CN100457257C - Zirconia-containing support material for catalysts - Google Patents

Abstract

The present invention relates to at least four different aspects relating to catalyst structures, methods of making the catalysts, and methods of making alkenyl alkanoates using the catalysts. Separately or in combination, various aspects of the present invention are directed to improving the production of alkenyl alkanoates, particularly VA, including reducing by-products and improving production efficiency. A first aspect of the invention relates to a unique palladium/gold catalyst or procatalyst (optionally calcined) comprising rhodium or another metal. A second aspect relates to a palladium/gold catalyst or procatalyst based on a layered support material, wherein one layer of the support material is substantially free of catalytic components. A third aspect relates to a palladium/gold catalyst or procatalyst supported on a zirconia containing support material. A fourth aspect relates to a palladium/gold catalyst or procatalyst produced from a substantially chloride free catalytic component.

Description

Zirconia containing support material for catalysts

The requirement of priority

The application requires the U.S. Provisional Patent Application No.60/531 of application on December 19th, 2003,415 rights and interests, thereby it is for reference to be introduced into this paper.

Invention field

The present invention relates to catalyst, this Preparation of catalysts method, and the preparation method of alkenyl alkanoates.More specifically, the present invention relates to the preparation method of vinyl acetate.

Background of invention

Some alkenyl alkanoates such as vinyl acetate (VA) are the high household chemicals of monomer whose form demand.For example, utilize the VA preparation to be usually used in the polyvinyl acetate (PVAc) of adhesive, in VA uses, account for larger proportion.Other application of VA comprises polyvinyl alcohol (PVOH), ethane-acetic acid ethyenyl ester (EVA), vinyl acetate-ethene (VAE), polyvinyl butyral resin (PVB), ethylene-vinyl alcohol (EVOH), polyvinyl formal (PVF) and vinyl chloride vinyl acetate copolymer.PVOH is usually used in textile, film, adhesive and photoactive coating.Film and wire cable insulating layer adopt a certain proportion of EVA usually.The main application of vinyl chloride vinyl acetate copolymer comprises coating, paint and adhesive, adopts the VAE that certain proportion VA is arranged usually.The VAE that contains more than 50%VA mainly is used as cement additire, paint and adhesive.PVB is mainly used in bottom, coating and the printing ink of lamination screen.EVOH is used for impermeable membrane and engineering polymers.PVF is used for wire enamel and tape.

Because VA is many bases that the raw material and the product of commercial value are arranged, so very big to the demand of VA, VA produces usually and carries out with fairly large (for example annual 50 000 tonnes or more).This large-scale production means that the less change that might produce sizable large-scale production and technology, process conditions or specificity of catalyst may have sizable economic impact to the production cost of VA.

A lot of technology have been reported in production about alkenyl alkanoates.For example, the technology that extensively adopts among the preparation VA comprises that ethene and acetate and oxygen carry out catalytic gas phase reaction, shown in following reaction:

C ₂H ₄+CH ₃COOH+0.5O ₂→CH ₃COOCH＝CH ₂+H ₂O

Some side reactions may take place, and comprise for example generating CO ₂With the space-time yield (STY) of reaction system the result of this reaction is discussed, wherein STY per hour is the gram number (g/l*h) that reaction time every liter of catalyst produces VA.

The composition of raw material can change in wide region.Usually, raw material comprises 30-70% ethene, 10-30% acetate and 4-16% oxygen.Charging may also comprise inert substance such as CO ₂, nitrogen, methane, ethane, propane, argon gas and/or helium.To the major limitation of feed composition is to leave in the effluent stream of reactor oxygen content must enough hang down and make this air-flow outside flammable area.Oxygen content in the effluent stream is subjected to the oxygen content in the feed stream, the O of reaction ₂The amount of any inert substance influence in conversion ratio and the effluent stream.

Carry out described gas-phase reaction at raw material under by the situation of fixed bed reactors always.By the result of the reaction temperature achieving success of employing in-125 to 200 ℃ of scopes, and reaction pressure is generally the 1-15 atmospheric pressure.

Though these systems provide enough output, but still the energy-consuming in the output of need minimizing accessory substance, raising VA output rating and the reduction production process.A kind of approach is to improve the CO of the performance of catalyst, particularly catalyst ₂Selectivity and/or activity.Another approach is to change reaction condition, for example O of material rate, reaction ₂The air speed of conversion ratio, charging (SV), and operating temperature and pressure.

Can improve catalyst minimizing CO by using ₂Growing amount.CO ₂Selectivity is to change into CO ₂The percentage of ethene.Reduce CO ₂Selectivity can be in existing equipment per unit volume and unit interval obtain more substantial VA, even keep all other reaction conditions.

The VA output quantity of specific reaction system is comprised the O of catalyst activity, material rate, reaction ₂The air speed of conversion ratio, charging (SV), and operating temperature and pressure in interior other factors influence.All of these factors taken together cooperates the space-time yield (STY) of decision reaction system, and wherein STY produces gram number or the g/l*h of VA by reaction time every liter of catalyst per hour.

In general, activity is the key factor of decision STY, but other factors may also have material impact to STY.Usually, activity of such catalysts is high more, and the fertile STY of catalyst is high more.

O ₂Conversion ratio is the tolerance that has how much oxygen to react in the presence of catalyst.O ₂Relevant consequently this conversion ratio with temperature of conversion ratio generally rises with reaction temperature.But produce CO ₂Amount also with O ₂Conversion ratio increases together.Therefore, select O ₂Conversion ratio is to obtain and CO ₂Generation keeps the desirable VA output quantity of balance.There is the catalyst of greater activity to mean and to keep O ₂Reduce the overall reaction temperature under the identical situation of conversion ratio.Perhaps, there is the catalyst of greater activity under to fixed temperature and air speed, to make O ₂Conversion ratio is higher.

It is very common that catalyst adopts one or more catalyst component that supports on the relative inertness carrier material.Under the situation of VA catalyst, catalyst component is metal mixture normally, can spread all over (" shell-type catalyst ") on the surface that carrier material evenly distributes (" spreading all over catalyst entirely "), only is distributed in carrier material, only be distributed in (" albumen formula catalyst ") below the carrier material shell or be distributed in the in-core (" yolk formula catalyst ") of carrier material.

Existing many dissimilar carrier materials are proposed to be used in the VA catalyst, comprise silica, mix cerium silica, aluminium oxide, titanium oxide, zirconia and oxide mixture.But it is few to the difference research between the carrier material.For major part, actual have only silica and aluminium oxide as the carrier material commercial applications.

A kind of metallic combination of the VA of being applicable to catalyst is palladium and gold.The Pd/Au catalyst provides suitable CO ₂Selectivity and activity, but still need in VA produces, can produce the improvement catalyst of large-scale production.

One of Pd/Au Preparation of catalysts method generally includes following steps: with the solution impregnating carrier of palladium with the water soluble salt of gold; The water soluble salt that makes dipping and the alkali compounds that is fit to for example NaOH reaction make these metallic elements with water-insoluble compound hydroxide form precipitation (being commonly referred to fixing) for example; Clean this fixing carrier material remove loose compound and otherwise cleaning catalyst remove for example chloride of any potential poisonous substance; For example hydrogen, ethene or hydrazine make described water-insoluble compound reduction with typical reducing agent; With add alkali metal compound for example potassium acetate or sodium.

Various improvement to this basic skills have been proposed.For example, US5, the sintering of palladium is carried out in suggestion after being reduced into the free metal form in 990,344.US6 may be favourable with carrier roasting in non-reduced atmosphere after proposing in 022,823 to flood with palladium and golden salt.Propose among the WO94/21374 after reduction and activation but before it uses for the first time, can carry out preliminary treatment to catalyst by in oxidation, inertia and reducing atmosphere, heating in succession.

US5 proposes not hydroxyl, halogen ion and barium in 466,652 and dissolves in the palladium of acetate and the salt of gold can be used for the impregnated carrier material.US4 also proposes similarly suggestion in 902,823, promptly uses not the palladium salt and the complex of the not substituted carboxylic acid that dissolves in 2 to 10 carbon atoms of Halogen ion and sulphur.

US6 proposes a kind of layered catalyst in 486,370 and can be used for certain embodiments, and wherein the internal layer carrier material is different with outer carrier material.Similarly, US5,935,889 propose a kind of layered catalyst can be used as acid catalyst.But all do not hint in the production of alkenyl alkanoates and use layered catalyst.

Consider that in the lump the inventor recognizes in the VA catalyst field need continue to improve the improvement VA production method that provides cost lower.

Summary of the invention

The present invention relates to relevant catalyst structure, this Preparation of catalysts method and with at least four different aspects of the method for this Preparation of Catalyst alkenyl alkanoates.Separately or combine, the purpose of different aspect of the present invention is to improve the particularly production of VA of alkenyl alkanoates, comprises reducing accessory substance and improving production efficiency.A first aspect of the present invention relates to a kind of palladium/Au catalyst of uniqueness or procatalyst (randomly passing through roasting), comprises rhodium or another kind of metal.Second aspect relates to based on the palladium/Au catalyst of layered support material or procatalyst, and wherein one deck carrier material is substantially free of catalyst component.The third aspect relates to and is supported on palladium/Au catalyst or the procatalyst that contains on the zirconic carrier material.Fourth aspect relates to by being substantially free of palladium/Au catalyst or the procatalyst that muriatic catalyst component is produced.

