CN85103686A - The method for preparing silver catalyst - Google Patents

Abstract

Make with molecular oxygen with the hydrocarbon solution impregnating carrier of the silver salt of the eo-acid that is no less than seven carbon atoms and to makethe oxidation of ethylene to silver catalyst on the carrier of oxyethane.Anhydrous in fact this eo-acid that there is no in this solution.Preferable hydrocarbon solvent is toluene, dimethylbenzene, ethylbenzene, cyclohexane or isopropyl benzene.Make impregnated carrier drying, activation silver under the condition that can make the silver catalyst that oxyethane is had best selective, having is enough to increase the silver catalyst selectivity again, the optionally alkali metal soln dipping activatory silver catalyst when making it be higher than alkali metal-free and exist.Alkali-metal amount is best to the carrier of special selection on the finished catalyst, and with about 1～6 * 10 ^-3The gew/kg catalyzer is for well.Catalyzer also can contain additional promotor, and as alkaline-earth metal, barium is better.

Description

The method for preparing silver catalyst

The present invention usually is about with molecular oxygen the ethene vapor phase oxidation being generated the reaction of oxyethane, and this is the important reaction in the chemical industry.This reaction is carried out on the silver catalyst on the carrier usually.The present invention is particularly about preparing improving one's methods of above-mentioned catalyzer.

Many methods that prepare catalyzer disclose.Mc-Kim and Cambron list general in the prior art SOME METHODS in the paper of delivering on the Canadian Studies magazine (Canadian Journal of Research, Vol.27, Sec.B, No.11, P.815-6,1949).Since then, many other methods are disclosed.

Silver (compound) should dissolve, and silver compound decomposes the fine particle uniform distribution that is generated in activation afterwards so that allow.This available Silver Nitrate reaches, and comes to this usually in the preparation of silver catalyst in early days, because Silver Nitrate is soluble in water.Afterwards, use the silver salt of lower molecular weight carboxylic acid.Usually, these carboxylic acid silver salts are only water-soluble to a certain extent, then at day disclosure application 46-19606, United States Patent (USP) 3,702,259, English Patent 1,533 proposes to use solubilising complexing agent, for example ammonia and amine again in 813 documents such as grade.The silver salt of often mentioning is a silver lactate, and it contains a hydroxyl, and this has illustrated that it has the solubleness more higher than other carboxylic acid silver salt in water.Because it is very important preparing dense silver-colored solution during the impregnation catalyst agent carrier, obviously, the solubleness of silver salt in the aqueous solution of higher molecular weight is increased, and the skilled artisan in the art just can not propose to adopt the suggestion of this silver salt.As United States Patent (USP) 2,391, shown in 842, in the lubricating grease of preparation hydrocarbon, the salt of higher molecular weight lipid acid, for example silver stearate has been used as thickening material.Above-mentioned silver salt has only very limited solubleness in water.However, the higher molecular weight carboxylic acid silver salt is considered to the potential source of silver in the epoxyethane catalyst.

The silver salt of lipid acid is as disinfectant.At United States Patent (USP) 3,255, such description is arranged in 222: after making the silver salt of the various lipid acid that comprise capric acid, by with amine with contain the oxygen organic solvent, alcohol for example is the silver salt wiring solution-forming.Above-mentioned silver salt concentration is very low, so, can contain up to 15% or be obsolete for preparation greater than the silver catalyst of 15% silver, prepared the ammonia soln of silver salt, (referring to United States Patent (USP) 3,255,223) in addition.

Above-claimed cpd is relevant with the metallic soap as siccative or the like, and as at United States Patent (USP) 2,807, illustrated in 553, these compounds are water-insoluble solid normally, therefore, uses some organic solvents for many purposes.As at United States Patent (USP) 2,955, described in 949 like that, the coating siccative is to have the C of trialkyl acetate configuration ₈To C ₂₀Cobalt, manganese and the lead salt of synthetic acid is feedstock production.

At United States Patent (USP) 4,262, to speak of in 040, the palladium-Yin mixture that is used for decorative porcelain adopts neodecanoic acid silver preferable as a composition effect.But the preparation of this silver compound is not described.

In order to prepare silver catalyst,, can not think that the high-molecular weight silver salt has been extensive use of although often there is description to occur with the data that the carboxylic acid silver salt prepares silver catalyst.Recently some disclosed patents propose, the salt of water-soluble lower molecular weight, lactic acid salt for example, the Silver Nitrate of perhaps available amine solubilising or silver oxalate, seemingly a criterion.But, have now found that, can use water-fast higher molecular weight carboxylic acid silver salt, generate active and catalyzer optionally by following preparation method.

