CN101637729B

CN101637729B - Palladium-containing catalyst, method for producing same, and method for producing alpha, beta-unsaturated carboxylic acid

Info

Publication number: CN101637729B
Application number: CN2009101398180A
Authority: CN
Inventors: 安川隼也; 松井俊树; 大谷内健; 姬野嘉之; 二宫航
Original assignee: Mitsubishi Rayon Co Ltd
Current assignee: Mitsubishi Kasei Corp
Priority date: 2005-02-18
Filing date: 2006-02-17
Publication date: 2012-06-27
Anticipated expiration: 2026-02-17
Also published as: CN101637729A; CN101151097A; SG137840A1; CN101151097B

Abstract

Disclosed is a palladium-containing catalyst which enables to highly selectively produce an alpha, beta-unsaturated carboxylic acid from an olefin or an alpha, beta-unsaturated aldehyde. Also disclosed are a method for producing such a catalyst and a method for producing an a,ss-unsaturated carboxylic acid wherein such a catalyst is used. Specifically disclosed is a palladium-containing catalyst containing 0.001-0.25 mole of antimony element per 1 mole of palladium element or a palladium-containing catalyst containing palladium element, tellurium element and bismuth element which constitute the metal component.

Description

Palladium-containing catalyst and preparation method thereof and α, the preparation method of beta-unsaturated carboxylic acid

The application invention is that application number is 200680009911.4, denomination of invention is palladium-containing catalyst and preparation method thereof and α, and the preparation method of beta-unsaturated carboxylic acid, the applying date are the dividing an application of application on February 17th, 2006.

Technical field

The present invention relates to be used for by alkene or α, beta-unsaturated aldehyde prepares α, the palladium-containing catalyst of beta-unsaturated carboxylic acid, this Preparation of catalysts method and α, the preparation method of beta-unsaturated carboxylic acid.

Background technology

α, beta-unsaturated carboxylic acid useful material in industry is a lot.For example, acrylic acid, methacrylic acid are used by a large amount of in the purposes of synthetic resin raw material etc.

As preparation α, the method for beta-unsaturated carboxylic acid, to alkene or α, beta-unsaturated aldehyde carries out the method that liquid phase oxidation prepares with molecularity oxygen and studies.As being used for alkene or α, beta-unsaturated aldehyde utilizes molecularity oxygen to carry out liquid phase oxidation to prepare α, and the catalyst of beta-unsaturated carboxylic acid has for example proposed palladium-containing catalyst in patent documentation 1.In addition, prepare α as being used for utilizing molecularity oxygen to carry out liquid phase oxidation in alkene, the catalyst of beta-unsaturated carboxylic acid has for example proposed to contain the palladium-containing catalyst of palladium and the intermetallic compound of lead, bismuth, thallium or mercury in patent documentation 2.

In addition; Be fit to the palladium-containing catalyst that the acetate benzyl ester prepares usefulness as being not suitable for carboxylic acid preparation usefulness; In patent documentation 3, propose palladium/bismuth atom than the carboxylate catalyst for preparing that is 3/1.4～3/0.8, in patent documentation 4, proposed palladium/bismuth (atomic ratio) and be 2.5～3.5 acetate benzyl ester catalyst for preparing.

Patent documentation 1: the spy opens the 2004-141863 communique

Patent documentation 2: the spy opens clear 56-59722 communique

Patent documentation 3: the spy opens flat 10-263399 communique

Patent documentation 4: the spy opens flat 10-7616 communique

Summary of the invention

But, in the liquid phase oxidation of the palladium-containing catalyst of in having used patent documentation 1 and 2, having put down in writing, target product α, the selection rate of beta-unsaturated carboxylic acid is insufficient, the further raising of expectation selection rate.In addition, though with the catalyst of record in patent documentation 3 and 4 as through molecularity oxygen with alkene or α, beta-unsaturated aldehyde carries out liquid phase oxidation and prepares α, the catalyst of beta-unsaturated carboxylic acid, its selection rate is also often little.