Detailed Description Of The Invention

Catalyst

For this paper, catalyst is any carrier material that contains at least a catalyst component and energy catalytic reaction, and procatalyst is any material by arbitrary generation of catalyst preparation step described herein.

Catalyst of the present invention and procatalyst can comprise having following attribute catalyst and procatalyst one of at least: 1) this catalyst is to comprise for example catalyst that contains palladium and gold of rhodium of at least a other catalyst component, and one or more of wherein said catalyst component passed through roasting; 2) this catalyst loading is on layered vector; 3) this catalyst loading is in containing on the zirconic carrier material; 4) this catalyst is with not produce or the above any combination of precursor of chloride.Therefore, effective utilization of this catalyst will help to improve CO ₂Selectivity, activity or both particularly produce for VA.

Should understand the present invention will be described in conjunction with some illustrational specific embodiments, but any aspect all can change according to the needs of concrete application.For example, without limitation, described catalyst can have spread all over the equally distributed catalyst component of carrier material or can be wherein catalyst component be present in around the carrier material core than the shell-type catalyst in the shell.Albumen formula catalyst also may be suitable for, and wherein catalyst component is basically outside the carrier material center.Yolk formula catalyst also may be suitable for.

Catalyst component

Usually, catalyst of the present invention and procatalyst comprise metal, comprise the combination of at least two kinds of metals particularly.Particularly, described metallic combination comprises from least a of VIIIB family and at least a from IB family.Should understand " catalyst component " and be used to represent finally to make catalyst to have the metal of catalysis, but also comprise the metal that is in various states, for example salt, solution, sol-gel, suspension, colloidal suspension liquid, free metal, alloy or its combination.Preferred catalyst comprises palladium and the gold as catalyst component.

A kind of embodiment of this catalyst comprises the catalyst component combination, and palladium and gold with the combination of the 3rd catalyst component are arranged.Described the 3rd catalyst component is preferably selected from VIIIB family, and Rh is most preferred.Other preferred catalyst comprises that the 3rd catalyst component wherein is selected from the catalyst of W, Ni, Nb, Ta, Ti, Zr, Y, Re, Os, Fe, Cu, Co, Zn, In, Sn, Ce, Ge, Ga and combination thereof.

Another embodiment of this catalyst comprises the catalyst component combination, comprises palladium, gold and rhodium.Alternatively, also can comprise the 3rd catalyst component (as top listed) that replaces Rh in this embodiment.In another embodiment, can adopt to be selected from top listed two or multiple catalyst component.

In the example, palladium and Jin Ke and Rh are combined to form the improved CO of Pd/Au catalyst that demonstrates than not containing Rh ₂Selectivity (is CO ₂Growing amount reduce).And, add Rh and as if activity of such catalysts is had no adverse effect.Also can be by roasting and/or by using the not CO of water-soluble precursor (as hereinafter described) improvement palladium-Jin-rhodium catalyst of halide in catalyst preparation process ₂Selectivity, but these are not that to observe the effect of Rh necessary.

The atomic ratio of the 3rd catalyst component and palladium can be about 0.005 to about 1.0, more preferably from about 0.01 to about 1.0 scope.In one embodiment, described catalyst contain every liter of catalyst about 0.01 and about 5.0g between the 3rd catalyst component.

Another preferred embodiment of described catalyst comprises the gold of every liter of catalyst between the palladium between about 1 to about 10g and about 0.5 to about 10g.The amount of gold is preferably about 10 to about 125wt%, based on the weight of palladium.

In a kind of embodiment of grained catalyst, the atom of Au and Pd may be preferred for grained catalyst between about 0.5 and about 1.00.Can regulate this atomic ratio with equilibrium activity and CO ₂Selectivity.Adopt higher Au/Pd weight or atomic ratio trend to help the catalyst that activity is higher, selectivity is higher.In other words, compare with the catalyst of atomic ratio about 0.8, the catalyst of atomic ratio about 0.6 is to CO ₂Selectivity lower, but lower activity is arranged also.Also can strengthen of the influence of high Au/Pd atomic ratio by using excessive more hydroxide ion to the powder carrier material, as the back at as described in the fixing step.Grained catalyst can be that wherein catalyst component contacts with carrier material then with the catalyst of particle size (for example by grinding or ball milling) reduction or the catalyst that contacts with carrier material that size has reduced of catalyst component wherein.

For the shell-type catalyst, on the carrier material thickness of catalyst component shell at about 5 μ m to the scope of about 500 μ m.Preferred scope comprises that about 5 μ m are to about 300 μ m.

Carrier material

As previously described, in one aspect of the present invention, catalyst component of the present invention carrier material load.The carrier material that is fit to generally includes the material or the mixtures of material of character basically identical.Generally speaking, carrier material inertia normally in the reaction that will carry out.Carrier material can be made up of any suitable material, and preferred selection like this so that carrier material have higher surface area in unit mass or volume, as loose structure, molecular sieve structure, honeycomb or other structure that is fit to.For example, carrier material can contain silica, aluminium oxide, silica-alumina, titanium oxide, zirconia, niobium oxide, silicate, alumino-silicate, titanate, spinelle, carborundum, silicon nitride, carbon, cordierite, talcum, bentonite, clay, metal, glass, quartz, float stone, zeolite, non-zeolite molecular sieve and combination thereof etc.Also can use the different crystal forms of these materials arbitrarily, for example α or gamma-alumina.Silicon oxide-containing and zirconic carrier material are most preferred.In addition, the multilayer carrier material also is applicable to the present invention.

Carrier material in the catalyst of the present invention can be by having various rules or irregularly shaped particle is arbitrarily formed, as ball, sheet, cylinder, disk, annular, star or other shape.Carrier material can have an appointment 1 to about 10mm, preferred about size of 3 to about 9mm such as diameter, length or wide.Particularly, its preferred full-size of regular shape (for example spherical) is about 4 to about 8mm.In addition, can use powder carrier material so that this carrier material regular or irregularly shaped, diameter between about 10 to about 1000 μ m, preferred size about 10 and about 700 μ m between, most preferably size about 180 and about 450 μ m between.Can adopt greater or lesser size, and the set of polydispersion granularity.For example, for fluid catalyst, the preferred sizes scope comprises 10 to 150 μ m.For the precursor that uses in the layered catalyst, the size range of 10 to 250 μ m is preferred.

The surface area of measuring by BET (Brunauer, Emmett, and Teller) method that can be used for the supported catalyst component generally can be about 1 and about 500m ²/ g, preferred about 100 is to about 200m ²Between/the g.For example, for porous carrier, the pore volume of carrier material generally can be about 0.1 to about 2ml/g, preferred about 0.4 to about 1.2ml/g.Mean pore size is for example about 50 to approximately Be desirable in the scope, but not necessarily.

The example of the silicon oxide-containing carrier material that is fit to comprises KA160 from Sud Chemie, from the Aerolyst350 of Degussa and the about 1mm of granularity extremely other pyrolysis of about 10mm or the silica of pore-free.

The example of the Zirconia containing support material that is fit to comprises from NorPro ZirconiaSales (America), those of Inc., Daichi Kigenso Kagaku Kogyo and MagnesiumElektron Inc (MEI).The Zirconia carrier material that is fit to has from less than about 5m ²/ g is extremely greater than 300m ²The surface area wide region of/g.Preferred Zirconia carrier material has about 10 to about 135m ²The surface area of/g.Carrier material can have the surface of handling through calcination steps, wherein the initial carrier material is heated.This heating makes the surface area of carrier material reduce (for example roasting).This provides the method that produces the carrier material with particular table area, otherwise this surface area may be not easy to obtain from supplier there.

In another embodiment, the compound of carrier material that different qualities is arranged adopted in plan.For example, at least two kinds have the carrier material (for example zirconia) of different qualities can demonstrate different activity and CO ₂Selectivity, thus can prepare catalyst with the one group of characteristic of wanting, can make the CO of activity of such catalysts and catalyst ₂Balance.

In a kind of embodiment, use multiple different carriers with the multilayer configuration.Can multiple different approaches realize layering arbitrarily, as a plurality of thin layers, generally be flat, rise and fall or its combination.A kind of approach is the encapsulated layer that uses in succession with respect to inner sandwich layer.In general, layered support material generally includes at least one internal layer and surrounds the skin of this internal layer to small part herein.Skin preferably contains obviously than the more catalyst component of internal layer.In a kind of embodiment, ectonexine is made by different materials; But this material can be identical.Though internal layer can be non-porous, other embodiment comprises the internal layer of porous.

Layered support material is preferably formed the shell-type catalyst mode.But layered support material is in the carrier material zone that catalyst component is arranged and do not have well-defined border to occur between the carrier material zone of catalyst component.And, can constitute the skin of as one man wanting thickness to some extent.Described border and outer field uniform thickness produce the shell-type catalyst together, and it is the catalyst component shell of even and known thickness.