Be used to makethe oxidation of ethylene to the hydrocarbon solution impregnating carrier preparation that silver catalyst on the carrier of oxyethane can pass through eo-acid (as hereinafter definition) silver salt, this solution is anhydrous and no corresponding eo-acid basically; Carrier comprises aluminium sesquioxide, silicon-dioxide, silicon-dioxide-aluminium sesquioxide or their binding substances, and the surface-area of carrier is about 0.2～1.5m ²/ gm.Then, the carrier of dipping carries out drying, and by being heated to about 200 to 600 ℃ of temperature, is more preferably 250～500 ℃ and activates, and activates the enough time to produce active live catalyst, and silver-colored mean particle size is about 0.1～2 micron in the catalyzer.

Eo-acid is defined as in its molecule carboxylic acid group and is connected with the carbon atom that directly is connected with other three carbon atoms, perhaps is connected with other carbon atom that is connected like this.Preferred eo-acid is a neodecanoic acid, still, has seven or are available more than the eo-acid of seven carbon atoms.

Be more preferably from Cs, K and Rb and select at least a basic metal to add in the catalyzer, be improved to oxyethane catalyzer selectively.This catalyzer also can contain other promotor, and for example alkaline-earth metal is preferable with barium.These promotors also can be the salt of eo-acid.

New acid silver salt can be used prepared in various methods, particularly with silver compound and eo-acid prepared in reaction in the presence of solubilizing agent such as ethanol.Silver salt can precipitate from solution, and the remaining eo-acid of flush away free is dissolved in it in hydrocarbon solvent again, and preferred solvent is toluene, dimethylbenzene, ethylbenzene, hexanaphthene, or isopropyl benzene.

Finished catalyst can contain up to about 15%(weight) silver and about 8 * 10 ^-3The basic metal of gew/kg (gew=gram equivalent weight, gram equivalent), preferred 5～13%(weight) silver and up to about 7 * 10 ^-3The basic metal of gew/kg, most preferably 8～11%(weight) silver and about 1-6 * 10 ^-3The basic metal of gew/kg.

Preferred carrier is to contain the weight up to 15%() aluminium sesquioxide of silicon-dioxide, its surface-area is up to about 2m ²/ gm, particularly about 0.1～1.5m ²/ gm is especially with about 0.3～1.0m ²/ gm is for well.Preferred carrier can selectively adsorb basic metal from solution, preparation method of the present invention will utilize this characteristic exactly.

For making the characteristic optimizing of catalyzer, need to select alkali-metal add-on, this amount depends on the surface-area of selected carrier.Promptly used basic metal is many on having on the carrier of large surface area than the carrier that small surface area is being arranged.

Catalyzer of the present invention can use prepare in the oxyethane technology typical oxidizing condition with the ethene vapor phase oxidation under, and improved result is arranged.

Catalyst composition and preparation method

Preferred catalyzer prepared in accordance with the present invention contains up to about 15%(weight) silver, be expressed as metal, this deposition of silver is on porous refractory support surface and all in the holes.Silver content is greater than the 20%(weight of catalyzer total amount) be effectively, but the result is the catalyzer unnecessary expensive.About 5～13% the silver content of representing with metal according to the catalyzer total is better, and good especially with silver content 8～11%.

Catalyzer can be with the preparing carriers that comprises aluminium sesquioxide, silicon-dioxide, silicon-dioxide-aluminium sesquioxide or their mixture.Preferred carrier mainly contains α-aluminium sesquioxide, particularly contains up to about 15%(weight) aluminium sesquioxide of silicon-dioxide.About 0.1～the 1.0ml/gm of particularly preferred carrier porosity, with about 0.3～0.8ml/gm for well.Preferred carrier also has lower surface-area, is about 0.2～1.5m ²/ gm, particularly 0.3～1.0m ²/ gm.Above-mentioned surface-area is measured [J.Am.Chem.Soc.60,309-16(1983)] with the BET method.Porosity is measured with mercury porosimeter method; Referring to the paper of Drake and Ritter [Ind.Eng.Chem.Anal.Ed., 17,787(1945)].Aperture and pore size distribution are determined by the mensuration and the performance measurement method of porosity of surface-area.

Preferred carrier can selectively adsorb basic metal, particularly potassium, rubidium and caesium from alkali-metal solution.This meaning is exactly than depositing by the relatively large basic metal of being predicted by the amount and the concentration calculating of carrier adsorbent solution that has.It is not clear to finish the alkali-metal mechanism of absorption, still may comprise with other metal ion that exists on carrier carrying out ion-exchange.In this respect, it should be noted that Britain publication application GB2,043,481 A explanation is opposed to use and is contained and the tradable ionic carrier of basic metal (12 pages, 50 row).Yet, have been found that alkali-metal promoter action has increased when carrier can optionally adsorb alkalimetal ion.The preparation method of silver catalyst of the present invention comprises the measure of planning to utilize this feature of preferred vector.

