CN1068320C - Process for making alkylene oxide - Google Patents

Abstract

Catalysts for the production of alkylene oxide by the epoxidation of alkene with oxygen comprise a silver impregnated support containing a sufficient amount of manganese component to enhance at least one of activity and/or efficiency and/or stability as compared to a similar catalyst which does not contain manganese component.

Description

The production method of alkylene oxide

This patent application is the U.S. Patent application 340242 of application on April 18th, 1989 and 340390 part subsequent application, and this paper should be in conjunction with the above-mentioned two parts of applications of reference.

The invention relates to alkene, especially the method for corresponding alkylene oxide of ethylene epoxidizing system such as oxyethane is wherein used argentiferous loaded catalyst, this catalyzer contain can improve stability and/or efficient and/active dosage contain the manganese composition.

Industrial, oxyethane is to carry out epoxidation reaction by ethene in the presence of temperature that raises and silver-containing catalyst to make.For raising the efficiency or catalyzer optionally of process for making ethylene oxide is provided, carried out number of research projects.

Utilizing oxygen or oxygen-containing gas and ethene to react in the presence of silver catalyst and producing oxyethane is an old flourishing technology.For example, US2040782 (mandate on May 12nd, 1936) has introduced the method for oxygen and ethene prepared in reaction oxyethane in the presence of the silver catalyst that contains a metalloid promotor.Leforte is explanation in the US20370 (May 18 nineteen thirty-seven) that announces again, and alkene is directly combined with molecular oxygen in the presence of silver catalyst, can generate alkylene oxide.Hereafter, prior art is tried one's best, and concentrates and improves the efficient of catalyzer in producing the oxyethane process.

When explanation feature of the present invention, the definition of used term " transformation efficiency ", " selectivity " and " yield " such as US3420784 (mandate on January 7th, 1969), the 3rd hurdle, 24-35 is capable described.The definition of " selectivity " and US2766261, the 6th hurdle, the capable and US3144916 of 5-22, definition was consistent described in 58-61 was capable." yield " and " transformation efficiency " definition in the prior art is not quite similar, so do not adopt as the definition among the above-mentioned US2766261.The used in the whole text term of specification sheets and claim " efficient " and " selectivity " are synonyms.

The silver catalyst that production oxyethane is used has experienced huge variation since the development phase at its initial stage.According to the prior art report, when loading to silver granuel on the solid support material at first, do not note very much carrier characteristics such as specific surface, pore volume and unreactiveness.Along with the development of technology, develop the special technique that relates to the argentiferous carrier of better effects if in the method for ethene and oxygen reaction epoxy ethane.Today, most silver catalyst carrier is the particulate material of moulding.These carriers can be put into inside reactor, and the gaseous product of reactant gases and reaction can flow in these particulate materials and on every side, and reclaims behind the reactor of flowing through.The particle diameter of carrier and shape are variable factors, through specific particle diameter and the shape of selecting, need the factor considered simultaneously with other, and the pressure that depends on reactor used, desired gas flow velocity and pass reactor falls.

The carrier of Shi Yonging generally all is that the inorganic materials that normally has mineralogical property is made by inorganic materials always.In most cases, preferred carrier is made by Alpha-alumina, as described in following patent documentation: US2294383 for example; US3172893; US3332887; US3423328 and US3563914.

The carrier that is used for most (if not whole words) the industrial epoxyethane catalysts of preparation all is to be produced by the company that does not produce this catalyzer.The method of general these carriers of preparation belongs to carrier manufacturer far reaching trade secret.Consequently, catalyst manufacturers can not know how carrier is made.Some factors are arranged, as the raw materials used purity of preparation carrier and other physico and the method that prepare carrier, concerning preparation be used to produce successful catalyzer especially the carrier of needs, be vital.

The silver that loads on these carriers is considered to exist with the fine particle form, because can only see this phenomenon with present microtechnique.Patent documentation points out that the particle diameter of silver is a factor that influences catalyst effect, and as a rule, utilizes the ordinary method of prior art, can obtain the silver of fine particle.The prior art can be referring to as US2554459; US2831870; US3423328 (specifying the silver granuel that adopts 150-400 ); US3702259 (disclosing the method for preparation particle diameter) and US3758418 (disclosing the silver granuel of particle diameter) less than 1000 less than 1 micron silver granuel.To the improvement of the micro-test of silver catalyst aspect, make to one can observe that even the particle size range of littler value.

Can adopt some kinds of technology that silver is loaded on the carrier, but two kinds of the most frequently used technology comprise: a kind of is to use silver-colored solution impregnating carrier, then the carrier after soaking is heat-treated, make deposition of silver on carrier, another kind be utilize the silver-colored precipitator method or silver is prefabricated into slurries and with silver-colored coated to carrier, when like this carrier being added the liquid of heat extraction on it, silver granuel just deposits on the carrier and is bonded in carrier surface.Exemplified various method in the different United States Patent (USP)s, as US2773844; US3207700; US3501407; US3664970 (referring to GB754,593) and US3172893.

The surface-area that carrier provided in the process of exploitation silver catalyst is a considerable exercise question always.The disclosure that relates to support of the catalyst surface-area aspect can (wherein disclose: 0.002-10m referring to US2766261 ²The surface-area of/g is more suitable); US3172893 (wherein having described porosity and the 80-200 micron pore size of 35-65%); US3725307 (has wherein introduced less than 1m ²The mean pore size of the surface-area of/g and 10-15 micron); US3664970 (wherein the porosity minimum of the carrier of Cai Yonging be about bore dia of 30%, at least 90% in the scope of 1-30 micron, and the mean value in these apertures is the 4-10 micron); And US3563914 (wherein the support of the catalyst of Li Yonging has less than 1m ²The particle diameter of the surface-area of/g, the pore volume of 0.23ml/g and 0.074-0.30mm).The prior art preferred surface is amassed little inert Alpha-alumina.

With regard to the impurity that exists in known catalysts and/or the gas phase reaction had considerable influence for a long time.In early days in the technology development process, also fubaritic or measure these impurity.Therefore can not find these impurity roles.But, even in the initial period of technological development, the promotor this point with basic metal is produced oxyethane as silver-colored catalysis method just has been widely known by the people in the prior art.The US2177361 that publishes October nineteen thirty-nine just once illustrated the application of basic metal in silver catalyst.US2238471 points out, make promotor with lithium and meet the requirements very much, but as when adopting its amount to be essentially the potassium hydroxide of 10wt% of the used silver suboxide of preparation catalyzer or cesium hydroxide, potassium and caesium are exactly deleterious.Thereafter, the US2404438 explanation, sodium and lithium are effective promotors of this reaction.Visible substantially similar explanation from US2424084.US2424086 generally mentions with basic metal and makes promotor, but has specifically noted sodium.The patentee of US2671764 (the vitriol patent of Sacken) believes that the promotor of making this class silver catalyst with alkali-metal vitriol is very effective.This patentee specifically notes that also the vitriol of available sodium, potassium, lithium, rubidium or caesium makes promotor.

US2765283 has introduced with the dilute solution of chlorine-containing compound carrier has been carried out pretreated method, points out simultaneously, and this chlorine-containing compound should be an inorganics.The suitable muriate of specifically enumerating comprises sodium-chlor, lithium chloride and Repone K.This patent specifies that the amount that deposits to the chloride mineral compound on the support of the catalyst is the 0.0001%-0.2% of vehicle weight.The US2615900 of Sears has described the purposes of metal halide in handling loaded catalyst, particularly points out, but the halogenide of these halogenide basic metal such as lithium, sodium, potassium and caesium.The charge capacity of metal halide is the 0.01%-50% of argent weight.This patent also specifies, with the halid mixture of generally enumerating in this article of single metal, can strengthen novel catalyst compositions useful highlightedly in the performance of break-in period simultaneously again can be during the normal operation that is extended, activity of such catalysts is remained on appropriateness and stable level.That is, handle catalyzer, may make the initial activity of catalyzer quite high at short notice, and another kind of metal halide may make catalyst activity remain on the level of appropriateness in long-time with a kind of specific metal halide.This patent thinks that the metal halide on the catalyzer can burn into the reaction of carbonic acid gas by ethene suppressing, so these materials are categorized as catalyst-initiator or anticatalysis material.

US2709173 has introduced the purposes of silver catalyst in preparation oxyethane, wherein silver is loaded on the solid carrier, muriate, bromide and the iodide of any metal halide such as lithium, sodium, potassium, rubidium in the load simultaneously are with the whole process of production of reinforced epoxy ethane.This patent is specifically noted, wishes to adopt the low dose of consumption less than about 0.5%.This patent lay special stress on, preferred alkali metal halide proportional range is about 0.0001-about 0.1%.Explanation simultaneously, though preferred catalyst compositions contains independently promotor, this point is always unessential, because preparation is during catalyzer, alkali metal halide can be converted into the corresponding alkali metal oxide compound to a certain extent, and this oxide compound plays the promotor effect.As if US2766261 has absorbed the instruction among the US2238474, thinks that caesium and the potassium in the silver catalyst is deleterious, suggestion is made promotor with sodium and lithium.But US2769016 finds that available sodium, potassium, lithium are made the promotor of silver catalyst.This patent also advises with the dilute solution of sodium-chlor, lithium chloride or Repone K carrier being carried out pre-treatment.

People's such as Gould US2799687 explanation adds metal halide by Sears in scope described in the US2615900 and can not get best effect.Particularly using alkali metal halide, when being specially the muriate of sodium and potassium and oxide compound, really so.This patentee's suggestion remains on 0.01-5wt% with the inorganic halides composition in the catalyzer, preferably in the 0.01-0.1wt% scope (with " oxidable silver-colored catalysis composition ", the weight that promptly changes the silver salt of elemental silver into is benchmark).US3144416 mentions with various metals and makes promotor, and one of them is a caesium.US3258433 points out that sodium is effective promotor.The US3563913 suggestion is made promotor with basic metal such as lithium compound.It is said that the preferable amount of promoter species is that benchmark is 0.03-0.5% by the metal oxide compound with the vehicle weight.US3585217 claims that " known " alkali metal chloride " hinders the reaction that generates carbonic acid gas ", " can be impregnated in catalyzer ".The disclosed loading type silver catalyst of US3125538 contains the basic metal on the common deposited, and this basic metal is selected from potassium, rubidium and caesium, by determining that with respect to one of silver grammeatom is than deposition.The consumption of preferred silver is the 2-5% of catalyst weight.This patentee's explanation, the characteristics of this catalyzer are the reactions that is specially adapted to nitrogen oxide and propylene.Method embodiment among the foregoing US3702259 itself has made same catalyzer, and this patent expands it to and is used to prepare oxyethane.US3962136 and US4012425 also disclose and same catalyzer can be used to prepare oxyethane.US3962136 has introduced basic metal and silver has been deposited on the carrier simultaneously.The last existence form of basic metal on carrier is oxide compound, and this oxide compound is made up of caesium, rubidium or both mixtures, optionally is combined with the oxide compound of the potassium of trace.Oxide compound dosage is about 4.0 * 10 ^-5The gew/kg catalyzer is to about 8.0 * 10 ^-3The gew/kg catalyzer.US4356312 has introduced the purposes of same catalyzer.US3962136, a parent application of US4010115 and other United States Patent (USP), the very significant data that have some to be worth mentioning in the U.S. Patent application 317349 of application on December 21st, 1972.According to the embodiment 2 that comprises some contrast experiments, prepared the catalyzer of the potassium that a kind of 310PPM of containing adds simultaneously, and when finding, the reaction that generates oxyethane has not been had activity used as ethylene oxide catalyst.

US4207210 is (corresponding to belgian patent 821439, based on GB specification sheets 1489335) disclose, employing order preparation method, basic metal is added on the carrier, the catalyzer of making is equivalent to US3962136, US4012425, the catalyzer of making in the so-called parent application of quoting among the US4010115.So, as if in the face of this open and US4033903 and the disclosed content of US4125480, promptly the back adds one or more in potassium, rubidium or the caesium on the exhausted silver-containing catalyst, is difficult to determine the key of the alkali-metal method of deposition on catalyzer.As if above-mentioned back is a kind of openly to show that this processing can make the ability of catalyzer be regenerated, thereby improves generating the selectivity of oxyethane.Another part patent, it is suitable with the effect that adds or add simultaneously earlier to add the effect that basic metal such as caesium obtain after promptly US4066575 tends to think.

The disclosed preparation oxyethane of embodiment in Germany's prospectus 2640540 contains sodium and potassium, rubidium or caesium thrin with silver catalyst.

Japanese Patent Application Publication specification sheets 95213/75 is about process for making ethylene oxide, and wherein the catalyst system therefor composition comprises silver, barium, potassium and the caesium of determining atomic ratio.This article table I has been summarized the result of use of various catalyst compositions in the example.

The disclosed preparation oxyethane of US4039561 contains silver, tin, antimony, thallium, potassium, caesium and the oxygen of determining atomic ratio with catalyzer.

Belgian patent 854904 disclosed silver catalysts contain the mixture of various sodium and caesium.UK Patent Application 2002252 disclosed loading type silver catalyst in table 2 contains the various mixtures of caesium and thallium, and the some of them catalyzer also contains potassium or antimony in addition.US4007135 loosely discloses production alkylene oxide silver catalyst (the 2nd hurdle, 25-30 is capable), this catalyzer contain silver " with at least a lithium, potassium, sodium, rubidium, caesium, copper, gold, magnesium, zinc, cadmium, strontium, calcium, niobium, tantalum, molybdenum, tungsten, chromium, vanadium and the barium of being selected from that helps catalytic amount ... promotor ".US3844981 and US3962285 disclose catalyzer and the epoxidizing method of alkene in the presence of many metal ingredients.Catalyzer in No. 3962285 patents contains one or more and a large amount of silver in palladium, ruthenium, rhenium, iron and the platinum of trace.In the method for making of the catalyzer of No. 3844981 patent disclosures, used a kind of decomposable salt of iron group in periodic table of elements 7b family, 1b family or the 8th family.This salt preferably is selected from gold, copper, rhenium, manganese and molysite.Though patentee's consideration points out that these metals are to exist with metallic state, under epoxidation reaction condition, one or more in these metals may be oxidized as rhenium, forms metallic oxo-anions.