Known several technology are used to produce layered support material, comprise US6,486,370; 5,935,889; With 5,200, those technology of describing in 382 all are incorporated herein for reference.In a kind of embodiment, the material of internal layer also can not be permeated by liquid basically, and for example metal includes but not limited to aluminium, titanium and zirconium.Other examples of material that is used for internal layer includes but not limited to aluminium oxide, silica, silica-alumina, titanium oxide, zirconia, niobium oxide, silicate, alumino-silicate, titanate, spinelle, carborundum, silicon nitride, carbon, cordierite, talcum, bentonite, clay, metal, glass, quartz, float stone, zeolite, non-zeolite molecular sieve and combination thereof.Preferred internal layer is a silica, particularly KA160.

These materials that constitute internal layer can be various forms of, as the object of the particle of regular shape, particle in irregular shape, pill, disk, annular, star, wheel shape, honeycombed or other shape.The spheric granules internal layer is preferred.The effective diameter of internal layer (no matter whether be spherical) is about 0.02 to about 10.0mm, preferably about 0.04 to about 8.0mm.

The outermost layer of any sandwich construction is a porous, surface area about 5 to about 300m ²In the scope of/g.This outer field material is metal, pottery or its combination, in a kind of embodiment, be selected from aluminium oxide, silica, silica-alumina, titanium oxide, zirconia, niobium oxide, silicate, alumino-silicate, titanate, spinelle, carborundum, silicon nitride, carbon, cordierite, talcum, bentonite, clay, metal, glass, quartz, float stone, zeolite, non-zeolite molecular sieve and combination thereof, preferably include aluminium oxide, silica, silica, zeolite, non-zeolite molecular sieve (NZMS), titanium oxide, zirconia and composition thereof.Instantiation comprises zirconia, silica and aluminium oxide or its combination.

Though skin surrounds whole internal layer usually basically, needn't be like this, also can adopt skin optionally to be applied on the internal layer.

The outer mode that can be fit to is applied on the lower floor (underlying layer).In a kind of embodiment, adopt the slurries of cladding material.Can finish with slurries by methods such as roller coat, dip-coating, spraying, washcoated, other slurries coating technique or its combinations and be coated with internal layer.A kind of preferred technology relates to the fixed bed that utilizes inner layer granule or fluid bed and described slurries is sprayed in the bed to be coated with described particle equably.Can repeat painting slurry slightly, carry out drying therebetween, to provide thickness well-proportioned skin.

The slurries that are used to be coated with internal layer can also comprise various additives such as surfactant, help outer and lower floor to adhere to organic or inorganic adhesive or its combination are arbitrarily.The example of this organic bond includes but not limited to PVA, hydroxypropyl cellulose, methylcellulose and carboxymethyl cellulose.The amount that adds the organic bond in the slurries can change, for example be skin and adhesive sum about 1 to about 15wt%.The example of inorganic bond be selected from alumina adhesive (for example Bohmite), silica binder (Ludox for example, Teos), zirconia binder (for example zirconia acetate or colloidal zirconia) or its combination.The example of silica binder comprises silica sol or silica gel, and the example of alumina adhesive comprises alumina sol, bentonite, Bohmite and aluminum nitrate.The amount of inorganic bond can be in about scope of 2 to about 15wt% of outer and adhesive sum.Outer field thickness can about 5 to the scope of about 500 μ m, preferably about 20 and about 250 μ m between.

After internal layer is coated with by skin, to make gained layered vector drying, for example by to about 320 ℃ temperature, heating (for example about 1 to about 24 hours time) at about 100 ℃, then can be randomly about 300 ℃ to about 900 ℃ roasting temperature (for example about 0.5 to about 10 hours time), to strengthen the bonding of outer and its lower floor, provide the layered catalyst carrier in its surperficial at least a portion.Dry and calcination steps can be merged into a step.The same with any other carrier material in the Catalyst Production, the gained layered support material is contacted, as hereinafter described with catalyst component.Perhaps, before being applied in the lower floor, outer carrier material makes it to contact with catalyst component.

In another embodiment of layered vector, add the initial skin of the second outer encirclement and form at least three layers.The second outer field material can be identical or different with first skin.The material that is fit to comprise at first outer described those.The second outer field method that applies can be with to apply the intermediate layer method therefor identical or different, the method that is fit to comprise at first outer described those.Form in second skin and can suitably use described organic or inorganic adhesive.

Initial skin can contain or not contain catalyst component.Similarly, second skin also can contain or not contain catalyst component.If two skins all contain catalyst component, then preferably in every layer, use different catalyst components, although needn't be like this.In a kind of preferred embodiment, initial skin does not contain catalyst component.Can realize that catalyst component contacts with outer by dipping or spraying, as hereinafter described.

Initial skin contains in the embodiment of catalyst component, and a kind of implementation method is that catalyst component is contacted with this material.Second skin can be applied on the initial skin pure or that contain catalyst component.

The available technology that other is fit to obtains three layers of carrier material, and wherein one or more skin contains catalyst component.Certainly, layered support material is not limited to three layers, can comprise four, five or more multi-layered, some of them or all can contain catalyst component.

In addition, the amount and the type of the interlayer catalyst component of layered support material can change, and other characteristic of carrier material (for example porosity, granularity, surface area or pore volume etc.) can change at interlayer.

The Preparation of catalysts method

Usually, described method comprises and carrier material is contacted with catalyst component and makes catalyst component reduction.The preferred method of the present invention comprises immerses in the carrier material catalyst component, will contain the carrier material roasting of catalyst component, makes the catalyst component reduction and makes reduction catalysts component modification on the carrier material.Can also comprise among the preparation method of catalyst or procatalyst such as catalyst component being fixed on the carrier material and cleaning additional step such as fixed catalytic component.More than some are optionally and other can cancel (for example cleaning and fixing step) in the listed step.In addition, some step can repeat (for example a plurality of dippings or fixing step) and step order can with above listed different (for example reduction step is before calcination stepses).To a certain extent, described contact procedure will determine to form catalyst needs any subsequent step.

Contact procedure

A kind of specific contact method is according to forming the method that yolk formula catalyst or procatalyst, formation albumen formula catalyst or procatalyst, formation spread all over formula catalyst or procatalyst entirely or forms shell-type catalyst or procatalyst or its combination.In a kind of embodiment, the technology that forms the shell-type catalyst is preferred.

Contact procedure can be carried out with above-mentioned any carrier material, silica, zirconia and to contain zirconic layered support material be best.Contact procedure is preferably carried out under environment temperature and pressure condition; But also can adopt the temperature or the pressure that reduce or raise.

In a kind of preferred contact procedure, with the aqueous solution (being called precursor solution) the impregnated carrier material of one or more catalyst component.The physical state of carrier material can be dried solid, slurries, sol-gel or colloidal suspension liquid etc. during the contact procedure.

In a kind of embodiment, contained catalyst component is the water soluble salt of being made by catalyst component in the precursor solution, include but not limited to chloride, other halide, nitrate, nitrite, hydroxide, oxide, oxalates, acetate (OAc) and amine, the salt of halide is not preferred, and the salt of chloride is not preferred.The example that is applicable to the palladium salt of precursor solution comprises PdCl ₂, Na ₂PdCl ₄, Pd (NH ₃) ₂(NO ₂) ₂, Pd (NH ₃) ₄(OH) ₂, Pd (NH ₃) ₄(NO ₃) ₂, Pd (NO ₃) ₂, Pd (NH ₃) ₄(OAc) ₂, Pd (NH ₃) ₂(OAc) ₂, at KOH and/or NMe ₄Pd among OH and/or the NaOH (OAc) ₂, Pd (NH ₃) ₄(HCO ₃) ₂With the oxalic acid palladium.In the palladium precursor of chloride, Na ₂PdCl ₄Be most preferred.Not in the palladium precursor salt of chloride, below four kinds be most preferred: Pd (NH ₃) ₄(NO ₃) ₂, Pd (NO ₃) ₂, Pd (NH ₃) ₂(NO ₂) ₂, Pd (NH ₃) ₄(OH) ₂The example that is applicable to the golden salt of precursor solution comprises AuCl ₃, HAuCl ₄, NaAuCl ₄, KAuO ₂, NaAuO ₂, NMe ₄AuO ₂, at KOH and/or NMe ₄Au among the OH (OAc) ₃And the HAu (NO in nitric acid ₃) ₄, KAuO ₂It is the golden precursor of most preferred not chloride.The example that is applicable to the rhodium salt of precursor solution comprises RhCl ₃, Rh (OAc) ₃, and Rh (NO ₃) ₂Also can select the class of above-mentioned the 3rd catalyst component saloid.

In addition, in given precursor solution, can use more than a kind of salt.For example, palladium salt can be combined in together with golden salt combination or two kinds of different palladium salt in single precursor solution.Precursor solution can be with or without the solubility improver as acid, alkali or other solvent by the selected water-soluble preparation of salt usually.Other nonaqueous solvents also can use.

Precursor solution can (for example flood) or one after the other be immersed on the carrier material and available one or more precursor solution dipping simultaneously altogether.Have three or the situation of more kinds of catalyst components under, can adopt simultaneously and the combination of dipping in succession.For example, available single precursor solution impregnation palladium and rhodium (being called common dipping), the precursor solution with gold floods then.In addition, catalyst component can multistep be immersed on the carrier material so that a part of catalyst component of each contact.For example, a kind of suitable scheme can comprise with the Pd dipping, flood with the Au dipping and then with Au then.