Be the application in the oxyethane industrial production, wish carrier is processed into the ball, ball, ring-type etc. of regular shape." equivalent diameter " of wishing the carrier granule of use is 3～10mm, and be for well, common with 4～8mm, equivalent diameter and the internal diameter fit of wherein adorning the pipe of catalyzer.Equivalent diameter is the ratio of diameter and volume that the ball of identical outside surface (promptly ignoring the surface in the particle hole) is arranged under the carrier granule applicable cases.

Silver is by being added to carrier impregnation on the carrier in containing the eo-acid silver salt solution, and eo-acid has seven or more than seven carbon atoms, the eo-acid silver salt solution is anhydrous and above-mentioned eo-acid basically.Argentiferous liquid by absorb and (or) capillary action infiltrates in the hole of carrier.Available single dipping or series dipping, dry in the middle of being with or without, this part ground depends on the concentration of silver salt in the solution.In order to obtain the catalyzer of silver content in preferable range, suitable steeping fluid generally contains 5-50%(weight) silver (represent with metal, add) with new acid silver salt form.Certainly, the accurate concentration of use also depends on the characteristic of carrier, the concentration of liquid and the solubleness of new acid silver salt except the silver content that depends on requirement.

Just as already noted, steeping medium is called have seven or more than the organic solution of the new acid silver salt of seven carbon atoms of anhydrous basically and eo-acid.Obviously, the hydrocarbon solvent of use for example, generally is anhydrous toluene, hexanaphthene, dimethylbenzene, ethylbenzene or isopropyl benzene.Owing to when using method of the present invention, think that water is deleterious to the preparation silver catalyst, in silver-colored steeping fluid so the water that exists should be not more than about 0.1%(volume), with approximately less than the 0.01%(volume) for well.

Though mentioned the organic acid of higher molecular weight as a rule for the preparation silver catalyst in the past,, from the example of prior art, clearly see, with more low-molecular-weight acid such as lactic acid (hydroxy-propionic acid) or oxalic acid for well.These sour silver salt are slightly soluble in water, or compound complexing preparations such as available and ammonia, amine.Organic Silver Nitrate of also using, it is also water-soluble.Along with the acid molecule amount increases, it becomes more organic in nature, and no longer water-soluble to a great extent.The acid of higher molecular weight also can generate silver salt like this, and still, these salt often are insoluble to organic liquid.Have been found that in the preparation silver catalyst have seven or be useful more than the organic acid of seven carbon atoms., discussed in 949 at United States Patent (USP) 2,995 as Kirshenbaum, trialkyl acetate is effective especially, and this will see in example.Above-mentioned acid obtains as " eo-acid " is commercial, and generates by carbonylation and hydrolysis or by hydroformylation and oxidation from alkene.Because these acid dissolve in organic liquid, so their metal-salt is used as coating siccative etc., at this, they are more stable than naphthenate.For purposes of the invention, term " eo-acid " meaning is that the carboxylic acid group is connected on the carbon atom that directly is connected other three carbon atoms, perhaps is connected on other carbon atom of such connection.At least one is the part of long alkyl in these carbon atoms, and this alkyl makes this compound have organic trait.With neodecanoic acid for good especially.As commercial available, neodecanoic acid is 67%2-ethyl-2-methyl enanthic acid, 31%2, the 2-dimethyl is sad and 2%2, the mixture of 2-diethylacetic acid.Other commercial available acid is PIVALIC ACID CRUDE (25) and new enanthic acid.Usually, have seven or are available, yet neodecanoic acid is diffluent greater than the eo-acid of seven carbon atoms, preferred.Owing to have only seemingly such insoluble of the acid of straight chain carbon atom so that make the high silver concentration of preparation in fact impossible, so must consider the configuration of eo-acid.

As indicated such, deposition of silver is being by carrier impregnation being contained in the anhydrous hydrocarbon solvent of new acid silver salt, carrying out on the hole of solution absorption at carrier on the carrier.At temperature 30-120 ℃, typical dipping time was enough to make silver content up to 7-15%(weight in 1 to 60 minute) (in silver).