US2605239 discloses the purposes of making promotor with beryllium oxide.Metal such as copper, aluminium, manganese, cobalt, iron, magnesium, gold, thorium, nickel, caesium and zinc that other can make promotor have also been advised.These promoter metals are added in the catalyzer by mechanically mixing or co-precipitation mode.

European patent discloses the mixture that 0003642 the disclosed silver-containing catalyst of table 3 comprises potassium and caesium, discloses a kind of catalyzer that contains sodium and caesium simultaneously.

Belgian patent 867045 disclosed loading type silver catalysts contain lithium and its amount basic metal much less, that be selected from caesium, rubidium and/or potassium of so-called significant quantity.

Belgian patent 867185 disclosed ethylene oxide production contain true quantitative potassium and the another kind of at least basic metal that is selected from rubidium and caesium with loading type silver catalyst.

The English Patent 2043481 of common transfer has been introduced caesium and another kind of at least basic metal synergistic combination, and loads to the catalyzer of making on the inert support with silver, and its performance is better than known those catalyzer of prior art at that time.These catalyzer have been widely used for industrial production.The basic metal composition is loaded to available various methods on the carrier.An alkali metal salt can be added on the carrier, this article has been introduced many an alkali metal salts.What specifically exemplify is with a kind of as in the multiple adoptable alkali metal compound of alkali metal sulfates.

European patent application 85237 has been introduced a kind of epoxyethane catalyst, and the applicant thinks that they wash by alcohol, makes caesium and/or rubidium quilt " chemical absorption " on support of the catalyst.

Japanese Patent Application Publication 56/105750 discloses the epoxyethane catalyst that contains cesium molybdate or wolframic acid caesium or boric acid caesium except that other content.It is said that this catalyzer is with the 0.07wt% of sodium content less than alumina supporter, and be that the Alpha-alumina of 1-5m2/g constitutes mainly by specific surface.Decomposed silver salt solution impregnated carrier with alkali metal containing boron complex, basic metal molybdenum complex and/or alkali metal tungstate complex compound.The specific examples of unexposed anion mixture.57/21937 disclosed containing in the thallium catalyzer of Japanese Patent Application Publication, but thallium borate or titanate.

On December 12nd, 1987 disclosed european patent application 247414 disclosed catalyzer contain can salt the form basic metal and/or the barium that add.Salt comprises nitrate, vitriol and halogenide.US4761394 and 4766105 disclosed catalyzer contain the rhenium composition, as rhenium oxide, rhenium positively charged ion or rhenate or perrhenate negatively charged ion.A disclosed concrete catalyzer is made with silver oxalate, cesium hydroxide, ammonium perrhenate and ammonium sulfate in No. 4761394 patents.No. 4766105 patent provides many examples that contain the silver catalyst of caesium, rhenate and collaborative cocatalyst salt.List the 7-1 of this patent report below, 7-2,7-3,7-4, the situation of 7-12 and the several experiments of 7-27.Experiment Ag, % Cs, ppm Re, other composition of ppm, ppm is initial

S ₄₀, % T ₄₀, ℃ 7-1 14.3 236 0 does not have 80.0 2427-2 13.9 360 186 and does not have 80.6 2417-3,14.2 438 372 nothings, 81.9 2487-4,13.3 405 186 (NH ₄) ₂SO ₄, 83.1 259

32(S)7-12 13.5 328 186 KMnO ₄,55(Mn)?80.8 2427-27 14.3 293+7Li 186 (NH ₄) ₂SO ₄,82.4 245

Provided S in 32 (S) this patent ₄₀And T ₄₀Definition, be respectively that the OTR measured in the time of 16 ± 4 hours is 40% o'clock efficient and a temperature.

Can find out several phenomenons from these data.Rhenate can be raised the efficiency, especially some " collaborative cocatalyst " as sulfate anion in the presence of, all the more so.In addition, when increasing the rhenate consumption or adding the collaborative cocatalyst that can raise the efficiency, as a rule, 40% oxygen transforms required temperature (" T ₄₀, ℃ ") also raise.Add the Mn of 55PPM (with KMnO among the experiment 7-12 ₄Form adds) look to S ₄₀(selectivity during OTR 40mol%) or T ₄₀Almost not influence.

Though wish to improve the efficient that changes into oxyethane, the temperature of following rising (being loss of activity) also is very thorny thing to industrializeding catalyst.The industrial installation of oxyethane generally all is to operate keeping productive rate and efficient to reach under the condition of required balance.Active lower catalyzer is turned round, to reach required productive rate under comparatively high temps.But the upper limit of catalyst temperature scope is restricted, therefore, for given transformation efficiency, the catalyzer that initial temperature is higher, its useful life is shorter.Concerning ethylene oxide production manufacturer, not only catalyzer is a big cost, and in order to take out spent catalyst, with the raw catalyst typical tubular fixed bed ethylene oxide reactor of packing into, device is stopped production significant period of time.So, lack as 2 years or effective work-ing life for more time, because of efficient improves the income that obtains, will lose at catalyzer and replace expense and install on the off-time.

M.M.Bhasin applies on February 20th, 1987 but shows in the resigned U.S. Patent application 18808, on August 13rd, 1984 application but in existing resigned No. 640269, and in No. 251573 of on October 3rd, 1988 application and No. 251814 U.S. Patent applications, the argentiferous loaded catalyst of production oxyethane is disclosed.This catalyzer contains the cesium salt of oxo-anions, and the ordination number of this oxo-anions is at least 15-83, and from the periodic table of elements (by chemical rubber company, (Cleveland Ohio) publishes, and sees CRC materialization handbook, the 46th edition, inside back cover) 3b-7b family and/or 3a-7a family.The oxo-anions that can exemplify out comprises vitriol, phosphoric acid salt, manganate, titanate, tantalate, molybdate, vanadate, chromic salt, zirconate, polyphosphate, tungstate, cerate or the like.Following table has been summarized the several examples in No. 251573 patent applications.Example number Ag, % Cs salt, other salt of consumption, use amount efficiency, the % temperature, ℃ 15 13.09 00 73.5 238 23 13.55 CsMnO ₄, 0.0101% 0 79.7 240 29 13.25 CsMnO ₄, 92ppm Cs KMnO ₄, 27ppm K 79.6 249 30 13.25 CsMnO ₄, 95ppm Cs KMnO ₄, 28ppm K 76.0 254

H ₂SO ₄, 48ppm 34 14.1 CsMnO ₄, 51ppm Cs KMnO ₄, 152ppm K 59.6 281 examples the 15,23,29, the 30th are carried out under oxygen method condition, and example 34 is to carry out under air method condition.Generality has been introduced oxygen method and air method in the literary composition.

Proposed manganese is used in the catalyzer of other purposes.For example, September 29 nineteen eighty-two, disclosed UK Patent Application 2095242A disclosed alkane carries out oxi-chlorination in the presence of the solid particle catalyst composition method, and this catalyst composition comprises one or more in (1) argent and/or its compound and (2) manganese, cobalt or the nickel compound.August 24 nineteen eighty-two, disclosed Japanese Patent Application Publication 57/136941 disclosed ozone decomposition catalyst.This catalyzer is that the silver of 0.1-20wt% and the cobalt oxide of 1-20wt% (by the atomic percent of cobalt) are added on the Manganse Dioxide and make.People such as Imamura are at " Oxidation ofCarbon Monoxide Catalyzed by Manganese-Silver Composite Oxides ", J. of Catalysis, vol, 109, PP198-205 (1988) and " Effectof Samarium on the Thermal Stabilityand Activity of the Mn/Ag Catalyst inthe Oxidation of CO ", J. of Catalysis, vol.115 discloses carbon monoxide oxidation manganese-silver catalyst in PP258-264 (1989) two literary compositions.US4800070 is with the katalysis of nitrate one nitrite system about separated oxygen from oxygen-containing gas such as air.This catalyzer comprises the transition metal oxide that is selected from manganese oxide, ruthenium oxide, rhenium oxide, osmium oxide, rhodium oxide, iridium oxide and composition thereof.

Need to seek improve produce the active and/or stable method of the loading type silver-containing catalyst that oxyethane uses, the efficient of these catalyzer is improved, but when it provides required efficient, it is active general lower, be used for industrial installation, must under comparatively high temps, turn round.But this higher service temperature can excessively shorten life of catalyst, makes it lose magnetism to full scale plant.

The loading type silver-containing catalyst of alkene epoxidation system alkylene oxide that is applicable to provided by the invention has enhanced activity and/or efficient and/or stability.This catalyzer contains deposition at least a manganese composition, q.s thereon, and does not contain this manganese composition, but the identical similar catalyst of other condition compares, and a kind of performance in its activity and/or efficient and/or the stability is enhanced at least.The dosage of manganese composition usually is at least about 20 or 60,70-1000 according to appointment, and preferably 80-500PPM (weight) by the weight of manganese, is a benchmark with the catalyzer gross weight.Can enhanced activity and/or the dosage of the manganese of efficient and/or stability change with the character and the consumption of other composition in the catalyst composition usually.

Catalyzer of the present invention preferably contains the manganese composition of the enhanced activity of the dosage that is enough to improve catalyst activity at least, is about to actively improve at least about 5 ℃ down in oxyethane standard technology condition (this paper definition), is preferably at least about 10 ℃.

After activity of such catalysts improves, determine that the required temperature of amount alkylene oxide (using the increase of the alkylene oxide concentration by beds to represent usually) can reduce determining to produce under the condition.The stability of catalyzer can be in efficient rate of ageing and the active rate of ageing at least a.Efficient rate of ageing and/or active rate of ageing than stable catalyst are lower than the catalyzer of less stable.

Term used herein " compound " is meant that a kind of concrete element passes through surface and/or chemical bond such as ionic linkage and/or covalent linkage and/or coordinate bond bonded binding substances with another kind of or several different elements.Term " ionic " or " ion " are meant the chemical electrically charged part on the electronics; " cationic " or " positively charged ion " is positively charged, and " anionic " or " negatively charged ion " is electronegative.Term " oxygen anion " or " oxygen anion " refer to contain the electronegative part of at least one and another element bonded Sauerstoffatom.Be that oxygen anion is oxygen containing negatively charged ion.Can understand, ion is not present in the vacuum, but but combines with the counter ion of balancing charge.

Catalyzer preferably contains at least a other promotor, compares with the similar catalyst that does not contain this promotor, and its content will be enough to improve the efficient of catalyzer.This promotor often comprises the compound of a kind of element beyond the demanganization, this element be selected from the periodic table of elements (by chemical rubber company, Cleveland, Ohio publishes, at CRC materialization handbook, the 46th edition inside back cover) 1a and/or 2a and/or 3b-7b or 3a-7a family.Preferred promotor comprises beyond the deoxygenation that 3b-7b family and 3a-7a family ordination number are the oxygen anion of those elements of 5-83 in the periodic table of elements.Most preferred promotor is one or more in the oxygen anion of nitrogen, sulphur, tantalum, molybdenum, tungsten, rhenium.Many this promotors have the advantages that to improve catalyst efficiency and reduce catalyst activity two aspects.The existence of manganese composition can obviously improve the activity of such catalysts as the oxygen anion that contains promotor as vitriol and one or more 3b-7b family elements such as molybdenum and rhenium.

Another preferred version of the present invention is, catalyzer contains the rhenium composition, but this rhenium composition positively charged ion or negatively charged ion, as rhenate.

Another preferred version of the present invention is that the epoxidation reaction of alkene in the presence of oxygen-containing gas comprises, under epoxidation conditions, in the presence of the right gaseous state member of at least a redox half-reaction of raising the efficiency, alkene contacted with catalyzer.This catalyzer comprises that at least a its amount as promotor can strengthen the salt of a right member of the redox half-reaction of efficient strengthened efficient.

In another preferred version of the present invention, catalyzer comprises base metal nitrate, and especially saltpetre and/or rubidium nitrate, particularly its content are benchmark greater than about 400 or 500PPM (weight) with potassium weight.In this invention scheme, can be added to the reaction zone that catalyzer is housed, with at least a performance in raising activity of such catalysts, efficient and the stability with the compound of nitrogenous and oxygen such as nitrogen oxide, nitrogen peroxide, Nitrous Oxide etc. as collaborative cocatalyst.

In another preferred version of the present invention, catalyzer contains less than about 50PPmw, the best potassium that leaches less than 25PPmw.Under some situation, under low like this potassium content, the manganese composition has more enhancement.

One aspect of the present invention is about above-mentioned catalyzer being used for alkene epoxidation system alkylene oxide, the especially purposes of ethene epoxy ethane.

With the alkylene oxide of Preparation of Catalyst of the present invention, available following structural characterizes:

R in the formula ¹And R ²Be low alkyl group such as methyl or ethyl or hydrogen preferably.Most preferred alkylene oxide is an oxyethane.Alkylene oxide is by corresponding alkene such as R ¹HO=CHR ²Make.Being easy to understand, will be that example is discussed with oxyethane and ethene below.

The feature of catalyzer of the present invention is, catalyzer is compared with the similar catalyst that does not contain this composition in conjunction with a kind of manganese composition of q.s, and activity of such catalysts and/or efficient and/or stability are enhanced.Though this catalyzer can use, for the purpose of the manganese composition that whether adds q.s in determining catalyzer, can adopt the processing condition of one group of standard under very wide different technology conditions.