Order with precursor solution impregnated carrier material is unimportant; Although some order has some advantages, as the back at as described in the calcination steps.The palladium catalyst component is immersed on the carrier material, after palladium or at last with the gold dipping.Rhodium or other the 3rd catalyst component (during use) can be with palladiums, with gold or independent dipping.And carrier material can be with identical catalyst component dipping repeatedly.For example, the part of contained total gold in the first contact catalyst, the second portion of contact gold then.Between gold and step that carrier material contacts, can insert one or more other step, for example roasting, reduction and/or fix.

The Acid-Base of precursor solution distributes to influence and adopts dipping or dipping altogether in succession.Therefore, the precursor solution energy one that has only Acid-Base to distribute similar is used from common impregnation steps; This has eliminated any Acid-Base reaction that may pollute precursor solution.

For impregnation steps, the volume of precursor solution select like this with make it corresponding to the carrier material pore volume about 85% and about 110% between.Volume the carrier material pore volume about 95% and about 100% between be preferred, more preferably pore volume about 98% and about 99% between.

Usually, precursor solution is added in the carrier material and make carrier material absorb precursor solution.This can the dropping mode carry out reaching just wetting substantially until carrier material.Perhaps, carrier material can be merotomized or put into precursor solution with intermittent mode.Available rotary dipping or other servicing unit are realized thorough contact the between carrier material and the precursor solution.Also can utilize sprayer unit to be absorbed so that precursor solution is sprayed onto on the carrier material by nozzle.Randomly, available decantation, heating or decompression are removed any excess liq of not suppressed by vector material absorption or make the carrier material drying behind dippings.

For impregnation steps, the volume of precursor solution select like this to make it the carrier material hole body and about 85% and about 110% between.Preferred volume the carrier material pore volume about 95% and about 100% between, more preferably pore volume about 98% and about 99% between.

Typically, precursor solution is added in the carrier material and make carrier material absorb precursor solution.This can the dropping mode carry out reaching just wetting substantially until carrier material.Perhaps, carrier material can be merotomized or put into precursor solution with intermittent mode.Available rotary dipping or other servicing unit are realized thorough contact the between carrier material and the precursor solution.Also can utilize sprayer unit to be absorbed so that precursor solution is sprayed onto on the carrier material by nozzle.Randomly, available decantation, heating or decompression are removed any excess liq of not suppressed by vector material absorption or make the carrier material drying behind dippings.

Available other contact technique is avoided fixing step and is still obtained the shell-type catalyst.For example, catalyst component is contacted with carrier material, described in US2001/0048970, be incorporated herein for reference by chemical vapor deposition method.And, the spraying or otherwise make carrier material stratification (as skin) on internal layer of even pre-preg form the shell-type catalyst effectively, also can be described as layered support material.In another technology, the Organometallic precursor of available catalyst component (particularly for gold) forms the shell-type catalyst, as US 5,700, described in 753, is incorporated herein for reference.

Physics becomes shell technology also to can be used for producing the shell-type catalyst.Here, precursor solution can be sprayed onto on the carrier material or layered support material of heating, the evaporation when solvent of precursor solution contacts with the carrier material of heating, thus catalyst component is deposited on the carrier material with the form of shell.Preferably adopt the temperature between about 40 and 140 ℃.The thickness of the flow velocity control shell that can pass through nozzle by the temperature and the solution of selection carrier material.For example, temperature is higher than under 100 ℃ the situation, forms thin shell.When promoting on carrier material, to form shell with the precursor of chloride not, this embodiment particularly suitable.

The combination that it will be appreciated by those skilled in the art that described contact procedure may be the appropriate methodology that forms the contact carrier material.

Fixing step

It may be desirable that at least a portion catalyst component on the contact carrier material is become water insoluble form by the water soluble formal transformation.This step can be described as fixing step.This can realize at least a portion catalyst component precipitation by apply fixative (for example the dispersion in liquid, as solution) on the impregnated carrier material.This fixing step helps to form the shell-type catalyst, but is not that formation shell-type catalyst is necessary.

Can use any suitable fixative, the hydroxide of aqueous solution form (for example alkali metal hydroxide), silicate, borate, carbonate and bicarbonate are preferred.Preferred fixative is NaOH.Can be before precursor solution be immersed on the carrier material, during or in carrier material, add fixative afterwards and realize fixing.Typically, after contact procedure, use fixative that contacted carrier material was soaked in fixative solution about 1 to about 24 hours.The concrete time is depended on the combination of precursor solution and fixative.As impregnation steps, also be beneficial to the use servicing unit in the fixing step, as US 5,332, rotary immersion system described in 710 is incorporated herein for reference.

Fixing step can be finished in a step or multistep, was called to unite to fix or separately fix.Unite fixing in, no matter contact still is that multiple precursor solution is finished with a kind of precursor solution, all with after carrier material contacts, on the carrier material after the contact, apply one or the fixative solution of many volumes at all precursor solutions of being correlated with.For example, unite with being fixed as after palladium precursor solution, golden precursor solution and the rhodium precursor solution dipping in succession fixing, with palladium/rhodium precursor solution flood altogether then with fixing of carrying out afterwards of golden precursor solution dipping also be unite fixing.Unite the visible US 5,314,888 of fixing example, be incorporated herein for reference.

On the other hand, separately fixedly comprise at every turn with during the precursor solution dipping or apply fixative solution afterwards.For example, following scheme is for separately fixing: a) palladium-impregnated is fixing then, fixing then with the gold dipping again; Or b) flood altogether then with palladium and rhodium fixing, fixing then with the gold dipping again.Between fixing and follow-up dipping, can remove any excessive liquid and make the carrier material drying, but this is optional.The separately fixing visible US 6,034,030 of example is incorporated herein for reference.

In another embodiment, fixing step and contact procedure are carried out simultaneously, and one of its example is described in US 4,048, in 096, are incorporated herein for reference.For example, fixingly simultaneously can be: fixing then with the palladium dipping, again with gold and fixative dipping.In a kind of remodeling of this embodiment, can carry out twice to catalyst component and fix.Can when contacting with carrier material, fix catalyst component (being called " pre-fixing ") with making catalytic component part, and then final the fixing of adding.For example: then with gold with pre-fix agent and flood, fix with final fixative again with palladium dipping.Available this technology assists in ensuring that and forms the shell-type catalyst relative with spreading all over the formula catalyst entirely.

In another embodiment, be particularly suitable for the not precursor of chloride, carrier material carried out preliminary treatment to regulate the character of carrier material with fixative.In this embodiment, earlier with acid or aqueous slkali (typically not containing metal) impregnated carrier material.After the drying, use the precursor solution impregnated carrier material that has with the opposite acidity/alkalescence of this dried carrier material.Consequential Acid-Base is reflected at and forms the catalyst component shell on the carrier material.For example, available nitric acid carries out preliminary treatment to carrier material, uses alkaline precursor solution such as Pd (OH) again ₂Or Au (OH) ₃Dipping.It is contact procedure then that this technology can be considered the employing fixing step.

The concentration of fixative is typically than the amount molar excess that is immersed in the catalyst component on the carrier material in the solution.The amount of fixative should and water soluble salt in the catalytic activity cationoid reaction aequum that exists about 1.0 to about 2.0, between preferred about 1.1 to about 1.8 times.Use in a kind of embodiment of high Au/Pd atom or weight ratio, the molar excess that increases hydroxyl ion improves the CO of gained catalyst ₂Selectivity and activity.

The volume of supply fixative solution should be the amount that is enough to cover the available Free Surface of impregnated carrier material.This can realize by for example adding greater than the volume of the pore volume of contact carrier material.

Dipping and fixing step combination can form the shell-type catalyst.But use not the precursor solution of halide also can form the shell-type catalyst under the situation of randomly eliminating fixing step.Do not having to avoid cleaning step, as hereinafter described under the situation of chloride precursor.In addition, this process can not comprise the step of fixed catalytic component, otherwise with the needs cleaning step that exists.Because do not need cleaning step, so needn't make catalyst component fixing with the cleaning step that exists.Subsequent step in this method for preparing catalyst does not need catalyst component is fixed, thereby remaining step can carry out under the situation that does not add preparation process.In a word, use not that the precursor of chloride makes catalyst or procatalyst production method can not have cleaning step, produce the refuse that the required step number of catalyst reduces and do not need to dispose chloride thereby make.

Cleaning step

Particularly when using the precursor solution of halide and in other application that needs, after the fixing step, can clean the carrier material of fixing and remove any halide remnants on the carrier or otherwise handle the negative interaction that the pollutant on the elimination carrier material may bring.Cleaning step is included in the carrier material that cleaning was fixed in the preferred deionized water of water.Can be intermittently or continuation mode clean.At room temperature cleaning the wash water halogen ion concentration should continue to outflow is lower than about 1000ppm, more preferably continues to final effluent obtain negative test in silver nitrate test.Cleaning step can carry out afterwards or carry out simultaneously with it reduction step (describing in the back), but is preferably carrying out before.As mentioned above, use not the precursor solution of halide can cancel cleaning step.

Calcination steps

At least a catalyst component can adopt calcination steps with after carrier material contacts.Calcination steps but also can carry out in the other places of this technology typically before reduction step and in fixing step (if using this step) afterwards.In another embodiment, calcination steps carries out after reduction step.Calcination steps comprises carrier material is heated in non-reduced atmosphere (being oxidation or inertia).In the roasting process, the catalyst component on the carrier material is resolved into the mixture of its oxide and free metal form at least in part by its salt.