And then, in the liquid phase oxidation of having used above-mentioned catalyst, the secondary great amount of carbon dioxide that generates.If the selection rate of secondary carbon dioxide of giving birth to increases, α then, the selection rate of beta-unsaturated carboxylic acid descends, and therefore expects the repressed catalyst of selection rate of carbon dioxide.

Therefore; The object of the present invention is to provide can be with high selectivity by alkene or α; Beta-unsaturated aldehyde prepares α, the palladium-containing catalyst of beta-unsaturated carboxylic acid, this Preparation of catalysts method and the α that uses this catalyst, the preparation method of beta-unsaturated carboxylic acid.

The present invention is used for by alkene or α, and beta-unsaturated aldehyde prepares α, and the palladium-containing catalyst of beta-unsaturated carboxylic acid is following (i) or catalyst (ii).

(i) a kind of palladium-containing catalyst is with respect to 1 mole of palladium element, contain 0.001～0.25 mole of antimony element.

(ii) a kind of palladium-containing catalyst contains palladium element and tellurium element and bismuth element, and said palladium element constitutes metal.

The palladium-containing catalyst of above-mentioned (i), and then, contain 0.001～0.4 mole of tellurium element with respect to 1 mole of palladium element.The palladium-containing catalyst of above-mentioned (i); Method through comprising following operation prepares; Said operation is the operation that operation that the compound of the palladium element that contains the state of oxidation is reduced with reducing agent and the compound of the antimony element that will contain the state of oxidation reduce with reducing agent.

Above-mentioned palladium-containing catalyst (ii); Can prepare through the method that comprises following operation; Said operation be with the compound of the palladium element that contains the state of oxidation, contain the state of oxidation tellurium element compound and contain the compound of the bismuth element of the state of oxidation, the operation of reducing with reducing agent.

In addition, the present invention is to use above-mentioned palladium-containing catalyst, with alkene or α, and the α that beta-unsaturated aldehyde carries out liquid phase oxidation with molecularity oxygen, the preparation method of beta-unsaturated carboxylic acid.

According to the present invention, can provide can be with high selectivity by alkene or α, and beta-unsaturated aldehyde prepares α, the palladium-containing catalyst of beta-unsaturated carboxylic acid.In addition, through using this palladium-containing catalyst, can prepare α with high selectivity, beta-unsaturated carboxylic acid.And then, can reduce carbon dioxide by-product.

The specific embodiment

Palladium-containing catalyst of the present invention (following also be called for short " catalyst ") is to be used for alkene or α, and beta-unsaturated aldehyde carries out liquid phase oxidation with molecularity oxygen and prepares α, the catalyst of beta-unsaturated carboxylic acid (following also abbreviation " liquid phase oxidation ").

< first embodiment of palladium-containing catalyst >

First embodiment of palladium-containing catalyst of the present invention is with respect to 1 mole of palladium element, contains the palladium-containing catalyst of 0.001～0.25 mole antimony element.This catalyst preferably further with respect to 1 mole of palladium element, contain 0.001～0.4 mole of tellurium element.

The palladium element that contains in the catalyst is preferably the metallic state of 0 valency.The antimony element that contains in the catalyst, be preferably+3 valencys ,+4 valencys ,+state of oxidation of 5 valencys or the metallic state of 0 valency.The tellurium element that according to circumstances contains in the catalyst, be preferably+6 valencys ,+state of oxidation of 4 valencys or the metallic state of 0 valency.

Molal quantity through making the antimony element in the catalyst with respect to 1 mole of palladium element (being the mol ratio Sb/Pd of antimony element and palladium element) in prescribed limit; Can form can be with high selectivity by alkene or α; Beta-unsaturated aldehyde prepares α, the catalyst of beta-unsaturated carboxylic acid.Sb/Pd is preferably 0.005～0.25, and more preferably 0.01～0.23.In addition; Molal quantity through making the tellurium element in the catalyst with respect to 1 mole of palladium element (being the mol ratio Te/Pd of tellurium element and palladium element) in prescribed limit; Can form can be with high selectivity by alkene or α, and beta-unsaturated aldehyde prepares α, the catalyst of beta-unsaturated carboxylic acid.Te/Pd more preferably 0.005～0.35, further is preferably 0.01～0.3.This Sb/Pd and Te/Pd, the proportioning of palladium compound, antimonial and the tellurium compound that uses in can the preparation through palladium-containing catalyst waits to be adjusted.