The oxyethane standard technology condition (abbreviation standard " condition ") that is used to characterize catalyzer of the present invention comprises makes the full gas re-circulation that comprises carbonic acid gas by the back-mixing stream autoclave of employing standard simultaneously.This condition allows some change of ethene, the gentle phase stopper of oxygen material in operation.Exemplified two kinds of technologies: the air method, adopt industrial air method to produce the typical process condition of oxyethane, promptly provide molecular oxygen by air, in back-mix-flow reactor, carry out simulated operation; The oxygen method adopts industrial oxygen method to produce the typical process condition of oxyethane, promptly uses molecular oxygen, carries out simulated operation in back-mix-flow reactor.Though the efficient difference of each method, its rule are that in fact in all experiments of making oxygen source with air, the efficient that the efficiency ratio of the generation oxyethane that more a spot of oxygen of usefulness and ethene obtain is made oxygen source with molecular oxygen is hanged down 2-4 percentage point.If catalyzer contains the right salt of a kind of redox half-reaction, and when attempting to be used in combination with the right gaseous state member of redox half-reaction corresponding, that can strengthen efficient, standard conditions provide this gaseous state member.Under following standard entry condition, standard conditions are to make the oxyethane that 1.0mol% is arranged in the exit gas: composition air law part oxygen method condition

The half-reaction that (when using vinyl chloride, for half of its amount of optimised quantity of optimised quantity) ppm can be raised the efficiency and can be raised the efficiency to the chloroethanes of mol% mol% oxygen 6.0 8.0 ethene 8.0 30 ethane 0.5 0.5 carbon dioxide 6.5 6.5 nitrogen surplus surplus ppm can be raised the efficiency gas can raise the efficiency attitude member (when the optimised quantity of the optimised quantity of catalyst needs)

Standard conditions are utilized stirring-type back-mixing stream " Magnedrive " autoclave of the well-known end, see Fig. 2 of " gas phase catalysis research reactor " literary composition of J.M.Berty, and this article is seen chemical engineering progress, the 70th volume, the 5th phase, 78-84 page or leaf, 1974.

Pressure is held constant at 275psig, and the general export flow remains on 22.6SCFH, the accurate temperature and pressure of SCFH index, and promptly ℃ and under the 1atm, cubic feet per footage hourly.By the conditioned reaction temperature, the exit ethylene oxide concentration is remained on 1.0%.Like this, with regard to usable temp (℃) and the performance of catalyst efficiency reflection catalyzer.

Under the standard conditions, the catalyst test method comprises the following steps:

1. the back-mixing of the 80CC catalyzer being packed into stream autoclave.The catalyzer of packing in the graduated cylinder of internal diameter 1 inch raps for several times, catalyzer is adorned fully measured its volume number after real, also can calculate catalyst volume from the amount of carrier tap density and silver and additive.Write down the weight of catalyzer.

2. at nitrogen flow rate 20SCFH, under the propeller rotating speed 1500rpm condition, back-mixing is flowed autoclave be heated to about temperature of reaction.Cut off nitrogen then,, the exit gas total flux is transferred to 22.6SCFH by above-mentioned streams.In afterwards several hours, attemperation makes discharge ring oxidative ethane concentration be approximately 1.0%.

3. afterwards in 4-6 days, monitoring outlet ethylene oxide concentration has reached its steady state operation performance to determine catalyzer.The periodic adjustment temperature makes the discharge ring oxidative ethane reach 1%.Obtain selectivity and the temperature of catalyzer thus to oxyethane.

According to aforesaid method, the standard deviation of the catalyst efficiency that single test produces is about 0.7% efficiency unit.According to aforesaid method, the standard deviation of the catalyst activity that single test produces is about 1.2 ℃.Certainly, standard deviation depends on the quality of testing equipment used and the precision of technology, so change.Can think that the experimental result of this paper is within above-mentioned standard deviation.By repeatedly testing and utilize the square root of experiment number, can reduce standard deviation.

The content of manganese composition generally will be enough to make activity to improve at least 5 ℃ under oxyethane standard technology condition, preferably at least 10 ℃.More wish to adopt the condition of oxygen method.When measuring active increasing, method and catalyzer all are under the steady state conditions, and can usually definite rapidly steady state conditions that is reached.In some cases, catalyzer reaches before the highest initial activity, activate even reach a week or longer time.The reason that some long catalyst activation phase is not still understood, and may be because of due to the chemistry of these catalyzer and/or physics regulates.So will after preferably about 120-170 hour, measure active again catalyzer operation at least 24 hours usually.

The optimum content of manganese composition can become with the content of silver content, other cocatalyst and chemistry, the physical property of type and carrier.But, the content of manganese composition often is 60ppmw (umbers of per 1,000,000 parts of weight) at least, by manganese weight.The manganese component content is too high, can influence the performance of catalyzer, as efficient and/or activity.Too low as its content, also may influence catalyst performance.When determining the manganese composition of required dosage, the manganese component content can the change back and forth with the catalyzer of performance to be evaluated in the catalyst composition.Sometimes wish to change other composition as silver and other cocatalyst content, to obtain the optimum performance of favourable combined effect and catalyzer.Usually the content of manganese composition is counted about 70-1000 by manganese weight, preferably 80-500ppmw.

Can various forms as with covalent linkage compound form as Manganse Dioxide, or provide the manganese composition with positively charged ion or negatively charged ion such as manganate anionic form.But the species of the manganese of enhanced activity and/or stability are still uncertain, and that composition that may add exactly also may be the species that produce in Preparation of Catalyst or use.Though can not be appreciated that specifically that still catalyzer provides the species form of the manganese of advantageous feature, as in catalyzer, add permanganate (MnO ₂ ^-) the manganese composition of form, general effect is all relatively good.Manganese that also available oxidation state is higher such as manganate (MnO ₄ ^-) and the manganese positively charged ion (as Mn (NO ₃) ₂), but need certain soak time this moment.In addition, the manganese composition difference of adding, it is also different to reach the required optimum content of certain effect.In the manganese composition oxidation state of manganese often be+2 ,+3 ,+4 and/or+7, preferably+3 ,+4 and/or+7.

The manganese composition includes, but is not limited to manganous acetate, manganous ammonium sulfate, manganese citrate, manganous dithionate, manganous oxalate, manganous nitrate, manganous sulfate and manganate negatively charged ion such as permanganate negatively charged ion, manganate negatively charged ion or the like.When adopting negatively charged ion, can acid, or add the manganese composition with the form of salt more frequently.The salt of above-mentioned salt such as 1a, 2a, 1b or 2b family, or ammonium salt such as alkaline or alkaline-earth salts such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium etc.The mixture of also available manganate composition.

For any production oxyethane catalyzer that optimum performance is provided, exist dependency between many factors.The factor that often is taken into account comprises: (ⅰ) character of carrier; (ⅱ) on the carrier or carrier in silver content; (ⅲ) on the carrier or carry intravital each composition and content thereof; (ⅳ) silver or other composition with impurity or pollutent; (ⅴ) program of preparation catalyzer; (ⅵ) condition of usefulness Catalyst Production oxyethane.

But, when attempting to limit any catalyzer, a basic value must be arranged, make and to determine other factors on this basis, especially when each factor is variable, make each factor determine its meaning according to this basic value.Among the present invention, but this basic value silver content, or the combination of silver content and carrier character.In most cases, incite somebody to action a kind of combination in back as basic value.Owing to have the basic value of two kinds of values formation catalyst performances at least, so the relation between these array configurations and the other factors is obviously very complicated.There is not a kind of common logic clue, can all these array configurations and/or factor are integrated.Therefore, put into practice the present invention and need make great efforts by experiment, to reach all of the present invention or whole basically advantages.Do not deviating under this paper situation, those of ordinary skills can be easy to realize the optimum operation performance of catalyzer of the present invention.It will be appreciated that the technician when any epoxyethane catalyst capable of being industrialized of preparation, generally follows this paper spirit.The technology that each key element of this paper is adopted when depending on the preparation catalyzer.

Silver content can be in 2-45wt% or higher value in the finished catalyst, and being everlasting changes between about 2-40wt% or the higher value, and industrial preferable range is the about 35wt% of about 6wt%-.Consider that from economic angle silver content is preferably lower.But, the best silver content on any concrete catalyzer will depend on economic factors and performance characteristic such as catalyst efficiency, catalyst aging speed and temperature of reaction.

In some catalyzer of the present invention, the outward appearance of discrete silver granuel is a polygon or irregular on the finished catalyst and/or on the used catalyst, sometimes look it is general parallelepiped-shaped, or even general cubes, these are different with sphere that has usually as disclosed catalyzer among the US3702259 or semisphere outward appearance.Particle overall dimension is often less than about 0.2, and is more normal less than about 0.1 micron.

Carrier in these catalyzer or supporter are selected from a large amount of porous high-temperature catalyst carrier or support body material in wide region, these materials ethylene epoxidizing material, product exist and reaction conditions under be considered to suitable inert.The material of many this respects is all for well known to those of ordinary skill in the art, and it still can be natural or synthetic, and preferred macroporous structure.

Chemical constitution to carrier there is no strict restriction.Carrier can be by constituting as Alpha-alumina, silicon carbide, silicon-dioxide, zirconium white, magnesium oxide and various clay.Preferred carrier is the alpha aluminium oxide particle that often is bonded together by tackiness agent, purity is very high, as the Alpha-alumina of 98wt% at least, other composition can be other containing metal of silicon oxide, alkalimetal oxide (as sodium oxide) and trace and/or contain nonmetallic additive or impurity; Carrier also can purity hang down the i.e. Alpha-alumina of about 80wt%, and surplus is silicon-dioxide, various alkalimetal oxide, alkaline earth metal oxide, ferric oxide and other metal and nonmetal oxide.Carrier is mixed with under Preparation of Catalyst and reaction conditions and is inertia.Various these class carriers all can buy on market.Alumina supporter is by United Catalysts, Inc., and Louisville, Kentucky and the NortonCompany, Akvon, Ohio produces.

Those are contained the carrier of Alpha-alumina, the preferred about 0.03m of carrier specific surface ²The about 10m of/g- ²/ g, better about 0.05-is about 5, the about 3m of better about 0.1- ²/ g (B.E.T. method mensuration), the water pore volume of measuring with conventional water adsorption technology is about the about 0.85CC/g of 0.1-(volume).B.E.T. method survey specific surface sees Brunauer for details, S., Emmet, P. and Teller, the J.Am.Chem.Soc. of E., 60,309-16 (1938).

The carrier that contains Alpha-alumina of preferred especially some type.These Alpha-aluminas have aperture quite uniformly, can utilize the about 0.1m of (1) B.E.T. specific surface ²The about 3.0m of/g- ²/ g, preferably about 0.1m ²The about 2.0m of/g- ²/ g and the about 0.85CC/g of the about 0.10CC/g-of (2) water pore volume, 2 of the about 0.75CC/g of preferably about 0.25CC/g-characterize more fully.The about 0.01-100 micron of the intermediate value bore dia of above-mentioned carrier, preferably about 0.5-50 micron.These carriers can have the pore distribution of a kind of form, two kinds of forms or various ways, and their general characteristic can find in the literature and be listed in the following table I.

Table I carrier A B C D E FB.E.T. surface-area m ²/ g (a) 0.21 0.42 0.42 0.48 0.57 2.06 water pore volume CC/g 0.26 0.36 0.41 0.49 0.44 0.65 crushing strength, FPCS. pound (b) 100% 97% average 21 90% 90% No data

20 pound of 15 15-30 14 15 total pore volume .Hg.CC/g, (c) 0.26 0.42 0.42 0.46 0.42 0.65 average pore size .Hg. , (c) 620 560 640 550 770 1000 mean pore sizes .Hg. μ m, (c.e) the 3.7 2.7 3.4 3.4 2.4 2.5 pore volume percentages greater than the hole of 350 , (c) the 90.0% 88.5% 89.5% 89.1% 91.5% 94.1% pore volume percentages greater than 1 μ m hole, (c) 87.0% 82.5% 83.4% 82.3% 83.5% 61.0%

Table I (continuing) carrier A B C D E F Alpha-alumina, the Na that wt% 99.5 98 98.5 98.5 98 70-75 water can leach, the Na that ppmw 12 53 21 24 18 No data acid can be leached, the K that ppmw 40 96 87 51 45 No data water can leach, the Fe that ppmw 5 22 21 22 10 No data acid can be leached, ppmw 25 No data 15 data SiO ₂, wt% 0.5 2 1.5 15 2 25-30 (a) Brunauer.Emmet and Teller measuring method are seen above-mentioned quoted passage.(b) dull and stereotyped crushing strength, the individual particle ball.(c) immersing mercury with accurate poroscope 9200 automatically or 9210 types (130 ° of contact angles, the surface tension of Hg are 0.473N/m) measures to 55000psia.(e) mean pore sizes represent total pore volume 50% hole diameter less than or greater than mean pore sizes.

No matter the character of used carrier how, its shape is particle, bulk, sheet, ball shape, annular, sphere and wheel shape etc. preferably, and size will be applicable to fixed-bed reactor.Typical commonly used commercial fixed bed ethylene oxide reactor is made up of the many pipes of vertically arranging (in a suitable shell), and the external diameter of these pipes approximately is the 0.7-2.7 inch, and when internal diameter was 0.5-2.5, the filling length of catalyzer was 15-45 Foot.In these reactors, can use a kind ofly can form certain garden shape, as sphere, ball shape, the carrier of annular and sheet etc., its diameter is when about 0.1-0.8.

With regard to loaded catalyst widely, best performance depends on the optimizing of carrier, the chemical constitution of carrier (comprising impurity), surface-area, porosity and pore volume in other words.But, adopt the present invention, when use was not optimized carrier, the raising of performance can be the most tangible.These have obtained the confirmation of embodiment, have wherein used various carriers.

Catalyzer of the present invention preferably contains another kind of at least cocatalyst or properties-correcting agent to improve the performance of catalyzer except that containing the manganese composition, for example raise the efficiency or reduce the incendivity of oxyethane or influential to activity.These cocatalysts or properties-correcting agent generally provide with compound.

