃ scopes.Thereby silver is just formed by reduction and is deposited on the outer surface of carrier and the inner surface of carrier pore with fine-grained form.

Water, the most handy boiling water washing disperses and has deposited the carrier of active silver on the inside and outside surface of pore.Washing can be removed the organic matter in the catalyst effectively, as formamide and ethylene glycol, has cleaned the surface of the active silver that generates simultaneously, has further activated silver.

After the washing, the carrier of depositing silver is heat drying in 50 ° to 150 ℃ temperature ranges.The catalyst that generates is immersed the aqueous solution that contains a certain amount of reaction accelerator, or in methyl alcohol, ethanol or other low-alcohol solutions.The catalyst that will soak heats in 50 ° to 150 ℃ scopes, to discharge solvent wherein by evaporation.The institute in steps in, should be careful, the temperature of avoiding heatable catalyst is above 200 ℃.

Produce in the oxirane by catalytic gas phase oxidation making ethene and molecular oxygen with the silver catalyst among the present invention, require to adopt a kind of in reacting gas volume content be that 0.1 to 10ppm halide is as the halogenation inhibitor, this halide can be chloride, bromide, fluoride and iodide, for example dichloroethylene, vinyl chloride, chlorinated diphenyl, monochlor-benzene and dichlorobenzene.

Use the silver catalyst among the present invention that ethene and molecular oxygen are produced in the oxirane by catalytic gas phase oxidation, can cause that when suppressing without halogenation the selectivity to oxirane descends, reaction temperature also rises.

Ethene and molecular oxygen are produced in the oxirane by catalytic gas phase oxidation when the halogenation inhibitor exists, and all conditions known in the art up to now can adopt.In commercial production scale, general condition is exactly, reaction temperature is 150 ° to 300 ℃ scopes, be preferably between 180 to 280 ℃, reaction pressure is preferably between 10 to 30 kilograms/square centimeter 2 to 40 kilograms of/square centimeter scopes, space velocity per hour 1,000 to 30,000(uses quota in short-term), preferably per hour 3000 to 8000(use quota in short-term).It is 0.5% to 40% ethene that feed gas by catalyst requires to contain volume ratio, 3% to 10% oxygen, and 5% to 30% carbon dioxide, all the other are inactive gas, as nitrogen, argon or water vapour and rudimentary hydrocarbon, as methane or ethane.

Now, narrate this invention in more detail by the operational instances and the comparative test of quoting below.The operational instances that this invention is not limited to here to be quoted as proof, and can under the situation that does not change spiritual essence of the present invention disclosed herein, implement otherwise.

The numerical value that conversion ratio of pointing out in this operational instances and comparative test and selectivity representative are calculated respectively by following formula.

Conversion ratio (%)=(participating in the ethene mole number of reaction)/(the ethene mole number in the feed gas) * 100

Selectivity (%)=(converting the ethene mole number of oxirane to)/(participating in the ethene mole number of reaction) * 100

Embodiment 1

300 milliliters of monoethanolamines are added in the thin pulp that is formed by 360 gram silver oxalates and 100 ml waters, fully stir and make it dissolving.100 ml waters are added mixture and the fully stirring that generates.Again 200 milliliters of aqueous solution that contain 2.3 gram cesium nitrates are added the diluted mixture solution that generates, fully stir to generate dipping solution.Be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3), spend the alpha-alumina supports of left and right sides preheatings with 4000 milliliters of this solution impregnation in Celsius temperature 100, the apparent porosity of this carrier is 55%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.32 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, and thickness (W) is 1.5 millimeters, and outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, apparent surface long-pending with the apparent volume ratio be 1.9/ millimeter.By heating, concentrate and dry impregnated carrier, in the air bath that Celsius temperature 120 is spent, heated three hours then, then in the air stream of Celsius temperature 280 degree, activate 48 hours.

Put the catalyst that generates into a container, this is that an external heat, internal diameter are that 25 millimeters, pipe range are 11,000 millimeters two-tube stainless steel reactor.