For example, calcination steps about 100 ℃ to about 700 ℃ of scopes, preferably under the temperature between about 200 ℃ and about 500 ℃, carry out.The used non-reduced gas of roasting can comprise one or more inertia or oxidizing gas such as helium, nitrogen, argon gas, xenon, nitrogen oxide, oxygen, air, carbon dioxide or its combination etc.In a kind of embodiment, calcination steps carries out in the atmosphere of pure basically nitrogen, oxygen, air or its combination.Roasting time can change, but preferably between about 1 and 5 hour.The degree of decomposition of catalyst component salt is relevant with the length of used temperature and impregnated catalyst roasting time, can follow the tracks of by the monitoring volatile decomposition products.

One or more calcination steps can be adopted, so that after at least a catalyst component contact carrier material, whenever all roasting can be carried out.Preferred last calcination steps occurs in before the golden catalyst component catalytic oxidation zirconium carrier material.Perhaps, contain the roasting of golden Zirconia carrier material in about temperature below 300 ℃.By avoiding containing the Zirconia carrier material of gold, reduce CO to the gained catalyst in about temperature roasting more than 300 ℃ ₂The risk that selectivity has a negative impact.

The typical scenario that comprises calcination steps comprises: a) flood roasting then, flood with gold with palladium; B) flood roasting then altogether, flood with gold again with palladium and rhodium; C) flood roasting then, flood roasting then, flood with gold again with rhodium again with palladium; Or d) floods, uses again gold dipping, roasting then with palladium and rhodium.

Reduction step

Another general herein step is to make any remaining catalyst component be transformed into the catalytic activity state by salt or oxide form at least in part, for example passes through reduction step.Typically finish by salt or oxide are exposed in the reducing agent, the example of reducing agent comprises ammonia, carbon monoxide, hydrogen, hydrocarbon, alkene, aldehyde, alcohol, hydrazine, primary amine, carboxylic acid, carboxylate, carboxylate and combination thereof.Hydrogen, ethene, propylene, alkaline hydrazine and alkaline formaldehyde and combination thereof are preferred reducing agents, and ethene that mixes with inert gas and hydrogen are particularly preferred.Although it is preferred adopting the reduction of gaseous environment, also can adopt the reduction step (for example adopting reducing solution) of liquid environment carrying.Reducing selected temperature can be in environment temperature to about 550 ℃ scope.Recovery time typically changed in the scope at about 1 to about 5 hours.

Because the method that catalyst component reduction is adopted may influence the characteristic of finished catalyst, can change according to some balance that is requirement high activity, high selectivity or these character so reduce used condition.

In a kind of embodiment, make palladium contact with carrier material, fix and reduction, contact and reduce with gold then, as US 6,486,093,6,015,769 with described in the relevant patent, all is incorporated herein for reference.

The typical scenario that comprises reduction step comprises: a) flood randomly roasting then, reduce then with the gold dipping with palladium; B) flood randomly roasting then, reduction then altogether with palladium and gold; Or c) floods randomly roasting then, reduction then, floods with gold again with palladium.

Modification procedure

Usually after reduction step and after the catalyst use, wish to have modification procedure.Though this catalyst can use having under the situation of modification procedure, this step has several beneficial effects, comprises the service life that prolongs catalyst.Modification procedure is sometimes referred to as activation step, can carry out in the usual way.That is, the carrier material that makes reduction after using and modifier such as alkali metal carboxylate and/or alkali metal hydroxide contact.Adopt conventional alkali metal carboxylate such as C for this reason _2-4The sodium of aliphatic carboxylic acid, potassium, lithium and cesium salt.Preferred activator is an alkali metal acetate among the production VA, most preferably potassium acetate (KOAc).

Can randomly use the solution impregnating carrier material of modifier.After the drying, catalyst can comprise for example about 10 to about 70, preferred about 20 to about 60g modifier/L catalyst.

The preparation method of alkenyl alkanoates

The present invention is used in catalyst and exists down by alkene, alkanoic acid and oxygen-containing gas production alkenyl alkanoates.Preferred olefin feedstock comprises 2 to 4 carbon atoms (for example ethene, propylene and n-butene).The preferred alkanoic acid raw material that uses contains 2 to 4 carbon atoms (for example acetate, propionic acid and butyric acid) in the method for production alkenyl alkanoates of the present invention.The preferred product of this method is VA, propionate, vinyl butyrate and allyl acetate.Most preferred raw material is ethene and acetate, and VA is most preferred product.Therefore, the present invention is applicable in the presence of catalyst by alefinically unsaturated compounds, carboxylic acid and oxygen production ethylenically unsaturated carboxylic acids ester.Although this specification remainder is only discussed VA, should understand described catalyst agent, Preparation of catalysts method and production method and be equally applicable to other alkenyl alkanoates, description is not application of the present invention will be limited to VA like this.

During with Catalyst Production VA of the present invention, make air-flow (comprising ethene, oxygen or air and acetate) pass through catalyst.Consider the zone of flammability of effluent stream, the composition of air-flow can change in wide boundary.For example, the mol ratio of ethene and oxygen can be about 80: 20 to about 98: 2, and the mol ratio of acetate and ethene can be about 100: 1 to about 1: 100, preferred about 10: 1 to 1: 10, most preferably from about 1: 1 to about 1: 8.Described air-flow can also comprise alkali metal acetate and/or inert gas such as nitrogen, carbon dioxide and/or the saturated hydrocarbons of gaseous state.Spendable reaction temperature is to heat up, preferably in about 125-220 ℃ scope.Used pressure can be reduce pressure a little, normal pressure or pressurization, the pressure of the highest preferred about 20 atmospheric pressure gauge pressures.

Except that fixed bed reactors, the production method of alkenyl alkanoates of the present invention and catalyst also can be used for the reaction of other type, for example fluidized-bed reactor.

Embodiment

Provide following examples only to be used to illustrate and do not plan and limit.The amount of solvent and reactant is similar to.Available following equation is converted into Au/Pd weight ratio and opposite with the Au/Pd atomic ratio: Au/Pd atomic ratio=0.54* (Au/Pd weight ratio), Au/Pd weight ratio=1.85 (Au/Pd atomic ratio).Reduction can be abbreviated as ' R ', the temperature that and then reduce the back (℃).Similarly, roasting can be abbreviated as ' C ', the back and then carry out roasting temperature (℃), and drying steps can be abbreviated as " drying ".

Catalyst that can preparation embodiment 1-11 as be shown in the examples is also tested by the method for back, and wherein the catalyst from embodiment 1-7 can compare mutually, can compare mutually from the catalyst of embodiment 8-11.Provide the result under the obtainable situation.

Catalyst to these embodiment is tested, and tests it in the selectivity of producing the active and various accessory substances in the vinyl acetate by ethene, oxygen and acetic acidreaction.For finishing this test, the catalyst that about 60ml is prepared as described is placed in the stainless SteelBlue, can use thermocouple measuring temperature in the top and the bottom of indigo plant.Indigo plant is put into circular form Berty continuous stirred tank reactor, and the electricity consumption heating mantles remains on the temperature that about 45% OTR is provided.The admixture of gas that makes about 50 standard liters (under N.T.P, measuring) ethene, about 10 standard liter oxygen, about 49 standard liter nitrogen, about 50g acetate and about 4mg potassium acetate under about 12 atmospheric pressure by described indigo plant, catalyst was worn out 16 hours under these reaction conditions at least, carry out 2 hours test then, afterwards cessation reaction.Online gas chromatographic analysis combines with the off-line liquid product analyses that under about 10 ℃ the product gas flow condensation is carried out and carries out product analysis acquisition end-product carbon dioxide (CO ₂), the optimized analysis of heavy ends (HE) and ethyl acetate (EtOAc), its result can be used for calculating the percentage selectivity (CO of these materials of each embodiment ₂Selectivity).Can calculate by computer with a series of related equatioies of a series of kinetic parameters that react in active factor and catalyst temperature (between the stage of reaction), OTR and the synthetic VA process that make with the relative activity of the reaction of active factor (activity) expression.More general ground, active factor typically with obtain that constant OTR is temperature required to be inversely proportional to.