Sb/Pd can calculate according to the quality and the atomic weight of antimony element that contains in the catalyst and palladium element.The quality of antimony element that contains in the catalyst and palladium element can be come quantitatively through elementary analysis.In addition; The method that the palladium element that can use filling perforation (pore filling) method that kind to make to contain in Pd raw material and the Sb raw material and the total amount in fact of antimony element are included in the catalyst prepares under the situation of catalyst, calculates the quality of two elements according to the antimony containing ratio and the use level of the Sb raw material of the palladium containing ratio of the Pd raw material that uses and use level, use.Te/Pd also can use the same method quantitatively.

Quantitative approach as the quality of palladium element in the catalyst that utilizes elemental microanalysis method and antimony element can illustration go out, the method that modulation following A treatment fluid and B treatment fluid are analyzed.Tellurium element also can be measured equally.

The modulation of A treatment fluid: red fuming nitric acid (RFNA), the concentrated sulfuric acid, the hydrogen peroxide solution of catalyst 0.2g and ormal weight are put into テ Off ロ Application (registration mark) system decompose pipe, (CEM society system, MARS5 (trade name)) carries out dissolution process with the heating using microwave decomposer.After with sample filtering, merging filtrate and washings, constant volume are in volumetric flask, as the A treatment fluid.

The modulation of B treatment fluid: the filter paper that will collect the portion of not dissolving during A handles is transferred in the crucible of platinum system, after the heating ashing, adds lithium metaborate, uses the gas arc lamp fusion.After cooling, in crucible, add hydrochloric acid and low amounts of water, dissolving back constant volume is in volumetric flask, as the B treatment fluid.

With ICP apparatus for analyzing luminosity (サ one モエレメ Application タ Le society system IRIS-Advantage (trade name)) antimony element that contains in the A treatment fluid that obtains and the B treatment fluid and the quality of palladium element are carried out quantitatively; According to the aggregate value of the quality of each element in two treatment fluids, can obtain the quality of each element in the catalyst.

In addition, the catalyst of the present invention of above-mentioned that kind can be non-supported, on carrier, supports the loaded of palladium element and antimony element or palladium element, antimony element and tellurium element but be preferably.As carrier, for example can enumerate out active carbon, carbon black, silica, aluminium oxide, magnesia, calcium oxide, titanium oxide and zirconia etc.Wherein, preferred silica, aluminium oxide, magnesia, calcium oxide, titanium oxide and zirconia, preferred especially silica, titanium oxide, zirconia.Carrier can use a kind, also can use more than 2 kinds.Under situation about using more than 2 kinds, for example can enumerate out, with silica and aluminium oxide mix and the mixture of the mixed oxide of acquisition etc., as the compound of the silica-alumina of composite oxides etc. etc.

Can not decide without exception by difference along with the difference of the kind of carrier etc. for the preferred specific area of carrier, but under the situation of silica, specific area is for being preferably 50m ²/ g is above, 100m more preferably ²More than/the g, be preferably 1500m ²Below/the g, 1000m more preferably ²/ g.The specific area of carrier is more little, can prepare useful component (palladium element, antimony element) more and be supported on more near the catalyst on surface, and the specific area of carrier is big more, can prepare the catalyst that supports more useful components more.

Pore volume to carrier does not have special qualification, but is preferably more than the 0.1cc/g, more preferably more than the 0.2cc/g, is preferably below the 2.0cc/g, more preferably below the 1.5cc/g.

The shape of carrier, size be according to the shape of reaction unit, size etc. and different, and not special the qualification can be enumerated out different shapes such as for example Powdered, granular, spherical, graininess.Wherein, preferred filtration waits the granular, spherical of processing ease.Carrier is that the particle diameter (average diameter) under Powdered, the granular situation is preferably more than the 0.5 μ m, more preferably more than the 1.0 μ m, is preferably below the 200 μ m, more preferably below the 100 μ m.The particle diameter of carrier is big more, and catalyst is easy more with separating of reactant liquor, and the particle diameter of carrier is more little, and the dispersiveness of the catalyst in the reactant liquor is high more.