Is volume ratio 20% ethene, 7% oxygen, 7% carbon dioxide gas and remaining methane, nitrogen, argon gas and ethane, the mist that also contains millionth dichloroethylene is sent catalytic bed to, in reaction pressure is that 24 kilograms/square centimeter, space velocity are realization response under 5,500/ hours the condition.The results are shown in table 1.

Embodiment 2

Step according to embodiment 1 is prepared catalyst, and in reaction, use this catalyst, the consumption of different is cesium nitrate changes to 7.0 grams, 48 hours catalyst of activation in the air stream of Celsius temperature 280 degree is put into the stainless steel closed container that can be introduced inactive gas by the outside, when catalytic bed temperature keeps 670 ℃, be reflected at continuous nitrogen and flow down and carry out three hours.This reaction is to be undertaken by the step among the embodiment 1, the results are shown in table 1.

Embodiment 3

Prepare catalyst by the step among the embodiment 1, different is to replace being shaped as Ying Telaokesi shape of a saddle carrier with being shaped as bohr shape of a saddle alpha-alumina supports (Fig. 4-6), the external diameter (D) of bohr shape of a saddle carrier is 6.0 millimeters, thickness (W) is 1.5 millimeters, outer perimeter (A) is 15.4 millimeters, interior girth (C) is 6.2 millimeters, apparent surface long-pending with the apparent volume ratio be 1.9/ millimeter, what another point was different is to add 2.7 gram cesium nitrates in 200 ml waters.Reaction is undertaken by the step among the embodiment 1.The results are shown in table 1.

Reference examples 1

Catalyst is pressed the step preparation among the embodiment 1; different is to replace being shaped as the saddle-shaped carrier of Ying Telaokesi with the alpha-alumina supports that is shaped as Raschig ring (Fig. 7-9); the apparent surface of Raschig ring carrier long-pending with the apparent volume ratio be 1.3/ millimeter; external diameter (D) is 7.0 millimeters; internal diameter (B) is 3.0 millimeters; length (E) is 7.0 millimeters, and what another point was different is to add 3.7 gram cesium nitrates in 740 ml waters.Reaction also is to be undertaken by the step among the embodiment 1.The results are shown in table 1.

Reference examples 2

Catalyst is pressed the step preparation among the embodiment 1; different is to replace being shaped as Ying Telaokesi shape of a saddle carrier with the alpha-alumina supports (Figure 10-12) that is shaped as Raschig ring; the apparent surface of Raschig ring carrier long-pending with the apparent volume ratio be 2.1/ millimeter; external diameter (D) is 7.0 millimeters; internal diameter (B) is 4.8 millimeters; length (E) is 7.0 millimeters, and what another point was different is to add 2.3 gram cesium nitrates in 100 ml waters.Reaction is also carried out according to the step among the embodiment 1.The results are shown in table 1.

Reference examples 3

Catalyst is pressed the step preparation among the embodiment 1, different is with being shaped as sphere (3.2 millimeters of diameters), apparent surface is long-pending to replace being shaped as the saddle-shaped carrier of Ying Telaokesi with apparent volume than the alpha-alumina supports that is 1.9/ millimeter, and what another point was different is to add 4.4 gram cesium nitrates in 900 ml waters.Reaction is also undertaken by the step among the embodiment 1, the results are shown in table 1.

Reference examples 4

Catalyst is pressed the step preparation among the embodiment 1, and reaction is also undertaken by the step among the embodiment 1, and different is without dichloroethylene, the results are shown in table 1.

Reference examples 5

Catalyst is pressed the step preparation among the embodiment 3, and reaction is also undertaken by the step among the embodiment 3, and different is without dichloroethylene, the results are shown in table 1.

Continuous table 1

Embodiment 4

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.300 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 22.4 gram cesium nitrates are added the dilute solution that generates, fully stir.Thereby all set a kind of dipping solution.With 9000 milliliters of this solution impregnation be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3), in the alpha-alumina supports of 100 ℃ of left and right sides preheatings of temperature, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.40 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, length (E) is 10.0 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.Concentrate and dry impregnated carrier by heating, then in 120 ℃ of air baths, heated three hours, in 280 ℃ of degree air streams, activate 48 hours then.