Except silver salt, the liquid of impregnated carrier can contain promotor, and alkaline-earth metal promotor for example is as barium.Opposite with common aqueous silver-colored solution, using anhydrous basically dipping solution is the feature of present method, and this solution is not easy to dissolve common metal-salt., preparation promotor new acid metal salt is feasible, and this salt is dissolved in silver salt and uses and the solvent selected, therefore, promoter metals is introduced in the silver-colored dipping solution.In other words, promotor can add by the secondary deposition behind deposition of silver, and the secondary deposition allows the wide solubility in used solution, promptly behind deposition of silver, may utilize the water-soluble metal salt promoter of solution deposition.

With the practice was opposite usually in the past, have been found that if obtain best specificity of catalyst to remove free acid.In the past, except silver salt, comprised also that some free acids were to use always as lactic acid.In the method, any free eo-acid does not promptly have going out separated of reaction with silver, stays the just silver salt of eo-acid in the steeping fluid.

Catalyzer is by the hydrocarbon solution impregnating carrier preparation with anhydrous new acid silver salt through selecting, the then silver of activation dipping.Secondly, can obtain the improved selectivity that ethylene oxy changes into oxyethane by solution impregnation activatory silver catalyst, although this is unwanted with alkali metal catalyst.

In one embodiment, the eo-acid of selection and silver suboxide, or alkali formula silver salt react as silver carbonate.Although be not important, have been found that in reaction mixture, to comprise solubilizing agent that for example Fatty Alcohol(C12-C14 and C12-C18), particularly ethanol or methyl alcohol are favourable.Usually, reaction mixture contains the 10%(volume of having an appointment) ethanol.Have been found that silver and sour complete reaction generally are inaccessible.Yet the generation of initial silver salt is carried out very soon, just stops at about 20% acid-respons afterreaction.In order to promote to generate more salt, the silver salt of generation comes out with precipitate and separate from reaction mixture.This can by add abundant excess ethanol in the reaction mixture basically all silver salt of generating of precipitation reach.Precipitate available usual method, for example filter or centrifugal removing, the remaining acid in the flush away solid.

Though the direct reaction as above-mentioned silver compound and eo-acid is preferred,, silver salt can be used and additive method similar in metallic soap technical field preparation, for example metathesis or method of fusion.

Dipping solution can be by dissolving washing in hydrocarbon solvent and the preparation of exsiccant throw out, and hydrocarbon solvent has toluene, ethylbenzene, dimethylbenzene, hexanaphthene, or isopropyl benzene.Preferably contain 7～15%(weight in order in single-steeping, to make to prepare) silver-colored silver catalyst, solvent can dissolve a large amount of silver salt., the adjustable ratio of solvent and silver salt joint, this is easily to the preparation catalyzer, and thinks not harsh.The typical proportions of spendable silver salt and solvent is 1/2～2/1, particularly about 2/1.Decide with solvent, silver salt and the ratio of the two, the temperature of dipping solution can be room temperature and be higher than room temperature, the result who obtains requiring.Also answer selective solvent, it can be removed easily, and reclaim for utilizing again.

The dipping of the carrier of selecting reaches with usual method, promptly in above-mentioned silver salt solution the impregnated carrier time enough with the hole of saturated carrier.Saturated carrier takes out from solution, gets rid of rest solution.After silver salt was added on the carrier, catalyzer activated by the particle of heating dipping, was heated to sufficiently high temperature with except that desolvating and decomposing silver salt, had at least a part to be decomposed into elemental silver.

The activation of silver can be by being heated to 200 to 600 ℃ of temperature, and preferred 250 to 500 ℃ are carried out, and in the presence of air that meets the requirements or hypoxic atmosphere to control the decomposition of silver salt.Temperature should be controlled so that the particle of silver changes into oxyethane to ethylene oxy high activity and stable, therefore, also can use even without the advantage catalyzer that obtains by secondary deposition basic metal.Temperature preferably is elevated to about 300 ℃ of maximum value gradually, and keeps top temperature about 1 hour, meets the requirements of size up to silver particles and is removed with all organic substances.In particularly preferred method, the carrier of dipping is being heated to about 100 ℃ within an hour, then, is heated to about 250 ℃ within 2 hours.Air, is present on the carrier surface to guarantee oxygen by being full of the carrier of silver with enough speed between pot-life.Though air is preferred gas, other gas also can use, and thinks that the existence of oxygen meets the requirements.Usually beginning to decompose the back temperature at silver salt raises.This temperature deviation can be controlled by the adjusting of activation condition.Activation with the impregnated carrier of thin layer distribution on the moving belt is useful especially, owing to guaranteed the even activation of catalyzer, can obtain average characteristics preferably.