Rhodium catalyst embodiment

Embodiment 1: be prepared as follows the carrier material that contains palladium and rhodium metal: tetrachloro palladium sodium (the II) (Na that at first is enough to provide the every liter of about 7g element of catalyst palladium and about 0.29g elemental rhodium by incipient wetness method with 82.5ml ₂PdCl ₄) and three hydration radium chloride (RhCl ₃3H ₂O) aqueous solution dipping 250ml carrier material, described carrier material is by nominal diameter 7mm, the about 0.569g/ml of density, the about 0.568g H of absorptivity ₂O/g carrier, the about 160-175m of surface area ²The Sud Chemie KA-160 silicon oxide ball of/g and the about 0.68ml/g of pore volume constitutes.Carrier shaken in solution guaranteed that solution absorbed fully in 5 minutes.Make the carrier handled and 283ml by 50%w/w NaOH/H by rotary dipping with about 5rpm then ₂Its amount of O preparation makes palladium and rhodium be fixed on the carrier with palladium dydroxide (II) and rhodium hydroxide (III) form for 120% the sodium hydrate aqueous solution that makes palladium and rhodium change into its hydroxide aequum contacts 2.5 hours.From the carrier of handling, discharge solution, then with the carrier washed with de-ionized water, in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.Adopt incipient wetness method with containing 1.24g then from NaAuCl ₄The aqueous solution (81ml) of Au and 2.71g 50%NaOH solution (is 1.8 equivalents with respect to Au) the dipping carrier material that contains palladium dydroxide and rhodium hydroxide.The spherolite standing over night that NaOH was handled guarantees that Au salt precipitation forms insoluble hydroxide.These spherolites are thoroughly cleaned (～5 hours) with deionized water remove chlorion, then in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.The carrier that then these is contained palladium, rhodium and gold in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.This carrier and gas phase C ₂H ₄(1% in nitrogen) made palladium, rhodium and gold reduction in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 2: preparation contains the carrier material of palladium dydroxide and rhodium hydroxide as described in example 1 above.The carrier that will contain palladium and rhodium then in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.Adopt incipient wetness method with containing 1.24g then from NaAuCl ₄The aqueous solution (81ml) of Au and the carrier material that contains palladium dydroxide and rhodium hydroxide that 2.71g 50%NaOH solution (is 1.8 equivalents with respect to Au) impregnation-calcination is crossed.The spherolite standing over night that NaOH was handled guarantees that Au salt precipitation forms insoluble hydroxide.These spherolites are thoroughly cleaned (～5 hours) with deionized water remove chlorion, then in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made palladium, rhodium and gold reduction in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 3: preparation contains the carrier material of palladium dydroxide and rhodium hydroxide as described in example 1 above.The carrier that will contain palladium and rhodium then in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made the baked carrier material reduction that contains palladium dydroxide and rhodium hydroxide in 5 hours in 150 ℃ of contacts.Adopt incipient wetness method with containing 1.24g then from NaAuCl ₄The aqueous solution (81ml) of Au and 2.71g50%NaOH solution (is 1.8 equivalents with respect to Au) the dipping carrier that contains palladium and rhodium metal.The spherolite standing over night that NaOH was handled guarantees that Au salt precipitation forms insoluble hydroxide.These spherolites are thoroughly cleaned (～5 hours) with deionized water remove chlorion, then in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made palladium, rhodium and gold reduction in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 4: preparation contains the carrier material of palladium dydroxide and rhodium hydroxide as described in example 1 above.The carrier that will contain palladium and rhodium then in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made the baked carrier material reduction that contains palladium dydroxide and rhodium hydroxide in 5 hours in 150 ℃ of contacts.Adopt incipient wetness method with containing 1.1g then from KAuO ₂The aqueous solution (81ml) dipping of Au contain the carrier of palladium and rhodium metal.Make these spherolites in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made palladium, rhodium and gold reduction in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 5: preparation contains the carrier material of palladium dydroxide and rhodium hydroxide as described in example 1 above.The carrier that will contain palladium and rhodium then in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.Adopt incipient wetness method with containing 1.1g then from KAuO ₂The aqueous solution (81ml) dipping of Au contain the carrier of palladium and rhodium metal.Make these spherolites in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made palladium, rhodium and gold reduction in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 6: preparation contains the carrier material of palladium dydroxide and rhodium hydroxide as described in example 1 above.The carrier that will contain palladium and rhodium then in 400 ℃ of roastings 2 hours, makes it to naturally cool to room temperature again under air.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made the baked carrier material reduction that contains palladium dydroxide and rhodium hydroxide in 5 hours in 150 ℃ of contacts.Adopt incipient wetness method with containing 1.1g then from KAuO ₂Au and the aqueous solution (81ml) of the 10g potassium acetate dipping carrier that contains palladium and rhodium metal.Make these spherolites in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.

Embodiment 7 (reference catalyst): the carrier material that is prepared as follows palladium-containing metal: tetrachloro palladium sodium (the II) (Na that at first is enough to provide the every liter of about 7g element of catalyst palladium with 82.5ml by incipient wetness method ₂PdCl ₄) aqueous solution dipping 250ml carrier material, described carrier material is by nominal diameter 7mm, the about 0.569g/ml of density, the about 0.568g H of absorptivity ₂O/g carrier, the about 160-175m of surface area ²The Sud Chemie KA-160 silicon oxide ball of/g and the about 0.68ml/g of pore volume constitutes.Carrier shaken in solution guaranteed that solution absorbed fully in 5 minutes.Make the carrier handled and 283ml by 50%w/w NaOH/H by rotary dipping with about 5rpm then ₂Its amount of O preparation changes into 110% the sodium hydrate aqueous solution contact 2.5 hours of its hydroxide aequum for making palladium, and palladium is fixed on the carrier with palladium dydroxide (II) form.From the carrier of handling, discharge solution, then with the carrier washed with de-ionized water, in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.Adopt incipient wetness method with containing 1.24g then from NaAuCl ₄The aqueous solution (81ml) of Au and 2.71g 50%NaOH solution (is 1.8 equivalents with respect to Au) the dipping carrier material that contains palladium dydroxide.The spherolite standing over night that NaOH was handled guarantees that Au salt precipitation forms insoluble hydroxide.These spherolites are thoroughly cleaned (～5 hours) with deionized water remove chlorion, then in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made the carrier reduction that contains palladium and gold in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.Table 1 illustrates the Catalyst for CO of embodiment 1 and 7 ₂Selectivity and active contrast.

Table 1

	CO 2Selectivity	Active
			Embodiment 1	9.89	2.32
Embodiment 7 (reference catalyst)	11.13	2.36

Layered vector embodiment

Embodiment 8: with 40g ZrO ₂(RC-100, DKK provides) was 650 ℃ of following roastings 3 hours.The BET surface area of gained material is 38m ²/ g.With this material with 120ml DI water ball milling 6 hours.The zirconium acetate adhesive (ZA-20) that this colloidal sol and 22.5g DKK are provided mixes, and is sprayed onto on the bentonite KA-160 ball of 55g OD～7.5mm.With the coating after ball in 600 ℃ of roastings 3 hours.Examine under a microscope the even shell that demonstration has formed thick 250 μ m.

Embodiment 9: with 20g ZrO ₂(XZ16075, BET surface area 55m ²/ g) with Pd (NO ₃) ₂Solution (Aldrich) dipping reaches 39mg/g ZrO ₂Pd load.Make impregnated material dry and in 450 ℃ of roastings 4 hours.This material with 60ml DI water ball milling 4 hours, mix with 11g adhesive (ZA-20), is sprayed onto on the 30g bentonite KA-160 ball.With these balls in 450 ℃ of roastings 3 hours.Cause forming the even shell of thick 160 μ m.

Embodiment 10: will reach the load of 40mgKOAc/ml KA-160 with the potassium acetate solution dipping from the ball of embodiment 8, and dry and in 300 ℃ of roastings 4 hours.9.4mM Pd (Pd (the NH that provides from Heraeus will be provided then ₃) ₄(OH) ₂) and 4.7mM Au (, be dissolved in the Au (OH) of 1.6M KOH from 1M solution ₃" Alfa ") solution be sprayed onto on these balls.Use 5%H ₂/ 95%N ₂Mixture makes material reduction 4 hours in 200 ℃.These balls are pulverized, in micro fixed-bed reactor, under the described condition of test portion, tested.Be issued at 45% OTR～6% CO ₂Selectivity.

Embodiment 11 (reference catalyst): the catalyst of using preparation among the embodiment 7 is as the reference catalyst.Table 2 illustrates the Catalyst for CO of embodiment 9-11 ₂Selectivity and active contrast.

Table 2

	CO 2Selectivity	Active
			Embodiment 9	9.33	2.08
Embodiment 10	9.03	1.69
			Embodiment 11 (reference catalyst)	11.13	2.36

The Zirconia carrier material and the precursor embodiment of chloride not

This group embodiment adopts following general operation.Be prepared as follows the Zirconia carrier material catalyst: the catalyst carrier of different shape is pulverized and screening.The Zirconia carrier material is provided by NorPro (XZ16052 and XZ16075), DKK and MEI.The silica support material is provided by Degussa and Sud Chemie.Pd and Au precursor solution dipping (flood simultaneously or in succession, 110 ℃ middle drying steps and the middle calcination steps of choosing wantonly are arranged) is partly used in the screening of 180-425 μ m, and to just wetting, 5%H is used in randomly roasting in air ₂/ N ₂Generate gas reduction, with flooding behind the KOAc solution, at N ₂In 100 ℃ of dryings, in the 8x6 multichannel fixed bed reacter, screen down.With Au (OH) ₃KOH solution make the Au precursor.With Pd (NH ₃) ₄(OH) ₂, Pd (NH ₃) ₂(NO ₂) ₂, Pd (NH ₃) ₄(NO ₃) ₂And Pd (NO ₃) ₂The aqueous solution make the Pd precursor.