The catalyst that so makes is put the sealing rustless steel container that can be introduced inactive gas by the outside into.Catalytic bed flows down at continuous nitrogen, and heating is three hours in 630 ℃ electric furnace.

Putting catalyst into an internal diameter is 33 millimeters, and catalytic bed length is 10, but the two-tube stainless steel reactor of 000 millimeter external heat.Introducing a volume ratio to catalytic bed is 20% ethene, 7% oxygen, the mist that 7% carbon dioxide and remaining methane, nitrogen, argon gas and ethane are formed, and be 24 Kilograms Per Square Meters in reaction pressure, space velocity is to carry out reaction in 30 days under 5,500/ hours the condition.Reaction result is shown in table 2.

Embodiment 5

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.300 ml waters are added the solution that generates, fully stir.Again 400 milliliters of aqueous solution that contain 21.5 gram cesium nitrates are added the diluted mixture solution that generates, fully stir to be prepared into a kind of maceration extract.Be shaped as the bohr shape of a saddle (Fig. 4-6) with 9000 milliliters of this solution impregnation, alpha-alumina supports 100 ℃ of left and right sides preheatings, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, and pore volume is 0.40 a cubic centimetre/gram, and external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 15.4 millimeters, and interior girth (C) is 6.2 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ of air baths, activated 48 hours then in 280 ℃ of air streams.

The catalyst that so makes is put the stainless steel airtight container that can be introduced inactive gas by the outside into, flows down heating three hours at continuous nitrogen, and catalytic bed temperature remains on 630 ℃.Use the reaction of this catalyst to be undertaken by the step of embodiment 4.The results are shown in table 2.

Embodiment 6

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.300 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 10.0 gram cesium nitrates are added the diluted mixture liquid that generates, fully stir to be prepared into a kind of maceration extract.With 9000 milliliters of this solution impregnation be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3), in the alpha-alumina supports of 100 ℃ of left and right sides preheatings, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.40 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, length (E) is 10.0 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.By heating concentrated and dry impregnated carrier, then in 120 ℃ air bath, heated three hours, in 280 ℃ air stream, activate 48 hours then.

Put the catalyst that so makes into the rustless steel container that can be introduced the sealing of inactive gas by the outside, flow down at continuous nitrogen, heating is three hours in electric furnace, and catalytic bed temperature remains on 570 ℃.Use this catalyst, react by the step of embodiment 4.The result shows table 2.

Embodiment 7

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.300 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 46.5 gram rubidium sulfates are added the dilute solution that generates, stir and make maceration extract.Be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3) with 9000 milliliters of this solution impregnation, alpha-alumina supports 100 ℃ of left and right sides preheatings, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.4 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, length (E) is 10.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ air bath, activated 48 hours then in 280 ℃ of air streams.

Put the catalyst that so makes into the sealing rustless steel container that can be introduced inactive gas by the outside, flow down at continuous nitrogen, heating is three hours in electric furnace, and catalytic bed temperature remains on 630 ℃.Use this catalyst to react by the step of embodiment 4.The results are shown in table 2.

Embodiment 8

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.300 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 19.4 gram potassium nitrate are added the dilute solution that generates, stir and make a kind of maceration extract.

Be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3) with 9000 milliliters of this solution impregnation, alpha-alumina supports 100 ℃ of left and right sides preheatings, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.40 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, length (E) is 10.0 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ air bath, activated 48 hours then in 280 ℃ of air streams.

Put the catalyst that so makes into the sealing rustless steel container that can be introduced inactive gas by the outside, flow down at continuous nitrogen, heating is three hours in electric furnace, and catalytic bed temperature remains on 630 ℃.Use this catalyst, react by the step of embodiment 4.The results are shown in table 2.