When using basic metal, its amount on finished catalyst is general similar with previously used amount.Like this, sedimentary amount is generally up to 8 * 10 ^-3The gew/kg catalyzer is preferably up to about 7 * 10 ^-3Gew/kg, particularly about (1～6) * 10 ^-3Gew/kg(gew=gram equivalent weight, gram equivalent).Basic metal in the periodictable comprises sodium, lithium, potassium, rubidium, and caesium, though sodium and lithium needn't be got rid of, back three basic metal are particularly preferred, especially caesium.Basic metal is adding for example oxyhydroxide, nitrate, fontanelle compound, formate, and acetate, particularly acetate with various negatively charged ion bonded metallic compounds.Alkali metal compound can be dissolved in water or the alcohol-water solution expediently, preferably contains the aqueous ethanolic solution of enough water with the solubilising alkali metal compound.

By the catalyzer of method for preparing, in molecular oxygen vapor phase oxidation ethylene production oxyethane, improved application characteristic.Oxidation reaction condition, for example reaction conditions known in the prior art all can be used in the past.Reaction conditions generally includes about 150～400 ℃ of temperature of reaction, and general 200～300 ℃, reaction pressure 0.5～35 crust.Reacting feeding mixture contains 0.5～20% ethene and 3～15% oxygen usually, and rest materials, comprises comparison inert material, resembles nitrogen, carbonic acid gas, methane, ethane, argon, or the like material.The per pass catalyzer only has the part ethylene reaction usually, in the ethylene oxide product of separation requirement with for after preventing that the uncontrolled generation of rare gas element and by product from removing the air-flow and carbonic acid gas of suitable purification, and unreacted material Returning oxidation reactor.

Following embodiment will illustrate Preparation of catalysts and application according to the present invention, and support the front aspect those of the disclosed present method of severe condition, to reach satisfied result.Except as otherwise noted, to liquid and solid, all marks and percentage number average represent with weight, and gas composition then represents with mol%, and flow velocity is represented (promptly under 0 ℃ and 760mm Hg) with standard cubic meter per hour.Conversion of ethylene is that the mark of oxyethane is with general in the prior art percentage ratio selective presentation.

Embodiment 1

Prepare silver-colored dipping solution and be the 173gm silver suboxide is dissolved in the solution that 173gm dehydrated alcohol and 520gm neodecanoic acid (being provided by EXXON Chemical Co.) form, contain 67%2-ethyl-2-methyl enanthic acid, 31%2 in the neodecanoic acid, the 2-dimethyl is sad and 2%2,2-diethyl caproic acid.Neodecanoic acid and ethanol are mixed, and be heated to 80 ℃.Under vigorous stirring, increase progressively the adding silver suboxide.In order to clarify the solution of too early reduction silver, add 10 30% hydrogen peroxide.Dehydrated alcohol with 3000gm is added in the precipitation of neodecanoic acid silver then, and filters, and twice mixing pulping in 3000gm ethanol filters then, and at air drying.Form with neodecanoic acid silver reclaims about 85% silver suboxide.For the dipping of carrier, 217gm neodecanoic acid silver powder is dissolved in the 117gm toluene, and with mixture heating up to 80 ℃.

150gm solid support material (ring of Norton 5552,1/4 " * 1/4 ") is given heat to 85 ℃, and in neodecanoic acid silver-toluene solution, soaked 20 minutes.The carrier that suction filtration is saturated carries out program thermal treatment in air, decompose organic residue, and argent forms precipitation to be suitable for finished catalyst.The carrier of dipping exposes 1.5 hours to the open air with evaporation toluene at 100 ℃, exposes to the open air again under 250 ℃ then.When temperature approximately arrived 200～225 ℃, organic substance began to decompose, and makes temperature rise to 335～350 ℃ again, after 30 minutes, removes catalyzer from thermal source, subsequently cool to room temperature.

In order to improve the performance of fresh activation silver catalyst, with the solution impregnation of cesium acetate in water-ethanol admixture.The preparation of cesium acetate solution is that the 4.19gm cesium acetate is dissolved in the 15.8gm distilled water, and the solution of generation mixes with the 380gm dehydrated alcohol.In the solution that generates, contain 7000ppm(weight approximately) caesium.Above-mentioned dipping solution was by activatory silver catalyst bed circulation 2 hours, and suction filtration goes out excess solution, uses pure absolute ethanol washing catalyzer three times subsequently.With the catalyzer drying, be ground into 12～18 order particles then again to be used for test.By analysis, catalyzer contains 9% silver medal and 183ppm caesium (1.39 * 10 ^-3Gew/kg).Use the solution of making by the ethanol of 0.05gm cesium acetate and 0.5gm water and 9.8gm, the dipping dry catalyst, deposition is replenished 100ppm(weight) caesium.