For the ease of understanding, cocatalyst can be divided into the positively charged ion cocatalyst, as basic metal and alkaline-earth metal and negatively charged ion cocatalyst.Alkalimetal oxide or MoO ₃And so on non-ionic compound can change into ionic compound, as transforming in Preparation of Catalyst with between the usage period.Whether take place no matter transform, they all are expressed as positively charged ion and negatively charged ion at this, as basic metal or molybdate.

Usually, catalyzer contains basic metal and/or alkaline-earth metal as the positively charged ion cocatalyst.Basic metal and/or alkaline-earth metal can exemplify out lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium and barium.Other positively charged ion cocatalyst comprises 3b family metal ion, and they comprise scandium, yttrium, lanthanum and lanthanide series metal.In some cases, cocatalyst comprises positively charged ion such as caesium and another kind of at least alkali-metal mixture, and to obtain synergistic function, as English Patent 2,043,481 is described.Certainly, the positively charged ion cocatalyst can be used as opposite ion and offers manganese negatively charged ion composition.Cesium salt usually uses separately or uses with other salt binding.

In many cases, preferred catalyzer comprises that at least a atom sequence number is 5-83 and is selected from periodic table of elements 3b-7b or the salt of the oxo-anions of the element of 3a-7a family (deoxygenation is outer).In some cases, have found that the sum total of desired basic metal that offers catalyzer of the anion ratio that is added and alkaline-earth metal some more be useful.The reason that excessive negatively charged ion is useful it be unclear that.Excessive negatively charged ion can add with forms such as acid, ammonium salt and amine salt, and perhaps a part of basic metal and/or alkaline-earth metal add with the salt form of acid, for example cesium hydrogen sulfate.

The concentration of salt in the catalyzer finished product (comprising other basic metal and alkaline earth salt) does not have strict restriction, can be in very wide range.The best salt concn of concrete catalyzer depends on characteristic features, as catalyst efficiency, and catalyst aging speed and temperature of reaction.

The concentration of salt in the catalyzer finished product (by positively charged ion weight, as caesium) can be preferably in about 0.005-0.1wt% in approximately 0.0005-1.0wt% scope change.Deposition or the cationic preferred amounts that loads on carrier or the catalyst surface are about 10-4000ppm, preferred 15-3000ppm, and 20-2500 most preferably is by the positively charged ion weight on the whole solid support material.Common most preferred amount is about 50-2000ppm.When caesium mixes use with other positively charged ion, the ratio of cesium salt and other basic metal and alkaline earth salt, (if), as long as can meet the requirements of performance, there is not strict restriction, its ratio can change in getting wide scope.Cesium salt can be about 0.0001: 1 to 10000: 1 to the ratio of other salt, is preferably about 0.001: 1 to 1,000: 1.Preferably, caesium is add basic metal and alkaline-earth metal gross weight in the catalyzer finished product about 10%, and the best is 20～100%.

In preferred implementations more of the present invention, when with non-oxide reduction during to catalyzer, the amount of the positively charged ion potassium that can leach is in the weight of catalyzer, less than about 50ppmw, be preferably less than about 25ppmw, as 0-25ppmw, the mensuration of above-mentioned amount is to leach with a kind of mineral acid, particularly be the nitric acid of 10% (volume), under about 90 ℃, carried out about 1 hour, record with distilled water wash then with concentration.In some cases, can leach potassium on a small quantity and be used in combination, make the manganese composition increase substantially activity of such catalysts and/or stability to strengthen or to say with the manganese composition.Also have under many situations, the catalyzer that the present invention uses on a selective basis has closed less than about 100ppmw, and for example less than the positively charged ion sodium that leaches of about 50ppmw, measuring method as above.

The negatively charged ion cocatalyst or the properties-correcting agent kind that are applicable to catalyzer of the present invention comprise (only illustrating): oxo-anions, vitriol for example, SO ₄ ^-2, phosphoric acid salt is as PO ₄ ^-3, titanate is as TiO ₃ ^-2, tantalate is as Ta ₂O ₆ ^-2, molybdate is as MoO ₄ ^-2, vanadate is as V ₂O ₄ ^-2, chromic salt is as CrO ₄ ^-2, zirconate is as ZrO ₃ ^-2, polyphosphate, nitrate, oxymuriate, bromate, borate, silicate, carbonate, tungstate, thiosulphate and cerate or the like.Halide ions also can exist with anionic form, comprises fluorochemical, muriate, bromide and iodide.

As everyone knows, many negatively charged ion have complicated chemical property, can exist with one or more forms, as ortho-vanadate and metavanadate and various molybdate oxo-anions, as MoO ₄ ^-2, Mo ₇O ₂₄ ^-6And Mo ₂O ^{7 -2}Oxo-anions can also comprise the hybrid metal oxo-anions, and it comprises the polyoxy anion structure.For example, manganese and molybdenum can form the hybrid metal oxo-anions.Equally, other metal, as long as can be with negatively charged ion, positively charged ion, form element or covalency provides all and can enter anion structure.

Oxo-anions or its parent can use with the solution form of impregnated carrier, and under Preparation of catalysts and/or working conditions, it is possible that initial specific oxygen-bearing cation that exists or parent change into other form.In fact, element can change into positively charged ion or covalency form.Preferably element combines with oxygen, that is to say, forms oxygen-bearing cation, covalent oxides or oxygen containing negatively charged ion.As a rule, analytical technology still is not enough to identify exactly existing type.The definite type of the above-mentioned substance that exists on the final catalyst prod can not limit the present invention, during use with reference to oxo-anions just in order to guide the understanding of the present invention and enforcement.

Particularly preferred negatively charged ion cocatalyst comprises the oxo-anions of vitriol and rhenium, molybdenum, tungsten and/or chromium.The anions containing sulfur that is suitable for can exemplify out sulfuric acid, sulfurous acid, hydrosulfate, hydrosulphite, sulfonate, persulphate, thiosulphate, dithio vitriol, hyposulfite and halogenosulfuric acids salt, as the sulfuric acid fluorine etc.The compound of preferentially selecting for use is ammonium sulfate and alkali metal sulfates.The anionic example of molybdenum, tungsten and the chromium that is suitable for comprises molybdate, two molybdates, paramolybdate, other different one and heteropolymolybdate etc.; Tungstate, para-tungstate, metatungstate, other different-and assorted poly-tungstate etc.; And chromic salt, two chromic salt, chromite, halo chromic salt etc.What preferentially select for use is vitriol, molybdate, tungstate and chromic salt.

When catalyzer contained rhenium, the rhenium composition can provide with various forms, as with metal, and with covalent compound, forms such as positively charged ion or negatively charged ion.To in order raising the efficiency and/or active and rhenium-containing type that add does not have certain requirement, can to add with the composition that requires type, or in Preparation of catalysts process or use, produce required type.Rhenium compound can exemplify out the rhenium salt of rhenium halide, zirconyl oxyhalides rhenium, rhenate, mistake rhenate etc. and so on, the acid of oxide compound or rhenium.But, also can also use basic metal to cross rhenate, alkaline-earth metal is crossed rhenate, crosses rehenic acid silver and crosses rhenate and seven rhenium oxides with other.When seven rhenium oxide Re ₂O ₇When water-soluble, i.e. hydrolysis generated rehenic acid HReO ₄Or mistake rehenic acid hydrogen salt.Therefore, according to this explanation, can be considered as rhenate to seven rhenium oxides, i.e. ReO ₄Other metal such as molybdenum and tungsten also have similar chemical property.

The quantitative range of negatively charged ion cocatalyst can be very wide, by total catalyst weight, can be about 0.0005-2wt%, preferably about 0.001-0.5wt% is usually in use, the rhenium composition that adds, in total catalyst weight, it is worthwhile to press rhenium weight, and its amount is at least about 1ppmw, in other words, at least about 5ppmw, as 10-2000ppmw, that commonly used is 20-1000ppmw.

The catalyzer of type of the present invention comprises at least a salt composition that can raise the efficiency of redox half-reaction centering, said redox half-reaction is to being that epoxidizing method is used, in the method, redox half-reaction centering will have a kind of synergy gas ingredients to have (below will with explanation) at least.Term " redox half-reaction " is meant at standard reduction or oxidation potential, also claim to find in standard or the single electrode gesture table those half-reactions of reaction formula, for example, in " chemical handbook " (N.A.Lange, the publication of McGraw-Hill Book company, P1213-1218 (1961)) or " CRC physical chemistry handbook " (the 65th edition, CRC press, Boca, Raton, Florida, PD155-162 (1984)) can find this reaction type on.Term " redox half-reaction to " is meant the atom pairs that participates in oxidation or reduction reaction in half-reaction equation, molecule to or ion pair or their mixture right.At this, using the redox half-reaction is those members that can make in the class material that performance is improved in order to comprise to this term, rather than chemical reaction mechanism.Be preferably, these compounds are when fashionable with the salt member and the catalyst junction of half-reaction centering, and they are salt, and negatively charged ion wherein is an oxo-anions, preferably the oxo-anions of polyad; In other words, the atom of bonding aerobic is had the ability with the inhomogeneity atom, with the different valence state bonding in the negatively charged ion.Potassium is preferred cation, but sodium, rubidium and caesium also can adopt, and preferred anionic surfactants is a nitrate, and nitrite and other can generate those ions of nitrate ion by displacement or other chemical reaction under epoxidation conditions.Preferred salt comprises KNO ₃And KNO ₂, use KNO ₃Best.

The amount of one of redox half-reaction centering member's who is added salt should be enough to improve the efficient of epoxidation reaction.Consumption is along with the variation of the form of surface-area, processing condition such as the space velocity of the concentration of other composition in the used gas synergy composition of redox half-reaction and concentration thereof, the gas phase, catalyzer institute silver content, carrier and temperature and carrier changes accurately.But in general, add the suitable concentration of synergy salt, based on the gross weight of catalyzer, it is worthwhile to press positively charged ion, is at about 0.01-5wt%, preferred 0.02-3wt%.The optimum addition of salt approximately is 0.03-2wt%.

Under any circumstance, the positively charged ion of adding and/or negatively charged ion cocatalyst all should reach and have the amount that helps caloytic action." having the amount that helps caloytic action " at a certain composition of this said catalyzer is meant that the consumption of this composition can make one or more catalysis characteristicses of said catalyzer compare tangible improvement with the catalyzer that does not contain this composition.Said catalysis characteristics comprises, particularly as suitability (the anti-escape), selectivity, activity, transformation efficiency, stability and productive rate.Those skilled in the art know by " having the consumption that helps caloytic action " can improve one or more catalysis characteristicses, and other catalysis characteristics can or not improve, even may reduce.Really, by measuring as can be known under standard oxyethane processing condition, cocatalyst can improve the efficient of catalyzer, has reduced its activity also.And understand that further different processing condition can improve different catalysis characteristicses.For example, under a certain operational condition, can improve optionally catalyzer by different conditional operations, at this moment, what improve may be activity rather than selectivity, the operative employee of oxyethane equipment always takes all factors into consideration factors such as raw materials cost, energy cost and byproduct separation costs and attempts to change operational condition to improve some catalysis characteristics, and sacrifice other characteristics, therefrom obtain maximum benefit.

By the influence of urging effect may be subjected to multiple changing factor that helps that cocatalyst produced, for example, the surface-area of reaction conditions, catalyst preparation technology, carrier, the structure in hole and surface chemistry, other positively charged ion and anionic existence on the silver in the catalyzer and collaborative cocatalyst content and the catalyzer.Other activator, stablizer, cocatalyst, the existence of reinforcer or other catalyzer improving agent also can have influence on to help urges effect.

According to the present invention, Preparation of catalysts can adopt the whole bag of tricks.Preferable methods comprises: (1) is with the solution impregnation porous catalyst carrier that contains solvent or solubilizing agent and silver complex of q.s, make the silver that is deposited on the carrier and aforementioned negatively charged ion and/or oxonium ion cocatalyst reach desired weight, (2) soaked carrier is handled so that silver salt is converted into silver metal, and silver and negatively charged ion and/or positively charged ion cocatalyst are deposited on the inside and outside surface of carrier effectively.In order to show repeatability, use and reuse in the process at steeping fluid, carrier preferably do not contain excessive can be dissolved in the steeping fluid and/or can with the ion that in Preparation of catalysts or use, is carried on the cocatalyst generation permutoid reaction on the catalyzer so that keep catalyzer to strengthen desired cocatalyst consumption.If this class ion of vector contg, in general, these ions should pass through the standard chemical technology, remove as leaching-out technique.Usually at high temperature heating evaporation is removed year intravital liquid, silver and cocatalyst is deposited on the inside and outside surface of carrier effectively, thereby finishes its deposition.For the deposition of silver, this method of impregnated carrier is an optimized technical scheme, because it can more effectively utilize silver than coating process, the latter can not make a large amount of silver be deposited on effectively on the internal surface of carrier usually.In addition, the easier loss that causes silver owing to mechanical wear of application type catalyzer.

Process sequences with silver and cocatalyst dipping or deposition carrier surface is random.Therefore, the silver and the dipping of salt and deposit can combine simultaneously and carries out also can successively carry out, just, cocatalyst can be before silver adds carrier, among or deposit afterwards.Several cocatalysts itself also are can deposit simultaneously and can successively carry out.For example, one or more salt can mix deposition simultaneously, or silver and additive elder generation deposition, or other salt elder generation deposition.

By known while sedimentation or step deposition, with one or more argentiferous and cocatalyst solution impregnated catalyst carrier.For the while sedimentation, behind the dipping, to the heating of impregnated carrier or carry out chemical treatment so that Ag-containing compound is reduced to silver metal and make salt sedimentation on catalyst surface.

For the substep deposition,, heat as mentioned above then or chemical treatment earlier with silver or cocatalyst (depending on the order of selecting for use) impregnated carrier.After this, carry out for the second time dipping and corresponding heating or chemical treatment to obtain the catalyzer finished product of argentiferous and cocatalyst.