Reference examples 6

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir into solution.600 ml waters are added the solution that generates, fully stir.500 milliliters of aqueous solution that contain 25.0 gram cesium nitrates are added the dilute solution that generates, stir and make maceration extract.With this solution impregnation 9; 000 milliliter is shaped as Raschig ring (Fig. 7-9); alpha-alumina supports 100 ℃ of left and right sides preheatings; the apparent porosity of this carrier is 60%, and the specific area that records with the BET method is 0.7 meters squared per gram, and pore volume is 0.40 a cubic centimetre/gram; apparent surface long-pending with the apparent volume ratio be 1.3/ millimeter; external diameter (D) is 7.0 millimeters, and internal diameter (B) is 3.0 millimeters, and length (E) is 7.0 millimeters.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ air bath, activated 48 hours then in 280 ℃ of air streams.

Reference examples 7

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir into solution.1600 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 33.1 gram cesium nitrates are added the dilute solution that generates, stir and make dipping solution.Be shaped as sphere (3.5 millimeters of diameters) with 9000 milliliters of this solution impregnation, alpha-alumina supports 100 ℃ of left and right sides preheatings, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 4.0 a cubic centimetres/gram, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ air bath, activated 48 hours then in 280 ℃ of air streams.

Put the catalyst that so makes into the sealing rustless steel container that can be introduced inactive gas by the outside, flow down at continuous nitrogen, heating is 3 o'clock in electric furnace, and catalytic bed temperature remains on 590 ℃.Use this catalyst to react by the sequential steps of embodiment 4.The results are shown in table 2.

Reference examples 8

1240 milliliters of monoethanolamines are added in the thin pulp that is formed by 1440 gram silver oxalates and 300 ml waters, fully stir and make it dissolving.50 ml waters are added the solution that generates, fully stir.Again 500 milliliters of aqueous solution that contain 19.7 gram potassium nitrate are added the dilute solution that generates.With 9000 milliliters of this solution impregnation be shaped as Raschig ring (Figure 10-12), in the alpha-alumina supports of 100 ℃ of left and right sides preheatings; the apparent porosity of this carrier is 60%; the specific area that records with the BFT method is 0.7 meters squared per gram; pore volume is 0.40 a cubic centimetre/gram; apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter; external diameter (D) is 7.0 millimeters, and internal diameter (B) is 4.2 millimeters, and length (E) is 7.0 millimeters.By heating, concentrated and dry impregnated carrier then heated three hours in 120 ℃ air bath, activated 48 hours then in 280 ℃ of air streams.

Put the catalyst that so makes into the sealing rustless steel container that can be introduced inactive gas by the outside, flow down at continuous nitrogen, heating is three hours in electric furnace, and catalytic bed temperature remains on 640 ℃.Use this catalyst, react by the step of embodiment 4.The results are shown in table 2.

Reference examples 9

Catalyst is pressed the step preparation of embodiment 4.

Reaction is also undertaken by the step of embodiment 4, and different is without dichloroethylene, and reaction result is shown in table 2.

Reference examples 10

Catalyst is pressed the step preparation of embodiment 5.

Reaction is undertaken by the step of check experiment 9, the results are shown in table 2.

Embodiment 9

1600 gram silver nitrates are dissolved in 1.8 liters of ethylene glycol, add 636 gram formamides, fully stir the solution that generates, to be prepared into silver-colored maceration extract.

The same carrier of using among 9000 milliliters of embodiment 4 is immersed solution.Generating

Dip compound be heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stir two hours again to cause that the silver-colored dispersed deposition of reduction is on carrier.The deposition of silver catalyst that obtains thus in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ degree.Then the catalyst of drying is immersed in 2400 milliliters of ethanol that contain 4.52 gram cesium carbonates.The deposition of silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.React the step that adopts embodiment 4 with this catalyst.The results are shown in table 3.

Embodiment 10

1600 gram silver nitrates are dissolved in adding 636 gram formamides in 1.7 liters of ethylene glycol, fully stir, to be prepared into silver-colored maceration extract.

Be shaped as the bohr shape of a saddle (Fig. 4-6) to 9000 milliliters, alpha-alumina supports 100 ℃ of left and right sides preheatings immerses this dipping solution, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, and pore volume is 0.40 a cubic centimetre/gram, and external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 15.4 millimeters, and interior girth (C) is 6.2 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.