This catalyst charge of 36gm is put into reactor, and reactor is that the U-shape stainless steel tube of 5.33mm is formed by internal diameter, and heats in molten salt bath.Incoming mixture consisted of 0.2% ethane, 14% ethene, 6.7% oxygen, 5.5% carbonic acid gas and 0.5ppm Ethylene Dichloride, all the other are the material of nitrogen, with gas space-time speed (GHSV) is 6000/ o'clock, pass through catalyzer, reaction pressure remains on 20.4 crust, temperature remains between 230～280 ℃, and its result is as shown in the table:

Table 1

Catalyzer silver caesium temperature of reactor discharge ring oxygen selective

(weight %) (ppm by weight) (℃) ethane (%)

Concentration (%)

1 9 260 236 1.52 82.3

Embodiment 2

If there is the free eo-acid in the silver salt solution, produce inferior catalyzer, this point will be found out by the following example.

Preparing silver-colored dipping solution is that 80gm silver suboxide and the solution reaction that is made of elementary neodecanoic acid of 240gm (being provided by EXXON chemical Co.) and the anhydrous industrial alcohol of 80gm (being provided by Ashland chemical Co.) are got final product, and silver suboxide added in 25 minutes.Hydrogen peroxide for 30 30% of settled solution addings.Evaporating solns is till the concentration of silver is 23.2 weight %.To generating every mole neodecanoic acid silver, 3 moles of free neodecanoic acids of needs.If when solution directly is used for preparing silver catalyst, just as described in example 1 above, precipitation is not a neodecanoic acid silver.

300 gram Nortion, 5552 support of the catalyst are immersed in the reducing solution of narration just now, taking-up was flooded after the carrier, extract excess solution out, then with carrier in baking oven in the air, 130 ℃ of heating 2 hours, 200 ℃ of heating 2 hours, 260 ℃ were heated 2 hours, and 300 ℃ of heating 2 hours.After the cooling, with the silver catalyst that the activated alcoholic solution double-steeping with caesium, as testing that embodiment 1 is narrated, its result is as shown in the table:

Table 2

Catalyzer silver caesium temperature oxyethane selectivity

(weight %) (ppm by weight) (℃) outlet (%)

Concentration (%)

2 8.6 154 250 1.52 79.6

The obtained result of the catalyzer of embodiment 2 than embodiment 1 obtain poor as a result, example 1 has been removed free neodecanoic acid.

Embodiment 3

As if when new acid silver salt was applied to carrier, solvent only was a kind of vehicle, still, find that solvent also has influence on the performance of finished catalyst, and its reason is not also understood this moment, still may comprise the decomposition of silver salt.This example shows the increase along with molecular weight, and the alkyl derivative influence as the benzene of neodecanoic acid silver solvent is also increased.

As embodiment 1,316gm is dissolved in the 166gm toluene the novel solid capric acid of preparation silver, and the solution of generation is used for flooding 464gm Norton5552 carrier.Behind the suction filtration excess solution, carry out drying, and in forcing air oven, be heated to 250 ℃ of impregnated carriers of activation by the program of being narrated as embodiment 1.The catalyzer that activated carries out double-steeping according to the program of embodiment 1 with the water-ethanol solution of cesium acetate.

For relatively, use dimethylbenzene to prepare catalyzer as solvent.165gm neodecanoic acid silver is dissolved in the 110gm dimethylbenzene, and floods 194gm Norton 5552 carriers as mentioned above like that.Impregnated carrier is placed on the mobile metallic sieve belt with an individual layer, and is exposed in 500 ℃ of air.Activated in about 2 minutes by belt.After the cooling, the activatory catalyzer carries out double-steeping with the hydrous ethanol solution of aforesaid cesium acetate.

The 3rd sample is by 142gm neodecanoic acid silver is dissolved in the 95gm isopropyl benzene, and prepares with 220gm Norton 5552 carrier impregnation.When lying in impregnated carrier on the mobile belt, be exposed in 500 ℃ the air two minutes and activate.

The catalyzer that activated uses the water-alcohol solution as the cesium acetate of narrating in the past to carry out double-steeping.