Be prepared as follows silica support material catalyst object of reference: be prepared as follows the carrier material that contains palladium and rhodium metal: tetrachloro palladium sodium (the II) (Na that at first is enough to provide the every liter of about 7g element of catalyst palladium with 82.5ml by incipient wetness method ₂PdCl ₄) aqueous solution dipping 250ml carrier material, described carrier material is by nominal diameter 7mm, the about 0.569g/ml of density, the about 0.568gH of absorptivity ₂O/g carrier, the about 160-175m of surface area ²The Sud ChemieKA-160 silicon oxide ball of/g and the about 0.68ml/g of pore volume constitutes.Carrier shaken in solution guaranteed that solution absorbed fully in 5 minutes.Make the carrier handled and 283ml by 50%w/wNaOH/H by rotary dipping with about 5rpm then ₂Its amount of O preparation changes into 110% the sodium hydrate aqueous solution contact 2.5 hours of its hydroxide aequum for making palladium, and palladium is fixed on the carrier with palladium dydroxide (II) form.From the carrier of handling, discharge solution, then with the carrier washed with de-ionized water, in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.Adopt incipient wetness method with containing 1.24g then from NaAuCl ₄The aqueous solution (81ml) of Au and 2.71g 50%NaOH solution (is 1.8 equivalents with respect to Au) the dipping carrier material that contains palladium dydroxide.The spherolite standing over night that NaOH was handled guarantees that Au salt precipitation forms insoluble hydroxide.These spherolites are thoroughly cleaned (～5 hours) with deionized water remove chlorion, then in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.This carrier and gas phase C then ₂H ₄(1% in nitrogen) made the carrier reduction that contains palladium and gold in 5 hours in 150 ℃ of contacts.Use the 10g potassium acetate at 81ml H by incipient wetness method catalyst at last ₂The aqueous solution among O dipping and in fluidized bed dryer in 100 ℃ of dryings 1.2 hours.Before the test, catalyst is pulverized and screening.Use the screening part of granularity at the 180-425 mu m range.

The design catalyst libraries that 8 row x6 row are arranged in vial is installed in 36 vials on the vortex agitator (vortexer), stirs and uses Cavro simultaneously ^TMLiquid distributor distributes metal precursor solutions.Synthetic and each reaction vessel of each unit, each vial uses the 0.4ml carrier.

KOAc load is with μ mol KOAc form report on g KOAc/L catalyst volume or the 0.4ml carrier.Be standard Au load, with the relative atom ratio of Au/Pd form report Au with Pd.The Pd loadmeter is shown mg Pd/0.4ml carrier bulk (being the absolute magnitude of Pd in the reaction vessel).

Screening scheme adopts 5 ℃ of increments from 145 ℃ to 165 ℃ temperature rise, 175% fixedly air speed (1.5mg Pd being arranged at the 0.4ml carrier).100% air speed is as giving a definition: 5.75sccm nitrogen, 0.94sccm oxygen, 5.94sccm ethene and 5.38 μ l/min acetate by as described in each (internal diameter of the 4mm that all has an appointment) of 48 catalyst containers.CO ₂Selectivity is drawn with respect to OTR, carries out linear fit, and is reported in (in most cases interpolated) CO that calculates under 45% OTR in the performance summary sheet below ₂Selectivity.Temperature under 45% OTR is calculated by temperature rise and (is also reported CO ₂Selectivity and OTR are with respect to the linear fit of reaction temperature).This accounting temperature is low more, and catalyst activity is high more.Space-time yield (STY under 45% OTR; The VA/ml catalyst volume that g produces/h) is the tolerance of catalyst production.

Embodiment 12: with 400 μ l ZrO ₂Carrier XZ16075 (55m ²/ g is during supply) and XZ16052 (make surface area reduce to 42m in 650 ℃/2h preroast ²/ g) with 3 kinds of different Pd solution impregnation to just wet, in 110 ℃ of dryings 5 hours, use KAuO ₂(0.97M Au feed liquid) dipping is to just wet, in 110 ℃ of dryings 5 hours, at 5%H ₂/ N ₂Generate in the gas in 350 ℃ of reduction 4 hours, with flooding behind the KOAc, and in 110 ℃ of dryings 5 hours.Then with these Pd/Au/ZrO ₂Sample (shell) is about to 43 μ l Pd/Au/ZrO with KA160 diluent (pre-loaded have 40g/l KOAc) dilution 1/9.3 ₂In shell and 357 μ l diluents (the total fixed bed volume 400 μ l) reaction vessel of packing into.Pd load is at 400 μ l ZrO ₂14mg Pd in the shell (perhaps 14*43/400=14/9.3=1.5mg Pd in the reaction vessel of all unit).The Pd precursor is: the 1st and 4 row Pd (NH ₃) ₂(NO ₂) ₂, the 2nd and 5 row Pd (NH ₃) ₄(OH) ₂, the 3rd and 6 row Pd (NH ₃) ₄(NO ₃) ₂The 2nd and 5 row Au/Pd=0.3, the 3rd row Au/Pd=0.6, the 4th, 6 and 7 row Au/Pd=0.9.KOAc load is: 2nd, 3 and 5 row, 114 μ mol, the 4th, 6 and 7 row 147 μ mol.The silica reference catalyst is loaded on the 1st row.Fixedly adopting described temperature rise screening scheme to screen under the SV.The selection result is shown in Table 3.

Table 3

	CO 2Selectivity	Temperature exists	STY
				The Cl precursor is at SiO 2On	7.37	156.6	729
Pd(NH 4) 2(OH) 2At ZrO 2On	5.79	152.4	787
				Pd(NH 3) 4(NO 3) 2At ZrO 2On	5.90	152.3	783
Pd(NH 3) 2(NO 2) 2At ZrO 2On	5.57	150.7	795

* data shown in are taken from two kinds of Au/Pd atomic ratios (promptly 0.3 and 0.6) and two kinds of different ZrO ₂The mean value of carrier.

Embodiment 13: with 400 μ l ZrO ₂Carrier XZ16075 (55m ²/ g is during supply) and XZ16052 (make surface area reduce to 42m in 650 ℃/2h preroast ²/ g) with Pd (NH ₃) ₄(OH) ₂(1.117M Pd feed liquid) dipping is to just wet, and roasting is 4 hours in 350 ℃ of air, uses KAuO ₂(0.97M Au feed liquid) dipping is to just wet, in 110 ℃ of dryings 5 hours, at 5%H ₂/ N ₂Generate in the gas in 350 ℃ of reduction 4 hours, with flooding behind the KOAc, and in 110 ℃ of dryings 5 hours.Then with these Pd/Au/ZrO ₂Sample (shell) is about to 33.3 μ l Pd/Au/ZrO with KA160 diluent (pre-loaded have 40g/l KOAc) dilution 1/12 ₂In catalyst and 366.7 μ l diluents (the total fixed bed volume 400 μ l) reaction vessel of packing into.The design and the unit in storehouse are composed as follows: 1-3 row ZrO ₂XZ16075 (left-half in storehouse) and 4-6 row ZrO ₂XZ16052 (650 ℃).Pd load is: unit G2, the 3rd row (unit B 3-G3), unit G5, the 6th row (unit B 6-G6) inherent 400 μ l ZrO ₂18mg Pd in the shell (perhaps 18*33/400=18/12mg Pd in reaction vessel); The 1st row (unit A1-G1) and the 4th row (unit A4-G4) inherent 400 μ l ZrO ₂10mg Pd in the shell (perhaps 10*33/400=10/12mgPd in reaction vessel); The 2nd row (unit B 2-F2) and the 5th row (unit B 5-F5) inherent 400 μ l ZrO ₂14mg Pd in the shell (perhaps 14*33/400=14/12mg Pd in reaction vessel).The 2nd and 5 row Au/Pd=0.3, the 3rd and 6 row Au/Pd=0.5, the 4th and 7 row Au/Pd=0.7 (except unit A1, A4, G2, the G5, wherein Au/Pd is 0.3).KOAc load is 114 μ mol (cells D 3, G3, D6, G6, wherein KOAc load is 147 μ mol).The silica reference catalyst is loaded on the 1st row.Fixedly adopting described temperature rise screening scheme to screen under the SV.The selection result is shown in Table 4.

Table 4

Embodiment 14: with ZrO ₂Carrier (NorPro provides, XZ16075, and 180-425 μ m sieves part, density 1.15g/ml, pore volume 475 μ l/g, BET surface area 55m ²/ g) with Pd (NO ₃) ₂Precursor solution dipping is to just wet, and in 110 ℃ of dryings, KAuO is used in roasting in 250 ℃ (1-2 row), 350 ℃ (3-4 row), 450 ℃ of (5-6 row) air ₂Solution (Au (OH) ₃Be dissolved in the KOH preparation) dipping, in 110 ℃ of dryings, use 5%H ₂/ N ₂Generate gas in 350 ℃ of reduction 4 hours, with flooding behind the KOAc solution.There is gradient from 25 to 50g/l KOAc in this storehouse at the 2nd to 7 row.Pd load is that 1.5mg Pd is on the 0.4ml carrier.Select two kinds of different Au load (the 1st, 3,5 row Au/Pd=0.5, the 2nd, 4,6 row Au/Pd=0.7).The silica reference catalyst is loaded on the 1st row.Fixedly in the MCFB48VA reactor, screening under the SV with described temperature rise screening scheme.The selection result is shown in Table 5.

Table 5

	CO 2Selectivity	Temperature under 45% conversion ratio	STY
				The Cl precursor is at SiO 2On	7.21	154.7	734
Pd(NO 3) 2At ZrO 2On	6.10	145.3	775

* data shown in are taken from the mean value of two kinds of Au/Pd atomic ratios (promptly 0.5 and 0.7) in 40g/L KOAc, 450 ℃ of roastings and 350 ℃ of reduction.