The dip compound that generates is heated to 130 ℃ of degree gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stirred again two hours, to cause that the silver-colored dispersed deposition of reduction is on carrier.With the deposition of silver catalyst that obtains thus in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ then.Then the catalyst of drying is immersed in 2300 milliliters of ethanol that contain 4.31 gram cesium carbonates.The deposition of silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.The step among the embodiment 4 is adopted in the reaction of carrying out with this catalyst, the results are shown in table 3.

Embodiment 11

1600 gram silver nitrates are dissolved in adding 636 gram formamides in 1.8 liters of ethylene glycol, fully stir, to be prepared into silver-colored maceration extract.

The same carrier of using among 9000 milliliters of embodiment 4 is immersed solution.The dip compound that generates is heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stir two hours again to cause that the silver-colored dispersed deposition of reduction is on carrier.The deposition of silver catalyst that so obtains in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ then.After this, dry catalyst is immersed in 2400 milliliters of ethanol that contain 9.61 gram rubidium carbonates.The deposition of silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.The reaction of carrying out with this catalyst is by the step among the embodiment 4.The results are shown in table 3.

Embodiment 12

Be shaped as the Ying Telaokesi shape of a saddle (Fig. 1-3) to 9000 milliliters, alpha-alumina supports 100 ℃ of left and right sides preheatings immerses this maceration extract, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.40 a cubic centimetre/gram, external diameter (D) is 6.0 millimeters, thickness (W) is 2.0 millimeters, outer perimeter (A) is 13.3 millimeters, interior girth (C) is 5.8 millimeters, length (E) is 10.0 millimeters, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.The dip compound that generates is heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stirred again two hours, to cause that the silver-colored dispersed deposition of reduction is on carrier.The deposition of silver catalyst that obtains thus in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ again.Then the catalyst of drying is immersed in 2400 milliliters of ethanol that contain 4.51 gram potassium acetates.The deposition of silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.The reaction of carrying out with this catalyst is by the step among the embodiment 4.The results are shown in table 3.

Reference examples 11

1600 gram silver nitrates are dissolved in adding 636 gram formamides in 2.14 liters of ethylene glycol, fully stir, to be prepared into silver-colored maceration extract.Be shaped as Raschig ring (Fig. 7-6) to 9000 milliliters; alpha-alumina supports 100 ℃ of left and right sides preheatings immerses maceration extract; the apparent porosity of this carrier is 60%; the specific area that records with the BET method is 0.7 meters squared per gram; pore volume is 0.40 a cubic metre/gram, apparent surface long-pending with the apparent volume ratio be 1.3/ millimeter, external diameter (D) is 7.0 millimeters; internal diameter (B) is 3.0 millimeters, and length (E) is 7.0 millimeters.The dip compound that generates is heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stir two hours again to cause that the silver-colored dispersed deposition of reduction is on carrier.The deposition of silver catalyst that so obtains in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ again.Then the catalyst of drying is immersed in 2700 milliliters of ethanol that contain 5.13 gram cesium carbonates.Dry between 80 ℃ to 100 ℃ the deposition of silver catalyst of so preparing.The reaction of carrying out with this catalyst is by the step among the embodiment 4.The results are shown in table 3.

Reference examples 12

1600 gram silver nitrates are dissolved in adding 636 gram formamides in 3.14 liters of ethylene glycol, fully stir, to be prepared into silver-colored maceration extract.Be shaped as sphere (diameter is 3.5 millimeters) to 9000 milliliters, alpha-alumina supports 100 ℃ of left and right sides preheatings immerses maceration extract, the apparent porosity of this carrier is 60%, the specific area that records with the BET method is 0.7 meters squared per gram, pore volume is 0.40 a cubic centimetre/gram, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter.The dip compound that generates is heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stir two hours again to cause that the silver-colored dispersed deposition of reduction is on carrier.With the deposition of silver catalyst that obtains thus in 9000 ml waters boiling washing several times, dry between 90 ℃ to 100 ℃ again.Then the catalyst of drying is immersed in 3700 milliliters of ethanol that contain 7.05 gram cesium carbonates.The deposition of silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.The reaction of carrying out with this catalyst is by the step among the embodiment 4.The results are shown in table 3.