When preparing catalyzer of the present invention, the cocatalyst of some used basic metal and alkaline earth salt and so on should have sufficiently high temperature of fusion, so that when they are deposited on the carrier that contains silver compound and carry out heat treated when making silver compound be converted into silver metal, said salt can remain unchanged basically.Certainly, they can become one or several stable oxidation state when should be understood that the basic metal of handling unstable oxidation state and alkaline earth salt, become sulfuric acid as sulfurous acid.For example, when basic metal or alkaline-earth metal during with oxyhydroxide or carbonate form deposition, under the situation that amine exists (dipping that can be used for catalyzer), said salt can change into different salt form (being nitrate) in heating (baking) step, and this depends on baking condition.

The Ag-containing solution that is used for impregnated carrier is made up of argentiferous chemicals and solvent or coordination agent/solubilizing agent, as the disclosed silver-colored solution of prior art.The concrete silver compound that uses can be selected from following material, for example, the carboxylate salt of the title complex of silver, nitrate, silver suboxide or silver is as the silver salt of silver acetate, silver oxalate, silver citrate, phthalic acid silver, silver lactate, silver propionate, butyric acid silver and higher fatty acid.Implement when of the present invention, the title complex of silver suboxide and amine is the preferred form of silver.

There are a variety of solvents or Synergist S-421 95/solubilizing agent to can be used to dissolve silver makes it to reach regulation in steeping medium concentration.This wherein is suitable for this purpose disclosedly in the prior art has lactic acid (U.S.2,477,436, contriver Aries, U.S.3,501,417, contriver DeMaio); Ammonia (U.S.2,463,228, people such as contriver West); Alcohol is as aqueous mixture (U.S.2,459,896, the contriver Schwarz of 1,2 ethylene glycol (U.S.2,825,701, people such as contriver Endier, U.S.3,563,914, contriver Wattimina) and amine and amine; U.S.3,563,914, contriver Wattimina; U.S.3,215,750, contriver Benisi; U.S.3,702,259, contriver Nielsen; And U.S.4,097,414; 4,374,260 and 4,321,206, contriver Cavitt).

The particularly preferred method of preparation high silver content catalyzer comprises using with or without the silver that cocatalyst is arranged carries out two steps or multistep dipping, behind each dipping can followed by bake or other step to propose not molten silver.When the charge capacity of silver is high, help carrier to have high pore volume and surface-area.

After with silver and cocatalyst impregnation catalyst agent carrier, from remaining unabsorbed solution, isolate the soaked carrier particle.What this step adopted usually is to discharge excessive steeping medium, or adopts isolation technique, as filtering or centrifugation.Then, soaked carrier is carried out heat treated (as baking) effectively argentiferous metallic compound (in most cases being title complex) decomposed and to be reduced into metallic state silver and to deposit basic metal and alkaline earth salt simultaneously.Said baking can be at about 100 ℃-900 ℃, preferably carry out under 200 ℃-700 ℃, the time of baking be to be enough to almost all silver salt be converted into silver metal.In general, temperature is high more, and the required recovery time is short more.For example, under about 400 ℃ of-900 ℃ of temperature, reduction can be finished in about 1-5 minute.Although in the prior art to having advised that very wide scope is (as U.S3 the heat-up time of thermal treatment soaked carrier, 563,914, suggestion is heated below 300 seconds to finish drying catalyzer, rather than bake reduction, U.S.3,702,259 disclose, and heat 2-8 hour so that the silver salt on the catalyzer is reduced under 100 ℃ of-375 ℃ of temperature; U.S.3,962,136 suggestions were above-mentioned same temperature range internal heating 1/2-8 hour), but for silver salt almost Restore All become metal, only importantly temperature and recovery time are to be mutually related.For this purpose, can adopt continuous or the substep heating schedule.Preferably with catalyzer roasting continuously at short notice, for example preferably be no more than 1/2 hour, this can finish when preparation catalyzer of the present invention effectively.

Said heat treated is preferably carried out in air, but also can adopt nitrogen or carbon dioxide atmosphere.Be used for the equipment of heat treated can use the static of described gas or dynamically atmosphere reduce, but dynamically atmosphere is much better.

When preparation catalyzer of the present invention, the important thing of required consideration is to avoid using strong acid or strong base solution, and they can destroy carrier, and the impurity that is harmful to catalyst performance may be deposited thereon.English Patent 2,043,481 described preferred dipping methods comprise that high temperature bakes and is detained method in short-term, and above-mentioned patent also is particularly conducive to and reduces catalyst contamination to greatest extent.But the present invention uses salt and high purity support The combined, makes the present invention can adopt lower temperature, and the preferred short residence time.

According to asserting of some prior aries, the granular size that is deposited on the silver metal on the carrier is relevant with the catalyst system therefor preparation method.This may be true, because can check effectively that the technology of catalyst surface is limited.Therefore, the space between the silver-colored particle on the carrier of being seen does not also have enough features to illustrate whether these silver-colored particles can represent the whole silver on the carrier.Yet, solvent of specifically selecting for use and/or Synergist S-421 95, silver compound, heat treated condition and support of the catalyst all may exert an influence to observable silver-colored particulate change degree of institute's energy on the carrier and size scope.For generally being applicable to the carrier of producing oxyethane, common silver-colored granular size be distributed in 0.005-2.0 μ m.But in preparation oxyethane process, the particle size of silver catalyst is still not fully aware of to the catalyst efficiency role.From in fact, when catalyzer is used for catalyzed reaction, silver particles has been moved to catalyst surface as can be known, obvious variation has all taken place in its size and shape, yet, this catalyzer still has very high efficient, and the silver particles size that can see on this explanation carrier may not be important factor to the performance of catalyzer.

Silver catalyst of the present invention is specially adapted to utilize the vapor phase oxidation of ethene and molecular oxygen to produce oxyethane.The condition of carrying out this oxidizing reaction is known, in the prior art much explanations.Used reaction conditions has, as temperature, pressure, the residence time, reactant concn, gas phase thinner (as nitrogen, methane and CO ₂), vapor-phase inhibitor (as ethylene chloride, Ethylene Dichloride) or the like.

The gas of sending into reactor can contain properties-correcting agent or inhibitor or as U.S.2, the disclosed additive of 279,469 and 2,279,470 people such as () Law, for example nitrogen oxide and can generate the oxidation nitrogen compound.Can also be with reference to European patent 3642, particularly the catalyzer that uses of this patent comprises at least a synergy salt of redox half-reaction centering and the redox in the reaction pair at least a gas synergy composition of coupling with it.

Term used herein " gas ingredients that the redox half-reaction is right ", " the gas synergy composition that the redox half-reaction is right " etc. have similar meaning with previously defined terms such as " the salt compositions that the redox half-reaction is right ".In other words, the half-reaction composition of these term indications, what represent in standard in canonical reference textbook or handbook or the single electrode gesture table is gaseous phase, in the reaction equation of representing in textbook, these materials can be oxidized, can be reduced again.Preferred gaseous state synergistic matter is the compound that contains the element of the above valence state existence of strong divalence, preferred nitrogenous and another kind of element, the preferably compound of oxygen.The example of the gaseous state synergy composition of preferred redox half-reaction centering comprises NO, NO ₂, N ₂O ₄, N ₂O ₃In at least a, or under epoxidation conditions, can form one of above-mentioned gas, particularly NO and NO ₂Gaseous substance, and they and PH ₃, CO, SO ₃, SO ₂, P ₂O ₅And P ₂O ₃One or more mixture.NO often is the gaseous state potentiating compounds of preferentially selecting for use.

In some cases, though preferential employing is the composition of same half-reaction centering in reactive system, promptly, adopt synergy salt composition relevant and the gas ingredients in the feedstream with catalyzer, be used in combination with nitric oxide as preferred saltpetre, but be not that the result institute that reaches satisfied in all cases is essential.In same system, also can also adopt other combination, as KNO ₃/ N ₂O ₃, KNO ₃/ NO ₂, KNO ₃/ N ₂O ₄, KNO ₃/ SO ₂, KNO ₂/ NO, KNO ₂/ NO ₂And KNO ₃/ SO ₂Gas mixture with NO.In some cases, find that salt can be in the different half-reactions of beginning in a series of half-reaction equation of entire reaction and final reaction representative with gas ingredients.

The gaseous state synergy composition of redox half-reaction centering also will have enough amounts to improve performance, as catalyst activity, and especially epoxy reactive efficient.To a certain extent, its accurate consumption is by redox half-reaction centering used concrete synergy salt composition and concentration thereof, and the concrete alkene and the other factors that influences redox half-reaction centering synergy salt composition consumption above-mentioned that carry out oxidizing reaction determine.The general N that works as ₂When deciding loading, the gas ingredients of redox half-reaction centering comprises that the suitable concentration of epoxidation of propylene is about 0.1-2 of gas streams, 000ppmV to most alkene.When the right gas ingredients of preferred redox half-reaction, when being used for the epoxidation of propylene, with N as NO ₂Be main loading, preferred concentration is about 2000ppmV.But, when ethylene oxide, be the gas feed component of about 0.1-100ppmV to the suitable concentration of ethene.In reaction mixture, there is 3% (volume) CO ₂The time, the preferably about 1-80ppm of the gaseous state synergy composition of redox half-reaction centering.When nitric oxide has CO in as the gaseous state potentiating compounds of ethylene epoxidizing system, reaction mixture ₂, as containing CO up to 3% (volume) ₂The time, the amount of said nitric oxide is about 0.1-60ppm, preferably about 1-40ppm.

Be with unreacted feedstock recycle, or adopt one pass systems, their reasonableness, perhaps design arranges the series reaction device to carry out the transformation efficiency that successive reaction improves ethene, and to these, those skilled in the art can make decision easily.The concrete operations mode of selecting can be subjected to the restriction of technology cost usually.

In general, industrial feasible method is: the feedstream that will contain ethene and oxygen is sent into the reactor that catalyzer is housed continuously, reactor temperature is about 200 ℃-300 ℃, and pressure can be from 5 normal atmosphere to 30 normal atmosphere, and this depends on the productive rate of material flow and regulation.The residence time in large-scale reactor generally is about 0.1-5 second.Oxygen can be with the form supply response of oxygenic flow such as air or commodity oxygen.The oxyethane that from reaction product, separates and reclaim generation with ordinary method.But to the present invention, the technology of producing oxyethane it is contemplated that and becomes to contain CO ₂General recycle gas with general concentration, circulate as about 0.5-6% (volume).

What adopt in embodiments of the present invention is special standard oxyethane processing condition, unless other explanation is arranged in addition.In industrial production, can change general operational condition, can regulate the amount of used composition, to reach optimum efficiency.Usually, when producing oxyethane, can change ethane, the amount of carbonic acid gas and organochlorine is optimized efficient.Ethane is the impurity that is contained in the ethylene raw, and its amount changes.Ethane can also be added in the industrial reactor so that control muriatic inhibitor effect better.The ethane amount that adopts in industrial production all can be about 0.001-5mol% under air processing condition and two kinds of situations of oxygen processing condition, in the hope of reaching best effect.Along with the increase of ethane concentration in the reactor, the concentration that can be sure of effective surface chlorination thing on the catalyzer thus, has reduced the ability of muriate to promotion/inhibited reaction reducing, and has increased the production efficiency of oxyethane.Can change muriate according to cocatalyst used in ethane amount of being run in the concrete technology and the catalyzer and properties-correcting agent kind, reach the promotor/inhibitor effect of needs as the consumption of ethyl chloride or Ethylene Dichloride.Under air processing condition and two kinds of situations of oxygen air conditions, desire to reach best effect, the amount that is used for the organic chloride of industrial production generally can be about 1.0ppm-100ppm.It has been generally acknowledged that carbonic acid gas is a kind of inhibitor, carbonic acid gas becomes with its concentration the restraining effect of production efficiency.In certain industrial process,, adopt the carbonic acid gas of different concns more to need according to the kind difference of preparation used cocatalyst of catalyzer of the present invention or properties-correcting agent.Generally, under air processing condition and two kinds of situations of oxygen processing condition, the amount of carbon dioxide that adopts in the industrial production can be that about 2-15mol% is so that reach best effect.The consumption of carbonic acid gas depends on the size and the type of used carbon dioxide cleanup system.Ethane, the optimum amount of carbonic acid gas and organic chloride can make catalyzer be particularly suitable for obtaining the ideal effect in the production of industrial oxyethane.Especially in epoxidation technique, when with at least a gaseous state synergy of redox half-reaction centering composition with when being carried at least a salt composition of redox half-reaction centering on the catalyzer, concentration of carbon dioxide preferably maintains below about 1.5% (volume), as about 1.0%, even below about 0.5% (volume).

Be suitable for the oxirane production technology condition, be considered to an importance of the present invention as the catalyzer of standard oxyethane processing condition.

Embodiment

Following detailed step is to prepare the method for catalyzer and the explanation of carrier to being suitable for according to the present invention.These embodiment only are in order to illustrate, but not limitation of the scope of the invention.

Said carrier is used the solution impregnation that contains silver complex and alkalies and alkaline earth salt in vacuum as described below.The component of alkali metal containing and/or alkaline-earth metal needn't be introduced with the form of its salt.For example, according to the condition of Preparation of Catalyst and use, cesium hydroxide can be used in combination with ammonium salt (as ammonium sulfate) or acid (as sulfuric acid) or organic compound (as the sulfonic acid ethyl ester), changes into desired kind.The concentration of prepared steeping fluid is wanted to make silver and cocatalyst or the properties-correcting agent that contains required amount in the catalyzer finished product.For given carrier, the concentration of silver and cocatalyst institute palpus in solution can and know that the two is known or can measures easily by the pore volume calculating of tamped density (g/cc) and carrier.But this relation can change according to the character of carrier, and for example, pore volume can have influence on the amount that silver is precipitated out from given solution.With solution contain silver concentration divided by the silver and the ratio of cocatalyst in the catalyzer finished product of regulation, can learn the concentration of cocatalyst institute's palpus in solution.