According to the program of embodiment 1, tested each sample of finished catalyst, its result is as follows:

Table 3

Catalyzer solvent silver caesium reactor oxyethane selectivity

(weight %) (ppm by weight) temperature exit concentration (%)

（℃） （%）

3a toluene 10.3 356 248 1.56 81.5

3b dimethylbenzene 7.47 212 246 1.49 82.8

3c isopropyl benzene 8.2 259 236 1,51 83.5

Basic metal and alkaline-earth metal are well-known as the promotor of silver catalyst.Usually adopt the aqueous solution from the Preparation of catalysts method of prior art, this just uses usually useful water-soluble basic metal and alkaline earth metal compound to become possibility.These compounds are insoluble in the applied organic solvent of preparation catalyzer of the present invention.If when these compounds are made the new hydrochlorate of the basic metal that is used for depositing silver and alkaline-earth metal, or during some approaching relevant homologues, they just can be used, will be from following embodiment as can be seen.

Embodiment 4

The aqueous solution of 50% cesium hydroxide of 11.27gm is added in the 6.50gm neodecanoic acid can generates the neodecanoic acid cesium salt, the uniform solution that evaporation produces, the crystallization of reclaiming the neodecanoic acid caesium.Again these crystallizations are added in the organic solution that contains neodecanoic acid silver, and are used for impregnated carrier.According to the program of embodiment 1,165gm neodecanoic acid silver is dissolved in the toluene of 86.3gm.Solution is removed by filter insoluble solid, add 0.365gm neodecanoic acid caesium then.Generate transparent even and stable solution.Impregnated carrier, and activate by embodiment 1 method, form a kind of promoted silver catalyst, when analyzing this catalyzer, find to contain 250ppm(weight) caesium

Though it is general that acid-base reaction generates the new hydrochlorate of silver, also may use other technology, for example by double replacement illustrated among the following embodiment (Double displacememt) method.

Embodiment 5

Neodecanoic acid and the reaction of 7.2gm sodium hydroxide of 31.1gm are generated neodecanoic acid sodium.Water is with this solution dilution to 500 milliliter.The 30.6gm Silver Nitrate is dissolved in prepares silver nitrate aqueous solution in the distilled water, being diluted with water to cumulative volume then is 500 milliliters.With two kinds of aqueous solution, generate neodecanoic acid silver again, and from solution, produce precipitation, leach solid and use distilled water wash, dry again.Thereafter, the method according to the embodiment of previous narration is used to prepare silver catalyst with the neodecanoic acid silver that makes.

Found that actual difficulty is that the application of method of the present invention is restricted, and should only not consider that prior art extends in the carboxylic acid of higher molecular weight, can see this point from the following example.

Embodiment 6

With 3.87gm silver suboxide and the new enanthic acid of 50gm (providing), in the 15gm dehydrated alcohol, in hot water bath, react the silver salt of generation neodecanoic acid in 80-85 ℃ by Exxon chemical Co..Some silver salt precipitate after 2 hours, but in order to obtain dissolved salt, and the additional ethanol of 1000ml is used for diluted reaction mixture, because dissolved salt is insoluble in the ethanol, and the precipitation that filtered and recycled produces, and before using, use washing with alcohol.

The new dissolving of enanthic acid silver in hydrocarbon solvent lacked than neodecanoic acid is silver-colored, 11gm enanthic acid silver is dissolved in the 87gm toluene at 85 ℃ prepare saturated solution.Filtering solution to be to separate insoluble solids, is used for preparing silver catalyst then.The peak concentration of silver only be a 1.5%(weight), this just makes and is difficult to acquisition to have typical silver content be 8-15%(weight) catalyzer.

Embodiment 7

Prepare the silver salt of PIVALIC ACID CRUDE (25) according to the program of embodiment 6, as mentioned above, silver salt precipitates in reaction mixture.Find that PIVALIC ACID CRUDE (25) silver is dissolved in aromatic solvent, ethanol acetone and the water hardly, therefore, can not prepare silver catalyst according to method of the present invention.

Reported and utilized α-ethyl acetic acid and capric acid to prepare silver catalyst, and obtained and be similar to these results that utilize PIVALIC ACID CRUDE (25) silver to be obtained.

The result who obtains with above various acid takes passages in following table.

From above-mentioned extracts, can find out the neodecanoic acid particularly suitable,, make it might prepare the silver catalyst that contains 8-15% silver because silver salt has sizable solubleness in toluene or similar aromatic solvent.Other sour silver salt is obsolete for actual purpose.Therefore has only about C with regard to the silver salt of considering eo-acid ₇Above eo-acid is just useful.Neodecanoic acid silver is optional especially to be because this acid obtains easily industrial, can use yet other generation dissolves in the eo-acid of the silver salt in the hydrocarbon solvent, and this also is to be considered within the scope of the invention.