Reference examples 13

1600 gram silver nitrates are dissolved in adding 636 gram formamides in 1.56 liters of ethylene glycol, fully stir, to be prepared into silver-colored maceration extract.Be shaped as Raschig ring (Figure 10-12) to 9000 milliliters; alpha-alumina supports 100 ℃ of left and right sides preheatings immerses maceration extract; the apparent porosity of this carrier is 60%; the specific area that records with the BET method is 0.7 meters squared per gram; pore volume is 0.40 a cubic centimetre/gram, apparent surface long-pending with the apparent volume ratio be 1.7/ millimeter, external diameter (D) is 7.0 millimeters; internal diameter (B) is 4.2 millimeters, and length (E) is 7.0 millimeters.The dip compound that generates is heated to 130 ℃ gradually, under this temperature, stirred two hours, be heated to 160 ℃ then, under this temperature, stirred again two hours, to cause that the silver-colored dispersed deposition of reduction is on carrier.Boiling washing is several times in 9000 ml waters with the deposition of silver catalyst that obtains thus.Dry between 90 ℃ to 100 ℃ again.Then the catalyst of drying is immersed in 2130 milliliters of ethanol that contain 4.04 gram cesium carbonates.The silver catalyst of so preparing is dry between 80 ℃ to 100 ℃.The reaction of carrying out with this catalyst is by the step among the embodiment 4.The results are shown in table 3.

Check experiment 14

Catalyst is pressed the step preparation among the embodiment 9.

Reaction is also undertaken by the step in the check experiment 9.Reaction result is shown in table 3.Check experiment 15

Catalyst is pressed the step preparation of embodiment 10.

Reaction is also undertaken by the step of check experiment 9.Reaction result is shown in table 3.

Errata

Errata

Claims

1, a kind of silver catalyst that is used to make ethene and molecular oxygen when the halogenation inhibitor exists, to produce oxirane by catalytic gas phase oxidation, it is characterized in that it contains silver and at least a accelerator that is selected from alkali metal and its compound, and silver-colored and accelerator is deposited on and is shaped as on the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr.

2, according to the silver catalyst of claim 1, the specific area that wherein said porous, inorganic refractory support has is in 0.01 to 10 meters squared per gram scope.

3, according to the silver catalyst of claim 1, the apparent surface of wherein said porous, inorganic refractory support is long-pending to drop on 0.1 to 10/ millimeter scope with the apparent volume ratio.

4, according to the silver catalyst of claim 1, the apparent porosity that wherein said porous, inorganic refractory support has is between 20% to 80%.

5, according to the silver catalyst of claim 2, the silver amount on the described carrier of wherein being deposited on be in described catalyst weight 5% to 30% between.

6, according to the silver catalyst of claim 5, the catalyst that each kilogram made wherein, described accelerator usage drops on 0.001 to 0.005 gram equivalent of scope.

7, according to the silver catalyst of claim 1, the specific area that wherein said porous, inorganic refractory support has is in 0.1 to 5 meters squared per gram scope.

8, according to the silver catalyst of claim 1, the apparent surface of wherein said porous, inorganic refractory support is long-pending to drop on 0.5 to 5/ millimeter scope with the apparent volume ratio.

9, according to the silver catalyst of claim 1, the apparent porosity of wherein said porous, inorganic refractory support is in 30% to 70% scope.

10, according to the silver catalyst of claim 1, the shape of wherein said porous, inorganic refractory support is the Ying Telaokesi shape of a saddle.

11, a kind of silver catalyst according to claim 10, the ratio pore volume that wherein said porous, inorganic refractory support has is 0.06 to 1.0 cubic centimetre/gram scope, outer perimeter (A) is 3 to 70 millimeters scopes, interior girth (C) is 1.5 to 68 millimeters scopes, thickness (W) is 0.1 to 4 millimeter scope, external diameter (D) is 0.5 to 20 millimeter scope, and length (E) is 0.5 to 65 millimeter scope.