In preparation catalyzer process, usually, the 1 (high-purity-grade) of specified amount is mixed with the distilled water of specified rate.Then with oxalic acid dihydrate (SILVER REAGENT) at room temperature (23 ℃) add to lentamente in the solution, constantly stir simultaneously.In adding the oxalic acid process, the temperature of solution generally is elevated to about 40 ℃ because of exothermic heat of reaction.Subsequently silver oxide powder (Metz company) is added in the diamines one oxalate aqueous solution, it is about below 40 ℃ that solution temperature is remained on.At last, add monoethanolamine, aqueous solution of alkali metal salt and distilled water and make solution.The normally about 1.3-1.4g/ml of the proportion of gained solution.

It is long that carrier can be immersed in one 12 inch, and in the garden cylinder glass container of internal diameter 2 inch, said container is furnished with a suitable stopcock so that discharge soaked carrier, still, also can adopt the suitable flask of other big or small type.Be inserted with a soft rubber ball on the sizeable separating funnel of splendid attire steeping fluid, have one on it and connect valve tube to the metal tube of dipping with container top.The dipping that carrier is housed is evacuated to about 20 minutes of about 2 inch mercurypressures with container, thereafter, open separating funnel and flood the stopcock of using between the container, make steeping fluid be added on the carrier lentamente, be immersed in the solution fully up to carrier, during this, the pressure in the container remains on about 2 inch mercury column.After solution added, container was opened to be exposed to and is reached normal atmosphere in the atmosphere.Under envrionment conditions, carrier continues to be immersed in the steeping fluid about 1 hour, then, discharges excessive solution in about 30 minutes.Thereafter with impregnated carrier as follows (except as otherwise noted) heat treated with the reduction silver salt and the deposition cocatalyst to the surface.That is, impregnated carrier individual layer is assisted

The wide circulation stainless steel conveying belt (spiral braid pattern) of inch is gone up and is carried by the square heating zone of one 2 inch * 2 inch 2.5 minutes, and this heating zone relies on upwards blows over the warm air holding temperature of conveying belt and granules of catalyst at 500 ℃ with 266SCFH speed.And warm air is to produce like this, and promptly air is long by one 5 Foot, the stainless steel pipes of internal diameter 2 inch, this pipeline by output rating be 5400 watts electric furnace (Lindberg ( ^TM) electric tube furnace: internal diameter

Inch, the long heating zone of 3 Foot) externally heating.Air after the heating in the pipeline unloads a discharge by the 2 inch * square row of 2 inch of the moving belt below that tightly is positioned at the carried catalyst carrier.The catalyzer finished product is weighed after heating zone baking, increases number according to the weight of carrier, and the ratio of silver-colored and cocatalyst as in the steeping fluid can calculate the silver that contains and the weight percentage of cocatalyst.

According to following method silver is analyzed: with the broken about 50g catalyst sample of abrasive dust, weigh up 10g and pulverize sample, weighing is accurate to 0.1mg.(80 ℃) concentration that silver in the catalyst sample is dissolved into heat is in the salpeter solution of 50% (volume).Filter out insoluble alumina particle and with distilled water wash to remove the nitrate of whole Ag that adhering to, Cs etc.With this solution volumetric flask of packing into, replenish with distilled water, make it to reach 250ml.Get the aliquots containig of this solution of 25ml,, make the indicator titration said sample, know the content of Ag in the 250ml solution thus, calculate the weight percent of silver in the catalyst samples again with it with the solution of 0.1N ammonium thiocyanate and iron nitrate according to standard operating procedure.

The silver of described all catalyzer of specification sheets and the concentration of cocatalyst all refer to the aforementioned calculation value.

Generally speaking, carrier is the annulation that is of a size of about 1/8 * 5/16 * 5/16 inch or about 1/8 * 1/4 * 1/4 inch.

Carrier " J "

Carrier J is a kind of alpha-alumina supports, is fired to top temperature behind its dipping by gama-alumina (N-6573) process 3.44wt% ammonium fluoride aqueous solution and makes for about 1025 ℃.This carrier contains the Alpha-alumina of 99.0wt% at least, approximately the fluorochemical of 0.2wt% and add under water can leach component:

Aluminium 118ppmw

Calcium 68ppmw

Magnesium 7ppmw

Potassium 3ppmw

Sodium 36ppmw

Fluorochemical 375ppmw

Nitrate 4ppmw

Phosphoric acid salt 30ppmw

Fluorophosphate 3ppmw

Vitriol 2ppmw

Silicon 6ppmw

The physical properties of carrier " J "

Surface-area 1.09m ²/ g

Pore volume 0.668CC/g

Mean pore sizes 1.85 μ m

Tamped density 0.53g/ml

The size distribution in hole accounts for the percentage ratio of total pore volume

Hole dimension (μ m) % total pore volume

P ₁(＜0.1) 0

P ₂(0.1-0.5) 1

P ₃(0.5-1.0) 6

P ₄(1.0-10) 88.5

P ₅(10-100) 1.5

P ₆(＞100) 3

Carrier " K "

Carrier K obtains after carrier J washs five times with hot deionized water (about 70 ℃).

Carrier " N "

The Chemical Composition of carrier " N "

At least the Alpha-alumina of about 98wt%

The impurity that acid can be leached:

But extract comprises 378ppm sodium and 330ppm potassium.

The physical properties of carrier " N ":

Surface-area (Kr) (1) 1.166m ²/ g

Pore volume (2) 0.697CC/g

Tamped density (3) 34.21bs/ft ³

Mean pore sizes (4) 15 μ m

Apparent porosity (%) 72

% water absorbs 65.4

Bulk density 1.1g/CC

Carrier " O "

Carrier O is fired to top temperature about 1025 ℃ and a kind of alpha-alumina supports of making after with about 3.4wt% ammonium fluoride solution dipping by gama-alumina (N-6573).The chemistry and the physical properties of this carrier are as follows:

The Chemical Composition of carrier " O "

Alpha-alumina 99wt%

Fluorochemical 0.28wt%

The impurity that water can leach:

64ppm aluminium, 9ppm calcium, 5ppm magnesium, 2ppm potassium, 12ppm sodium, 2ppm silicon, 173ppm fluorochemical, 11ppm nitrate, 3.2ppm phosphoric acid salt and 2ppm vitriol.

The physical properties of carrier " O "

Surface-area (1) 1.10m ²/ g

Pore volume (2) 0.69CC/g

Tamped density (3) 52.38g/ml

Mean pore sizes (4) 2.3 μ m

Pore size distribution accounts for the percentage ratio (4) of total pore volume

Hole dimension (μ m) % total pore volume

P ₁(＜0.1) 0

P ₂(0.1-0.5) 1

P ₃(0.5-1.0) 5

P ₄(1.0-10.0) 89.2

P ₅(10.0-100) 1.8

P ₆(＞100) 3

Carrier " P "

Carrier " P " is a kind of adhesive-free alpha-alumina supports.

The Chemical Composition of carrier " P "

Alpha-alumina 99wt%

The impurity that water can leach:

168ppm aluminium, 30ppm calcium, 1.3ppm magnesium, 102ppm potassium, 197ppm sodium, 148ppm silicon, 0.8ppm vanadium, 2.8ppm phosphorus, 1ppm muriate, 2ppm nitrate, 5ppm phosphoric acid salt, 1ppm vitriol, 3ppm fluorochemical, 4ppm acetate and 1ppm formate.

The physical properties of carrier " P ":

Surface-area (1) 1.35m ²/ g

Pore volume (2) 0.561CC/g

Mean pore sizes (4) 6.3 μ m

Tamped density (3) 0.61g/ml

The size distribution in hole accounts for the percentage ratio (4) of total pore volume

Hole dimension (μ m) % total pore volume

P ₁(＜0.1) 0.5

P ₂(0.1-0.5) 16.0

P ₃(0.5-1.0) 17.0

P ₄(1.0-10.0) 18.5)

P ₅(10.0-100) 38.5)

P ₆(＞100) 8.5

Carrier " Q "

Under 25 ℃, carrier " P " is immersed in the 10%HF solution 1 hour, then under this temperature with deionized-distilled water washing five times, 300 ℃ air drying 1 hour, promptly make carrier " Q " subsequently.

The impurity that water can leach:

266ppm aluminium, 313ppm calcium, 5.4ppm magnesium, 128ppm potassium, 106ppm sodium, 16ppm silicon, 0.2ppm vanadium, 0.3ppm zinc, 1.8ppm phosphorus, 1ppm muriate, 10ppm nitrate, 1ppm vitriol and 1011ppm fluorochemical.

Carrier R

Deionized water (about 70 ℃) wash vehicle O with heat promptly makes carrier R five times.

Carrier S

Carrier S is to carry out the calcining first time by the boehmite that contains the 3wt% fluoram-fluoram mixture under about 600 ℃, a kind of alpha-alumina supports that after calcining once more under about 1025 ℃, makes, and the chemistry and the physical properties of this carrier are as follows:

The Chemical Composition of carrier S

Alpha-alumina 99wt%

Fluorochemical 0.25wt%

The impurity that water can leach

6ppm aluminium, 9ppm calcium, 5ppm magnesium, 1ppm potassium, 13ppm sodium, 36ppm fluorochemical, 1ppm vitriol.

The physical properties of carrier S

Surface-area 1.24m ²/ g

Pore volume 0.77CC/g

Tamped density 0.50g/ml

Mean pore sizes 1.7 μ m

The size distribution in hole accounts for the percentage ratio of total pore volume:

Hole dimension (μ m) % total pore volume

P ₁(＜0.1) 0.5

P ₂(0.1-0.5) 3

P ₃(0.5-1.0) 9.5

P ₄(1.0-10) 81

P ₅(10-100) 2

P ₆(＞100) 4

Carrier T

Carrier T carries out the calcining first time by the boehmite that contains the 3wt% fluoram-fluoram mixture at about 600 ℃, a kind of alpha-alumina supports that makes after calcining once more under about 1025 ℃.The chemistry and the physical properties of this carrier are as follows:

The Chemical Composition of carrier T

Alpha-alumina 99wt%

Fluorochemical 0.25wt%

The impurity that water can leach

8ppm aluminium, 17ppm calcium, 8ppm magnesium, 5ppm potassium, 6ppm sodium, 55ppm fluorochemical, 1ppm vitriol.

The physical properties of carrier T

Surface-area 1.13m ²/ g

Pore volume 0.75CC/g

Tamped density 0.51g/ml

Mean pore sizes 2.1 μ m

The size distribution in hole accounts for the percentage ratio of total pore volume

Hole dimension (μ m) % total pore volume

P ₁(＜0.1) 0

P ₂(0.1-0.5) 1

P ₃(0.5-1.0) 4.5

P ₄(1.0-10) 90.5

P ₅(10-100) 1.5

P ₆(＞100) 2.5

Carrier U

Carrier U carrier T makes for five times through deionized water (the about 70 ℃) washing of heat.(1). measuring method has introduction in " the long-pending and porosity of absorbing surface " literary composition, author S.J.Gregg and K.S.W.Sing., academic press (AcademicPress) publishes (1967); P316-321.(2). measuring method is as described in the ASTMC20-46.(3). measure the weight of carrier in the container of known volume according to ordinary method, calculate numerical value.(4). measuring method is seen " using mercury infiltration carrying out material analysis ", author C.orr, powder technical journal, the 3rd volume, P117-123 (1970).

(AKron, Ohio) communique CC-11 in 1974 measure abrasion loss and shatter strength mean value and scope respectively according to test number 45 and test number 6 with reference to Norton support of the catalyst company.Measuring 25 Foot drop test is that the carrier pill is fallen on the block plate by the pipe of vertical range 25 Foot, observes the situation of breaking.Show the percentage ratio that passes through with non-cracked carrier granule numerical table.Measure impurity that acid can leach and be carrier granule is contacted 1 hour with 10% nitric acid under about 90 ℃, can know the positively charged ion that lixiviate goes out by the standard atomic absorption spectroscopy.This mensuration can also adopt the inductively coupled plasma spectroscopic techniques.

Rely on any easy analysis means can know that water in the carrier can leach the identity and the amount of component.Usually, place distilled water to be heated to about 50 °～95 ℃ in carrier, often be 90 ℃, the time is 0.5-2 hour, for example 1 hour.Do ion chromatography and the analysis of inductively coupled plasma spectroscopic techniques with this liquid then.

Embodiment 1 and 2

Embodiment 1 is a Comparative Examples.Following table II summary has provided about concrete catalyzer and the efficient under standard conditions.Should be realized that the specificity of catalyst that these embodiment characterize does not reflect the optimum formula of catalyzer.

Utilize following general method to prepare catalyzer.

The preparation of dipping solution

1. 1 (high-purity-grade) is mixed with distilled water.

2. at ambient temperature, oxalic acid (oxalic acid dihydrate, SILVER REAGENT) is added in the aqueous solution of 1 lentamente.Thermopositive reaction takes place, and the temperature of solution is increased to about 40 ℃.

3. then silver suboxide (powder-product of Metz company) is joined in the solution of step 2 lentamente.

4. monoethanolamine (no Fe and Cl) is added in above-mentioned 3 the solution.(note: step 1-4 is a collection of carrying out with 3 times of quantity to regulation, the part that classifies in three categories then, one of them is used for step subsequently).

5. add an alkali metal salt then.

6. add distilled water regulator solution volume to 150ml.

The dipping of carrier

1. at room temperature, carrier is vacuumized, in a vacuum above-mentioned steeping fluid is added on the carrier then.

2. discharge excessive solution

The baking of catalyzer

1. adopt the belt baking machine, utilize warm air baking soaked carrier, about 500 ℃ of temperature, 2.5 minutes time, air velocity is 66SCFH/in ²

Under the oxygen existence condition, by standard oxyethane experiment of process conditions catalyzer.

Embodiment 1 and 2 is summarized in the table II.