Embodiment 15: with ZrO ₂Carrier (NorPro provides, XZ16075, and 180-425 μ m sieves part, density 1.15g/ml, pore volume 575 μ l/g, BET surface area 55m ²/ g) with Pd (NO ₃) ₂The precursor solution dipping is to just wet, and in 110 ℃ of dryings, KAuO is used in roasting in 450 ℃ of air ₂Solution (Au (OH) ₃Be dissolved in the KOH preparation) dipping, in 110 ℃ of dryings, use 5%H ₂/ N ₂Generate gas in 200 ℃ (1-2 row), 300 ℃ (3-4 row) or 400 ℃ (5-6 row) reduction, with flooding behind the KOAc solution.There is gradient from 15 to 40g/l KOAc in this storehouse at the 2nd to 7 row.Pd load is that 1.5mg Pd is on the 0.4ml carrier.Select two kinds of different Au load (the 1st, 3,5 row Au/Pd=0.5, the 2nd, 4,6 row Au/Pd=0.7).The silica reference catalyst is loaded on the 1st row.Fixedly in the MCFB48VA reactor, screening under the SV with described temperature rise screening scheme.The selection result is shown in Table 6.

Table 6

	CO 2Selectivity	Temperature under 45% conversion ratio	STY
				The Cl precursor is at SiO 2On	7.11	154.2	738
Pd(NO 3) 2At ZrO 2On	5.51	145.4	797

* data shown in are taken from the mean value of two kinds of Au/Pd atomic ratios (promptly 0.5 and 0.7) in 40g/L KOAc, 450 ℃ of roastings and 400 ℃ of reduction.

It is conspicuous that the function of a plurality of assemblies or step or structure can be incorporated into that the function of single component or step or step or assembly or structure can be dispersed in a plurality of steps or the assembly.The present invention's plan comprises all these combinations.Except as otherwise noted, the size of various structures described herein and geometry are not to limit the present invention, and other size or geometry also can.A plurality of construction packages or step can be provided by single overall structure or step.Perhaps, single overall structure or step can be divided into a plurality of assemblies or step separately.In addition, though may be only describe feature of the present invention in an embodiment of enumerating explanation, this feature can be used for any given application with one or more further feature combination of other embodiment.Can find out also that from top the inventive method is also formed in the manufacturing and the operation thereof of unique texture herein.

Explanation that this paper is given and explanation are to make others skilled in the art understand the present invention, its principle and its practical application.Those skilled in the art can its multi-form employing the present invention, can make it the needs of suitable practical application.Therefore, given specific embodiments of the present invention are not to limit the present invention.Thereby scope of the present invention should not determine with the top benchmark that is described as, and should be that benchmark is determined with claims and the four corner that is called the equivalent of these claims.All papers and list of references comprise that patent application and disclosed content all are incorporated herein for reference.

Claims (40)

1. one kind is applicable to the catalyst of promotion alkenyl alkanoates production or the production method of procatalyst, comprising:

Palladium is contacted with containing zirconic carrier material with golden precursor, and the wherein said surface area that contains zirconic carrier material BET is 10 and 135m ²Between/the g; With

By making reducing environment contain zirconic carrier material and contact, make described palladium precursor reduction at least with described.

2. the process of claim 1 wherein that the described surface area of zirconic carrier material BET that contains is at 10m ²/ g and 55m ²Between/the g.

3. claim 1 or 2 method, the wherein said surface area of zirconic carrier material BET that contains is at 38m ²/ g and 55m ²Between/the g.

4. the method for claim 3, the wherein said surface area that contains zirconic carrier material BET is 42m ²/ g.

5. the method for claim 3, the wherein said surface area that contains zirconic carrier material BET is 55m ²/ g.

6. the method for claim 3, the wherein said pore volume of zirconic carrier material that contains is between 0.1ml/g and 0.575ml/g.

7. claim 1 or 2 method, wherein said contact procedure comprise with palladium and golden precursor dipping are described and contain zirconic carrier material.

8. the method for claim 7, wherein said impregnation steps comprises is immersed on the described Zirconia containing support material palladium and golden precursor in succession.

9. claim 1 or 2 method also comprise the fixing step that at least one adopts fixative.

10. claim 1 or 2 method, wherein said reduction step occurs in before the described golden precursor dipping.

11. the method for claim 7, wherein said impregnation steps comprise common palladium-impregnated and golden precursor.

12. the method for claim 7, wherein said impregnation steps comprise that the precursor solution of chloride dipping is not described contains zirconic carrier material with water miscible substantially.

13. the method for claim 12, wherein said substantially not the palladium precursor of chloride comprise Pd (NH ₃) ₂(NO ₂) ₂, Pd (NH ₃) ₄(OH) ₂, Pd (NH ₃) ₄(NO ₃) ₂, Pd (NO ₃) ₂, Pd (NH ₃) ₄(OAc) ₂, Pd (NH ₃) ₂(OAc) ₂, at KOH or NMe ₄Pd among OH or the NaOH (OAc) ₂, Pd (NH ₃) ₄(HCO ₃) ₂, oxalic acid palladium or its combination.

14. the method for claim 12, wherein said substantially not the golden precursor of chloride comprise KAuO ₂, NaAuO ₂, NMe ₄AuO ₂, at KOH or NMe ₄Au among the OH (OAc) ₃, the HAu (NO in nitric acid ₃) ₄Or its combination.

15. the method for claim 1 or 2, wherein said contact procedure also comprise the 3rd component precursor that contacts rhodium-containing.

16. the method for claim 1 or 2 also comprises making potassium acetate contain zirconic carrier material and contact with described.

17. the method for claim 16, the amount of wherein said potassium acetate are between every liter of catalyst about 10 and 70 grams.

18. the method for claim 1 or 2, wherein said contact procedure comprise that the palladium that makes between every liter of catalyst 1 to 10 gram and the gold of every liter of catalyst 0.5 to 10 gram contacts, golden amount is 10 to 125wt% based on the weight of palladium.

19. the method for claim 1 or 2, wherein the atomic ratio of gold and palladium is between 0.50 and 1.00.

20. one kind is used for the composition that the catalysis alkenyl alkanoates is produced, comprises:

A kind of BET surface area is at 10m ²/ g and 135m ²Contain zirconic carrier material between the/g, on it at least contact palladium and gold are arranged to form catalyst or procatalyst.

21. the composition of claim 20, the wherein said surface area of zirconic carrier material BET that contains is at 10m ²/ g and 55m ²Between/the g.

22. the composition of claim 20 or 21, the wherein said surface area of zirconic carrier material BET that contains is at 38m ²/ g and 55m ²Between/the g.

23. the composition of claim 22, the wherein said surface area that contains zirconic carrier material BET is 42m ²/ g.

24. the composition of claim 22, the wherein said surface area that contains zirconic carrier material BET is 55m ²/ g.

25. the composition of claim 22, the wherein said pore volume of zirconic carrier material that contains is between 0.1ml/g and 0.575ml/g.

26. the composition of claim 20 or 21, wherein said palladium and gold are reduced.

27. the composition of claim 20 or 21, wherein said catalyst or procatalyst comprise the 3rd component of rhodium-containing.

28. the composition of claim 20 or 21, wherein said catalyst or procatalyst are included in the palladium between every liter of catalyst 1 to 10 gram and the gold of every liter of catalyst 0.5 to 10 gram, the amount of gold is 10 to 125wt% based on the weight of palladium.

29. the composition of claim 20 or 21, wherein said catalyst or procatalyst comprise potassium acetate.

30. the composition of claim 20 or 21, the amount of wherein said potassium acetate is between every liter of catalyst 10 and 70 grams.

31. the composition of claim 20 or 21 wherein saidly contains zirconic carrier material and comprises particulate support material or powder carrier material.

32. the production method of an alkenyl alkanoates comprises:

The charging that comprises alkene, alkanoic acid and oxidant is contacted with catalyst or procatalyst, and described catalyst or procatalyst comprise and are supported on the BET surface area at 10m ²/ g and 135m ²Contain palladium and gold on the zirconic carrier material between/the g.

33. the method for claim 32, the wherein said surface area of zirconic carrier material BET that contains is at 10m ²/ g and 55m ²Between/the g.

34. the method for claim 32 or 33, the wherein said surface area of zirconic carrier material BET that contains is at 38m ²/ g and 55m ²Between/the g.

35. the method for claim 34, the wherein said surface area that contains zirconic carrier material BET is 42m ²/ g.

36. the method for claim 34, the wherein said surface area that contains zirconic carrier material BET is 55m ²/ g.

37. the method for claim 34, the wherein said pore volume of zirconic carrier material that contains is between 0.1ml/g and 0.575ml/g.

38. the method for claim 32 or 33, wherein said alkene are ethene, described alkanoic acid is an acetate, and described oxidant is an oxygen-containing gas.

39. the method for claim 32 or 33, wherein said catalyst or procatalyst comprise the 3rd component of rhodium-containing.

40. the method for claim 32 or 33, wherein said catalyst or procatalyst are included in the palladium between every liter of catalyst 1 to 10 gram and the gold of every liter of catalyst 0.5 to 10 gram, the amount of gold is 10 to 125wt% based on the weight of palladium.