12, according to the silver catalyst of claim 1, the shape of wherein said porous, inorganic refractory support is the bohr shape of a saddle.

13, according to the silver catalyst of claim 12, the ratio pore volume that wherein said porous, inorganic refractory support has is 0.06 to 1.0 cubic centimetre/gram scope, outer perimeter (A) is 3 to 70 millimeters scopes, interior girth (C) is 1.5 to 68 millimeters scopes, thickness (W) is 0.1 to 4 millimeter scope, external diameter (D) is 0.5 to 20 millimeter scope, and length (E) is 0.5 to 65 millimeter scope.

14, according to the silver catalyst of claim 1, wherein said alkali metal is an element that is selected from potassium, rubidium and the caesium at least.

15, according to the silver catalyst of claim 14, wherein said alkali metal is caesium.

16, a kind of method for preparing silver catalyst, the thin silver granuel dispersed deposition of this catalyst is at the outer surface of described porous, inorganic refractory support and the inner surface in hole thereof, be used to make ethene and molecular oxygen when the halogenation inhibitor exists, to produce oxirane by catalytic gas phase oxidation, the feature of this method is silver and at least a accelerator that is selected from alkali metal and its compound to be deposited on be shaped as on the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr, last product is no more than the 3%(volume in oxygen content) inactive gas in, in 550 ℃ to 950 ℃ scopes, stand high-temperature process.

17, according to a method of claim 16, the specific area that wherein said porous, inorganic refractory support has is in 0.01 to 10 meters squared per gram.

18, according to a method of claim 16, the apparent surface of wherein said porous, inorganic refractory support is long-pending to be compared 0.1 to 10/ millimeter scope with apparent volume.

19, according to a method of claim 16, the apparent porosity that wherein said porous, inorganic refractory support has is in 20% to 80% scope.

20, according to a method of claim 16, the silver amount that wherein is deposited on the described carrier is 5% to 30% of a catalyst weight.

21, according to a method of claim 16, wherein to per 1 kilogram of catalyst of making, the consumption of described accelerator is 0.001 to 0.05 gram equivalent of scope.

22, according to a method of claim 15, wherein said alkali metal is an element that is selected from potassium, rubidium and the caesium at least.

23, a kind of method for preparing silver catalyst, the thin silver granuel dispersed deposition of this catalyst is at the outer surface of porous, inorganic refractory support and the inner surface of hole wall thereof, be used to make ethene and molecular oxygen when the halogenation inhibitor exists, to produce oxirane by catalytic gas phase oxidation, the feature of this method is that handle is shaped as the Ying Telaokesi shape of a saddle or the saddle-shaped porous, inorganic refractory support of bohr is immersed in the silver compound solution that contains a kind of reproducibility compound, heat impregnated carrier, thereby make argent reduction dispersed deposition at the outer surface of carrier and the inner surface of its pore, then at least with a kind of mixture that is selected from the liquid scrubbing generation of water and lower alcohol, the mixture of dry wet, dried mixture is immersed in the solution that contains a kind of alkali metal and its compound at least, the mixture of dry wet, thus remove liquid component by vaporization.

24, according to a method of claim 23, the specific area of wherein said porous, inorganic refractory support is in 0.01 to 10 meters squared per gram scope.

25, according to a method of claim 23, the apparent surface of wherein said porous, inorganic refractory support is long-pending to be compared 0.1 to 10/ millimeter scope with apparent volume.

26, according to a method of claim 23, the apparent porosity of wherein said porous, inorganic refractory support is in 20% to 80% scope.

27, according to a method of claim 23 or 24, the silver amount on the above-mentioned carrier of wherein being deposited on be catalyst weight 5% to 30% between.

28, according to a method of claim 23, wherein to per 1 kilogram of catalyst of making, the consumption of described accelerator is 0.0001 to 0.03 gram equivalent of scope.

29, according to a method of claim 23, wherein said alkali metal is an element that is selected from potassium, rubidium and the caesium at least.