The table II

Other sun of silver is numbered wt from other the moon of other negatively charged ion of other positively charged ion from efficient temperature embodiment, % Cs, ppm negatively charged ion interest belong to % ℃ of 1a 31 of the sub-ppm carrier of metal ppm additive ^*60 Cs ₂Ta ₂O ₅ ²The K of---82.6 241 (contrast) 140 Cs ₂MoO ₄

750 Cs ₂SO ₄2b 30 ^* 220 CsMnO ₄ - - - - K 81.5 229

100 Cs ₂MoO ₄

750 Cs ₂SO ₄A.2.0ppm ethyl chloride, 6.0% carbonic acid gas that sucks.B.2.0ppm ethyl chloride, 6.0% carbonic acid gas that sucks.* adopt twice dipping, twice calcining process.

Embodiment 3-5

Adopt following general step to prepare catalyzer 3-5.

Under the constant speed agitation condition, in 100ml pyrex board beaker, add:

7.5g 1,

7.0ml water,

7.51g oxalic acid,

13.16g silver suboxide and 2.63g monoethanolamine.

Add interval at twice, cover beaker with transparent glass.Behind each the interpolation, the temperature of solution all changes in 25 ℃ of-60 ℃ of temperature ranges.Then with this mixture with distilled water diluting to 35ml.

The cesium hydroxide of equimolar amount and ammonium perrhenate added to promptly make the perrhenic acid caesium standardized solution that every gram solution contains 0.00531 gram caesium in the distilled water.With cesium sulfate be added to make in the distilled water every gram solution contain 0.015 the gram caesium the cesium sulfate standardized solution.

Above-mentioned standardized solution is added in the solution that contains silver suboxide to obtain dipping solution.Heating perrhenic acid caesium solution to 75 ℃ to be guaranteeing the salt dissolving, and with steeping fluid be warmed up to about 40 ℃ to guarantee the dissolving of perrhenic acid caesium.

10 gram carriers are added in the pyrex board impregnation chamber.The pressure of this chamber is reduced to about 2.0-5.0mmHg.Then steeping fluid slowly is added to above-mentioned indoor.Allow room pressure go back up to normal atmosphere.Discharge steeping fluid after 20 minutes.The steeping fluid of discharging is kept in the beaker of adding a cover.In roaster, calcined soaked carrier 3 minutes down in 500 ℃.Flood repeated impregnations and calcining step again with the solution of discharging.

The table III has been summarized these catalyzer.

Table III embodiment numbers silver-colored wt% Cs, ppm negatively charged ion carrier

3 30 ^* 395 ReO ₄ N

592 SO ₄

4 30 ^* 390 ReO ₄ N

592 SO ₄

160 MnO ₄

5 30 ^* 396 ReO ₄ N

594 SO ₄

330 MnO ₄

In a microreactor, use the catalyzer of embodiment 3,4 and 5 to estimate their performance.For microreactor test, be with catalyst pellet's with mortar and pestle fragmentation, and sieve out desired granular size (30-70 order).The broken catalyzer of the 2 grams diameter of packing into

Inch, long

In the stainless steel tube of inch.Again this pipe is put into test furnace and be connected with the gas input system.Control furnace temperature with temperature regulator, with pressing variable valve that the reactor outlet terminal pressure is controlled at 150psig behind the Groves.Gas flow rate is adjusted to the air-flow space-time speed (under standard temperature and pressure (STP), 12 liters/hour) of regulation.Come the measured reaction temperature with two thermopairs that are arranged on inside reactor.One of them is inserted in the catalyst bed, big below reactor head 2 o'clock position, another then is positioned at reactor exit.The mean value of two readings of record is as temperature of reaction.The gas ingredients of input comprises 30% (volume) ethene, 8% (volume) oxygen, and 6.5% (volume) carbonic acid gas is as the table ethane annotated of IV and the GN 2 of muriate and equal amount.

The table IV

Catalyzer 3 catalyzer 4 catalyzer 5

℃ % % ℃ of % ppm 1 1.0 87.9/86.0 of △ EO efficient temperature △ EO efficient temperature △ EO efficient temperature % ℃ of % % of ethane monochloroethane fate % ^a229 1.1 87.2 225 1.2 85.4 219 0.72 3.6 2-- -1.2 85.9 224 1.2 83.9 219 0.53 5.4 3 1.6 86.1 226 1.8 84.4 234 1.8 82.9 228 0.53 5.4 4 1.9 85.6 231 2.0 83.4 237 2.0 82.4 232 0.50 7.3 5 2.0 85.2 235 2.1 83.0 238 2.1 82.2 233 0.50 6.2 6 2.0 85.1 233 2.1 83.2 238 1.6 83.0 226 0.50 5.4 7 2.1 85.3 237 2.1 82.5 241 2.2 82.0 239 0.38 7.6 8 2.2 84.3 237 2.2 81.8 241 2.3 81.9 239 0.38 7.6 9 2.2 84.0 237 2.3 81.6 241 2.4 81.8 239 0.38 7.6 10 2.3 83.0 239 2.4 81.2 238 2.4 81.8 235 0.52 7.2 11 2.1 83.7 235 2.3 82.3 234 2.5 82.7 233 0.52 3.9 12 1.8 84.9 234 2.1 84.1 232 2.4 83.6 232 0.52 3.8 ^aLack material balance

Embodiment 6-23

Prepare catalyzer 6-23 by being similar to the described mode of embodiment 3-5.Urge catalyzer all to adopt twice following dipping technique preparation to every kind:

Use dipping to use the garden drum ladle, in a vacuum, with the solution impregnating carrier that contains normality silver salt and cocatalyst.After solution contacts 30-60 minute with carrier, discharge excessive steeping fluid from container.Subsequently soaked carrier was toasted 2.5 minutes in 500 ℃ airflow.Repeat again one time last time process, to obtain final catalyst prod.

The silver-colored weight of institute's load and cocatalyst amount depend on the concentration of steeping fluid and total pore volume of carrier on the catalyzer that makes.For every moles of silver in the solution, be with 1.05 moles of 1 (EDA), 0.525 mole of oxalic acid (OA), 0.378 mole of monoethanolamine (MEA) and an amount of water and cocatalyst.The preparation of said steeping fluid is: EDA is mixed with suitable quantity of water, slowly add oxalic acid then, constantly stir this solution simultaneously under envrionment conditions.But, because the adding of OA is heat release, so the temperature of solution may rise to about 40 ℃.Again silver suboxide and MEA are added in the EDA-OA-aqueous solution.At last, add cocatalyst solution and equal amount water so that silver and cocatalyst concentration meet the requirements.

In order to prepare catalyzer, the dipping that carrier is housed at room temperature be vacuumized with container.When contacting when steeping fluid introducing container and with carrier, carrier is in the vacuum all the time.Flood after 30-60 minute, discharge excessive solution from container.To assist on the stainless (steel) wire sheet through the carrier individual layer of dipping then, in 2 " * 2 " heating zone, be 500 ℃ by temperature, and speed is the hot blast drying 2.5 minutes of 244SCFH.All catalyzer all are the catalyzer through twice dipping.Therefore, repeat said process again one time with the steeping fluid that meets concentration requirement.The catalyzer finished product is weighed,, calculate the silver amount that is carried on the catalyzer finished product according to the weight gain of carrier.Can be desirably in for the first time that added cocatalyst dissolves once more in the steeping process when flooding for the second time.Therefore, in order to reach the desired cocatalyst amount of catalyzer finished product, the cocatalyst concentration of steeping fluid need be done some adjusting to cover the loss.

The table V has been introduced the deposition target content of every kind of component in per step steeping process and the ultimate aim content of catalyzer.

The table VI has been summarized the performance of every kind of catalyzer in the minitype high voltage tank reactor.This minitype high voltage tank reactor is a kind of 2 inch stainless steel internal recycle Berty reactors (autoclave engineering corporation produces, Erie, Pennsylvania, the U.S.).Reactor is by pressurized vessel, catalyst basket, and agitator and Magne transmission rig are formed.Pressurized vessel internal diameter 2 inch, its space can hold catalyst basket and agitator.Catalyst basket is diameter 1.25 inch, the stainless steel garden tube of long 1.06 inch, and its bottom is a stainless steel mesh, in order to the support catalyst sample with make the gas free flow.Periphery at this basket is welded with six roots of sensation stainless steel steel bar, and they are guiding the flow direction of pressurized vessel internal gas as traverse baffle, and when small basket was put into pressurized vessel, they can make upholder again.Agitator is arranged on the top of small basket and links with the interior axle of Magne transmission rig.And the inner shaft bearing seat is connected the top of pressurized vessel, forms the space of sealing with pressurized vessel.The magnetic force driving that outer magnet of axle produces in being somebody's turn to do, and said magnet is by air or motor drive.Generally speaking, agitator revolves biography with the speed of 1500rpm, is promoting the pressurized vessel gas inside, makes it to cycle through catalyst basket.Reactant gases is sent into pressurized vessel by the top and is discharged by the bottom.Temperature is by the thermocouple measurement and the control that are inserted in its bottom in the container." back-mixing formula autoclave under 275psig, carries out catalyst test with the 1.7-2ppm ethyl chloride normally according to the standard oxygen operational condition, to utilize 2.Adopt the catalyst test step of these standard conditions to comprise as follows:

1. the catalyzer of about 8CC is packed in the back-mixing formula autoclave.According to the tamped density of catalyzer, silver content and additive amount calculate catalyst volume.

2. be that 1500rpm, flow velocity are that the above-mentioned autoclave of heating cuts off nitrogen gas stream then to about 230 ℃ in the nitrogen of 2SCFH at rotation speed of fan, reactor is introduced in the materials flow of initial ring oxygenizement.The total gas flow rate in exit is transferred to about 2.2SCFH (regulating the loading capacity that flow velocity makes the realistic catalyzer of gas time space flow velocity).And then in 4 days progressively elevated temperature cause the concentration of oxyethane in the gas of exit to reach about 2%.

3. after catalyzer activates fully, it is operated 1-4 week under constant temperature.Go out active rate of ageing according to the change calculations of ethylene oxide concentration (mole %) under the constant temperature method condition.Because catalyst efficiency is the function of ethylene oxide concentration, and general ethylene oxide concentration is not to remain unchanged in the constant temperature test phase, therefore, and according to calculating the efficient aging speed along with ethylene oxide concentration changes the efficiency change value of adjusting.Utilize following equation can calculate the adjustment efficient of ethylene oxide concentration when being 2 moles of %.

Adjust efficient (%)=determination efficiency (%)+3.75 (%/mole %) * (ethylene oxide concentration of mensuration (mole %)-2.0 (mole %)).

The table V

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ₄ ^-) (as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 6 (1) 8.9 16 62-

〔2〕22.1 20 80 750 K

〔F〕31.0 36 142 750?7 〔1〕8.6 39 39 -

〔2〕22.2 50 50 750 K

〔F〕30.8 89 89 750?8 〔1〕8.5 62 15 -

〔2〕22.6 80 20 750 K

〔F〕31.1 142 35 750

Table V (continuing)

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ^- ₄) (as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 9 (1) 6.9 62 62-

〔2〕22.6 80 80 750 K

〔F〕29.5 142 142 75010 〔1〕8.2 40 88 -

〔2〕20.2 50 110 750 K

〔F〕28.4 90 198 75011 〔1〕8.6 86 39 -

〔2〕21.6 110 50 750 K

〔F〕30.2 196 89 750

Table V (continuing)

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ₄ ^-) (as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 12 (1) 8.6 158 63-

〔2〕21.1 200 80 750 K

〔F〕29.7 358 143 75013 〔1〕8.6 153 76 -

〔2〕23.5 200 100 - K

〔F〕32.1 353 176 -14 〔1〕7.2 132 39 -

〔2〕22.2 170 50 750 K

〔F〕29.4 302 89 750

Table V (continuing)

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ₄ ^-) ((as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 15 (1) 7.7 110 63-

〔2〕21.1 140 80 750 K

〔F〕28.8 250 143 75016 〔1〕7.8 132 - -

〔2〕22.2 170 - 750 K

〔F〕30 302 - 75017 〔1〕8.0 180 39 -

〔2〕21.8 230 50 750 K

〔F〕29.8 410 89 750

Table V (continuing)

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ₄ ^-) (as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 18 (1) 8.3 194--

〔2〕22.2 250 - 750 K

〔F〕30.5 444 - 75019 〔1〕7.6 131 39 -

〔2〕22.8 170 50 800 R

〔F〕30.4 301 89 80020 〔1〕8.2 156 47 -

〔2〕21.8 200 60 800 R

〔F〕30.0 356 107 800

Table V (continuing)

%Ag ppm Cs ppm Cs ppm Cs embodiment (as MnO ₄ ^-) (as MoO ₄ ⁼) (as SO ₄ ⁼) carrier 21 (1) 8.1-77-K

〔2〕23.0 - 100 750

〔F〕31.1 - 177 75022 〔1〕13.1 139 41 - Q

〔2〕18.2 170 50 800

〔F〕31.3 309 91 80023 〔1〕13.4 196 41 - Q

〔2〕18.2 240 50 800

The explanation of (F) 31.6 436 91 800 his-and-hers watches V

Symbol (1) is illustrated in the target quantity (in the final weight of catalyzer) of sedimentary material when flooding for the first time, and (2) are illustrated in the target quantity of sedimentary material in the steeping process second time.The target quantity of material in symbol (F) the expression catalyzer finished product.Adopt twice pickling process relatively good, because some material can dissolve again, and the concentration of cocatalyst can improve.Every kind of anionic amount can be with reference to the amount of positively charged ion (caesium) existence.