Embodiment 8

Because neodecanoic acid silver is dissolved in the aromatic hydrocarbons fully, and gets industrial, so particularly useful.Yet the silver salt of higher molecular weight eo-acid also can be produced, and it seems that they are dissolved in the aromatic hydrocarbons, so that can prepare silver catalyst.

114.19gm silver suboxide and new three capric acid of 393gm (being provided by Exxon chemical Co.) are reacted in the 30gm dehydrated alcohol, generate new three capric acid silver salt.As with neodecanoic acid, new three capric acid are not pure compounds, be sure of to contain the various acid of the configuration of " newly ", this configuration as previous definition, average about 13 carbon atoms.New three capric acid silver salt backflow after one hour, is added 5 30% hydrogen peroxide, generate clear soln.New three capric acid silver and responseless new acid mixture mix with excess ethanol (about 3000cc), and the silver salt precipitation makes might be easy to separate silver salt from unreacted acid.Contrast with the neodecanoic acid silver that obvious crystallization is arranged and form suspension in ethanol, new three capric acid silver forms the thickness piece of compression, uses the washing with alcohol solid, removes most of unreacted eo-acids.

The new three capric acid silver of 194.3gm are dissolved in the 77.7gm isopropyl benzene prepare catalyzer.Contain in the solution than may Duo 20% silver at least with neodecanoic acid silver.According to usual method, with silver-colored solution impregnation 278gm Norton 5552 carriers, impregnated carrier activates on the belt moisture eliminator of above-mentioned narration.

Claims (18)

1, preparation is applicable to that the method that ethylene oxy changes into the silver catalyst on the carrier of oxyethane comprises:

(a) with the hydrocarbon solution impregnating carrier of new acid silver salt, the anhydrous in fact and no said eo-acid of said solution, said carrier comprises aluminium sesquioxide, silicon-dioxide, aluminium sesquioxide-silicon-dioxide and binding substances thereof,

(b) from said solution, isolate impregnated carrier in (a), and in the presence of molecular oxygen the new isolated vectors of heating, to be long enough to produce the fresh silver catalyst of activatory heat-up time.

2, according to the process of claim 1 wherein that said silver salt is to have 7 or more than the silver salt of the eo-acid of 7 carbon atoms.

3, according to the method for claim 2, wherein said silver salt is a neodecanoic acid silver.

4, according to the process of claim 1 wherein said silver salt is dissolved in the hydrocarbon solvent, this hydrocarbon solvent is selected from by toluene.At least a in one group of material that dimethylbenzene, ethylbenzene, hexanaphthene and isopropyl benzene are formed.

5, be not more than about 0.1% water according to the process of claim 1 wherein that said silver salt solution contains.

6, according to the process of claim 1 wherein that said silver salt active catalyst contains the silver of the 15 weight % that have an appointment.

7, according to the process of claim 1 wherein that the surface-area of said carrier is up to about 2m ²/ gm.

8, according to the process of claim 1 wherein that said silver salt is by the prepared in reaction in the presence of solubilizing agent with silver compound and said eo-acid.

9, method according to Claim 8, wherein said solubilizing agent is ethanol.

10, method according to Claim 8, wherein said silver salt are isolating by the precipitation agent of introducing the said silver salt of separation.

11, according to the method for claim 10, wherein said isolated silver salt is washed to remove free acid.

12, according to the method for claim 1, wherein said silver salt is by an alkali metal salt with said eo-acid and the said eo-acid of alkali-metal oxyhydroxide reaction generation, and the silver salt of following said an alkali metal salt and the said eo-acid of silver compound reaction generation prepares.

13, according to the method for claim 1, it also comprises the following steps: (C) catalyzer with the activation in the solution double-steeping (b) of at least a alkali-metal compound, this basic metal is selected from least a in one group of material being made up of caesium, potassium and rubidium, generate finished catalyst, contain up to about 8 * 10 in every kilogram of finished catalyst ^-3The said basic metal of gew.

14, according to the method for claim 1, it comprises that also an alkali metal salt with eo-acid is added to the step in the dipping solution of (a), said basic metal is selected from least a in one group of material being made up of caesium, potassium and rubidium, presents in an amount at least sufficient to make in every kilogram of finished catalyst of production contain up to about 8 * 10 ^-3The basic metal of gew.

15, according to the method for claim 13 or 14, wherein said basic metal is caesium.

16, according to the method for claim 13 or 14, wherein said alkali-metal content is about (1-6) * 10 ^-3Gew/ kilogram finished catalyst.

17, generate the method for oxyethane with molecular oxygen oxidation ethene, this method is under oxidizing condition, adopts any one described catalyzer among the claim 1-16.

18, any method narrated in fact in the present invention or product or equipment or and any combination.