The table VI

At the 8th day, △ EO=2.0% ^cThe rate of ageing that calculates

Catalyst performance embodiment temperature ℃ efficient % % oxyethane/sky ^d% efficient/sky ^e6 258 78.4 -0.046 0.0 7 245 79.3 -0.011 -0.04 8 241 79.3 -0.021 +0.04 9 251 78.3 -0.027 -0.3010 253 77.1 -0.033 -0.0511 245 79.3 0.0 -0.0112 257 77.7 -0.011 +0.2013 ^a261 73.5-0.1--14 241 80.3-0.02-0.0715 255 76.8-0.1-0.28

Table VI (continuing)

At the 8th day, △ EO=2.0% ^cThe rate of ageing that calculates

Catalyst performance embodiment temperature ℃ efficient % % oxyethane/sky ^d% efficient/sky ^e16 239 80.0 -0.016 -0.06717 247 79.0 -0.017 -0.03518 250 76.3 -0.011 -0.08719 247 77.3 -0.026 +0.03520 251 76.0 -0.023 b 21 253 78.4 -0.01 -0.5222 240 78.8 -0.025 +0.02923 246 76.7 -0.019 0.0

A.6% carbonic acid gas, △ EO is 1.43,

B. reactor assembly obstacle,

C. be comparison basis with △ EO=2.0, according to the data that obtain, the temperature and the efficient that calculate by interpolation technique or epitaxial method,

D. activity calculated rate of ageing under constant temperature,

E. the efficient to regulate when the 2mol% oxyethane, the efficient rate of ageing that calculates.

Embodiment 24-26

Be prepared as follows two kinds of stock solutions: storing solution 88:11.47 weight part 1

20.00 weight parts water

11.60 weight part oxalic acid

19.82 weight part silver suboxide

4.01 weight part monoethanolamine storing solution 115:11.43 weight part 1

24.00 weight parts water

11.60 weight part oxalic acid

19.82 weight part silver suboxide

4.00 weight part monoethanolamine

During storing solution, control the input speed of oxalic acid and silver suboxide in preparation, make not reason heat release and of solution temperature above about 42 ℃.

Taking out a part of storing solution makes and has as three kinds of dipping solutions of composition as described in the table VII.

Table VII weight part component embodiment 24 embodiment 25 embodiment 26

(Comparative Examples) storing solution 88 190.25 178.88-storing solution 115--181.57KNO ₃1.1254 1.0452 1.0175KMnO ₄-0.1174-Mn (NO ₃) ₂--0.3674

Adopt the immersion process for preparing catalyzer twice, wherein the carrier S with certainweight is added in the steeper.Method by embodiment 1 is found time the container that carrier is housed, and adds specified storing solution again.Emptying makes it to reach normal atmosphere then.Drain carrier, in the belt roaster, calcine by the method for embodiment 1.Again this catalyzer is turned back to steeper and carry out the dipping second time.Add specified steeping fluid in steeper, container remains on as in the embodiment 1 described vacuum simultaneously.During the preparation steeping fluid, at first under vigorous stirring, add saltpetre.Secondly, add while stirring and contain manganic compound, and steeping fluid is come into operation immediately.The pressure release of steeper is reached normal atmosphere.Drain catalyzer, by calcining as mentioned above.About the details of catalyst preparation process and the catalyzer of gained are summarized in down:

Embodiment 24 embodiment 25 embodiment 26 are dipping for the first time: carrier (weight portion) 61.10 61.07 61.24 storing solutions 88 (weight portion) 192.5 193.2-storing solutions 115 (weight portion)--188.3 vacuum (mmHg), 30 30 30 dip times (minute) 30 30 30 drain the time (minute) 15 15 15 dippings for the second time: dipping solution (weight portion) 191.38 180.04 182.95 vacuum (mmHg) 30 30 30 dip times (minute) 30 30 30 drain the time (minute) 15 15 15 analyze: silver (wt%) 35.3 33.5 33.5 potassium (ppm; In K) Isosorbide-5-Nitrae 05 1,314 1350 manganese (ppm; In Mn)-136 334 sodium (ppm is in Na)) 25 35 20

Prepared every kind of catalyzer got about 80 cubic centimetres, in autoclave, as above estimate.It is the oxygen of 8% (volume) that the gas raw material of importing in autoclave is formed, the ethene of 30% (volume), the approximately ethyl chloride of 5ppmV, the approximately NO of 5ppmV and the nitrogen of equal amount.When catalyzer begins to do the time spent, temperature raise (220 ℃, 230 ℃, 240 ℃ and 255 ℃) to final 255 ℃ within 4 days.The concentration that integrated catalyst is active and efficient is come optimized choice ethylene chloride and nitrogen oxide.After test is carried out 25 days, the activity of the Catalyst Production oxyethane of embodiment 24 drops to about 70% of the 5th day value, and the activity of such catalysts of embodiment 25 and 26 that is to say still near the 5th day value, and the active scope that reduces was in about 5% than the 5th day.

Embodiment 27-43

Preparation of catalysts and evaluation are the process of repetition embodiment 6-23 basically, and different is that whole cesium salts add when flooding for the second time, and behind each dipping, catalyzer was 300 ℃ of following roastings 5 minutes.That these catalyzer use is carrier U.Their component and character are summarised in the table VIII.

The table VIII

1.5％EO ^*

Total Cs ppm Cs ppm Cs ppm Cs temperature efficiency, % difference embodiment as Cs ₂MoO ₄As Cs ₂SO ₄As CsMnO ₄℃ △％EO+27 600 400 200 - 248 83.3 0.6428 600 400 200 - 244 81.9 0.4729 700 500 200 - 259 83.8 0.7830 800 400 400 - 246 82.1 0.6131 800 500 300 - 256 83.3 0.8232 800 600 200 - 276 82.2 0.9633 700 400 200 100 250 80.2 0.6434 700 500 100 100 255 80.9 0.5635 700 500 150 50 252 81.6 0.5736 700 300 300 100 246 81.5 0.3537 800 500 200 100 268 79.2 0.58

Table VIII (continuing)

1.5％EO ^*

Total Cs ppm Cs ppm Cs ppm Cs temperature efficiency, % difference embodiment as Cs ₂MoO ₄As Cs ₂SO ₄As CsMnO ₄℃ △ %EO+38 800 400 200 200 262 75.7 0.7139 800 400 300 100 259 81.8 0.4240 900 300 200 400 276＜72.9 (0.75**) 41 900 400 200 300 266 75.5 0.4842 900 400 400 100 249 81.8 0.5843 1,300 400 800 100 262 80.5 0.59* were at the 7th day performance 8%O₂, 30%C ₂H ₄, 6.5%CO ₂, 2ppm ECl, 0.5%C ₂H ₆, 8000GHSV, 275 pounds/inch ²+ EO changes the % position in 5 days of measuring in the 8th day, ^*From testing the 4th day data computation

Embodiment 44-50

The following table IX has been summarized the details of catalyzer and the efficient under the standard operation condition.Should be understood that the catalyst performance that is characterized by these embodiment does not reflect the optimization formula of catalyzer.

Prepare these catalyzer with following step.

The preparation of dipping solution

1. 1 (high-purity-grade) is mixed with distilled water.

2. under envrionment conditions, oxalic acid (oxalic acid dihydrate, SILVER REAGENT) is added in the 1 aqueous solution lentamente.Thermopositive reaction takes place, and temperature is elevated to about 40 ℃.

3. lentamente silver suboxide is added in the solution of step 2 then.

4. monoethanolamine (no Fe and Cl) is added in above-mentioned 3 the solution.Step 1-4 large batch ofly finishes in the commercial catalysts producing apparatus.At this, get this steeping fluid of sub-fraction and be used for the laboratory with the preparation catalyzer.The weight ratio of 1, oxalic acid (dihydrate), silver suboxide and monoethanolamine is 0.6: 0.6: 1: it is 25.60wt% that 0.2 water that adds q.s makes silver concentration.Get the above-mentioned solution of sub-fraction and be used for the laboratory with the preparation catalyzer.

5. adding basic metal.

The dipping of carrier

1. at room temperature carrier is vacuumized, above-mentioned steeping fluid is added to is on the very aerial carrier.Be carrier T.

2. discharge excessive solution.

Baking of catalyzer

1. soaked carrier was baked in 500 ℃ warm air 2.5 minutes with the belt machine that bakes.Air velocity is 66SCFH/in ²

In air ambient, according to these catalyzer of standard oxyethane experiment of process conditions.

Embodiment 44-50 is summarised in the table IX.As can be seen, the manganese composition that no matter adds too much or very little, the performance of catalyzer all will be suffered a loss.

The table IX

Wt ppm Cs air ambient ^*

The Ag temperature efficiency embodiment wt% total amount MoO that wears out ₄MnO ₄SO ₄It ℃ % ℃ of/day % efficient/sky 44 21.4 517 206 154 157 2 264 73.7 2-0.545,21.4 520 310 159 51 2 276 71.6 2-0.346,20.4 492 246 99 147 2 257 74.9 1.35-0.1847,20.6 496 199 48 249 2 256 74.8 0.76-0.0548,20.6 499 296 54 149 2 266 73.2 3.2-0.749,21.2 518 256 30 232 2 267 74.4 2.82-0.7550 (Comparative Examples), 21.6 521 260 0 261 2 269 72 2.9-0.7^*Ingress's ethylene chloride, 2ppmV; Exit oxyethane 1.4%

Embodiment 51 and 52

The catalyzer for preparing embodiment 51 and 52 (Comparative Examples) with following step.

Under constant speed stirs, in 150 milliliters beaker, add:

36.72g 1

25.00ml water

36.83g oxalic acid

63.94g silver suboxide

13.57g monoethanolamine

Cover this beaker with transparent glass.Whenever add a kind of material, the temperature of solution all changes in 25 ℃ of-60 ℃ of scopes, makes mixed solution thus.Then with this mixture to 125 of distilled water diluting milliliter.

O adds to impregnation chamber the 1.0g carrier.Reducing room pressure to absolute pressure is about 2.0-5.0mmHg.About 31.25 milliliters steeping fluid is added to slowly this is indoor.Make room pressure go back up to normal atmosphere again.After 30 minutes, discharge steeping fluid.Soaked carrier bakes machine 500 ℃ of following roastings 2.5 minutes with aforementioned belt.Fresh steeping fluid (also containing rubidium salt) repeated impregnations and calcination steps with 31.25 ml aliquots.The catalyzer of embodiment 51 is with the formulations prepared from solutions that contains 0.8217g rubidium nitrate and 0.0854g permanganic acid rubidium, and the catalyzer of embodiment 52 is with the formulations prepared from solutions that contains the 0.8217g rubidium nitrate.The catalyzer finished product of embodiment 51 contains the silver of about 40wt% and the rubidium nitrate of 9273ppmw (calculating with rubidium).The catalyzer finished product of embodiment 52 contains the silver of about 40wt% and the rubidium nitrate of 8340ppmw (calculating with rubidium).

Performance with the microreactor evaluate catalysts.For the microreactor test, use mortar and pestle with the catalyst pellet's fragmentation, sieve out the particle that conforms with size (1.4-28 order) requirement.With the catalyzer of the about 0.9g fragmentation diameter 1/4 inch * length of packing into

In the stainless steel tube of inch, again this pipe is put into test furnace, and connect with the gas system of input.Furnace temperature is controlled by temperature regulator, and the top hole pressure of reactor is by pressing variable valve control behind the Groves.Gas flow rate will be adjusted to the gas hourly space velocity (under standard temperature and pressure (STP) 6 liters/hour) of regulation.The temperature of reactor is by the thermocouple measurement of two portions that set within it.Measure ingress's gas temperature for one, another surveys the exit gas temperature.Reaction is controlled by the temperature of inlet gas.

Unstripped gas is formed and is comprised 30% (volume) ethene, 8% (volume) oxygen, about 5～6ppmv ethyl chloride and about 6ppmv NO.Under 220 ℃ temperature of reactor, proceed to the 12nd day to reaction, embodiment 52 activity of such catalysts have only 1/3 of embodiment 51 catalyst activities.

Embodiment 53

With the catalyzer that is similar to embodiment 24 preparations, under embodiment 24 described conditions, about 255 ℃ of temperature of reaction was operated about 11 days.During operation, catalyzer loses activity.From conversion unit, take out catalyzer, with the KMnO that is dissolved in the 1 ₄,, make catalyzer contain about 200ppmw manganese (in total catalyst weight) by just wet these catalyzer of technical finesse.Again these catalyzer are placed under the embodiment 24 described ethylene oxide production conditions.Activity and efficient when at this moment activity of such catalysts and efficient are less than taking-up catalyzer from conversion unit; As if but it is active very stable, operate 15 days again after, its activity can compare with the activity of such catalysts of handling without potassium permanganate.

The manganese composition can be in catalyst preparation process or preparation before, even add when using.

Claims (7)

1. method of producing alkylene oxide by the reaction of alkene and oxygen, this method comprises the following steps:

A) alkene, oxygen, vapor-phase inhibitor and at least a gaseous constituent of redox half-reaction centering are sent in the catalytic bed, wherein said gaseous constituent is selected from NO, NO ₂, N ₂O ₃, N ₂O ₄Maybe can form the gas of above-mentioned any gas, described catalyzer comprises fire-resistant solid carrier, on this carrier, be loaded with: 1) silver metal, 2) at least a synergy salt of redox half-reaction centering, with 3) the manganese composition of q.s, described amount can make activity of such catalysts and at least a of stability and only contain above-mentioned 1) with 2) but the catalyzer that does not contain described manganese composition is compared height, describedly relatively under standard oxyethane processing condition, carry out;

B) in the presence of described catalyzer, alkene and oxygen are reacted to generate alkylene oxide under epoxidation conditions; With

C) from described reaction, take out alkylene oxide.

2. according to claim 1 method, it is characterized in that described salt comprises an alkali metal salt.

3. according to the method for claim 1, it is characterized in that the said gas that can form one of aforementioned gas is can form NO and/or NO under epoxidation conditions ₂Gas.

4. according to the method for claim 1, it is characterized in that said salt comprises saltpetre.

5. according to the method for claim 3, it is characterized in that said salt comprises saltpetre.

6. according to the method for claim 1, it is characterized in that said alkene comprises ethene or propylene.

7. according to the method for claim 3, it is characterized in that said refractory support contains to leach the Alpha-alumina of sodium less than 20ppmw.