Under the situation of supported catalyst, palladium element and antimony element support rate with respect to the total of carrier, and the carrier quality with respect to before supporting is preferably 0.1～40 quality %, and more preferably 0.5～30 quality % further is preferably 1.0～20 quality %.

The rate that supports under the situation of supported catalyst can be calculated according to the quality of the carrier of the quality of each element of obtaining with said method etc. and use.In addition, the quality of carrier also can use following method quantitative.That is, catalyst is got in the platinum alloy crucible, added sodium carbonate and carry out fusion.Add distilled water then, form uniform solution, come the element-specific in the quantitative sample solution with the ICP luminesceence analysis.For example under the situation of silica supports, quantitative Si element.

Catalyst of the present invention except palladium element, antimony element and tellurium element, can contain other metallic element.As other metallic element, for example can enumerate out platinum, rhodium, ruthenium, iridium, gold, silver, osmium, copper, lead, bismuth, thallium, mercury etc.Can contain other metallic element more than a kind or 2 kinds.From realizing the viewpoint of high catalytic activity, in the metallic element that contains in the catalyst, the total of palladium element, antimony element and tellurium element is preferably more than the 60 quality %, more preferably more than the 80 quality %.

Below, Preparation of catalysts method of the present invention is described.

Catalyst of the present invention; Preferably with comprising that the method for following operation prepares; Said operation is operation of reducing with reducing agent of the compound with the palladium element that contains the state of oxidation (below be also referred to as " Pd reduce operation ") and the compound that will contain the antimony element of the state of oxidation operation of reducing with reducing agent (below be also referred to as " Sb reduce operation ").And then, contain in preparation under the situation of catalyst of tellurium element, preferably with comprising that the method for following operation prepares, said operation is Pd reduction operation, Sb reduction operation and the interpolation operation that contains the compound of tellurium element (below be also referred to as " Te adds operation ").After Te adds operation, also can carry out the operation of the compound that contains this tellurium element being reduced with reducing agent.

As the palladium compound of the palladium element that contains the state of oxidation (below be also referred to as " Pd raw material "), for example can enumerate out, palladium salt, palladium oxide, palladium oxide alloy etc., wherein, preferred palladium salt.As palladium salt, for example can enumerate out, palladium bichloride, palladium, palladium nitrate, palladium sulfate, chlorination four ammino palladiums and two (acetylacetone,2,4-pentanedione) palladium etc., wherein, preferred palladium bichloride, palladium, palladium nitrate, chlorination four ammino palladiums.

As the antimonial of the antimony element that contains the state of oxidation (below be also referred to as " Sb raw material "), for example can enumerate out antimonic salt, pure antimony, metantimonic acid and salt thereof, organo-antimony compound, antimony oxide etc.As antimonic salt, for example can enumerate out antimony fluoride, antimony chloride, bromize antimony, antimony iodide, antimony acetate, potassium antimony tartrate, antimony tartrate, antimony trisulfide etc.As pure antimony, for example can enumerate out methyl alcohol antimony, ethanol antimony, isopropyl alcohol antimony, butanols antimony, antimony glycol etc.As meta-antimonate, for example can enumerate out ammonium metaantimonate etc.As organo-antimony compound, for example can enumerate out antimony triphenyl etc.Wherein, preferred antimony tartrate, ammonium metaantimonate etc.

As the tellurium compound that contains tellurium element (below be also referred to as " Te raw material "), can enumerate out tellurium metal, tellurium salt, telluric acid and salt, tellurous acid and salt, tellurium oxide etc.As tellurium salt, can enumerate out for example hydrotelluric acid, telluric chloride, tellurium chloride, tellurium hexafluoride, telluric iodide, telluric bromide, tellurium bromide etc.As tellurate, for example can enumerate out llurate, potassium tellurate etc.As tellurite, for example can enumerate out sodium tellurite, potassium tellurite etc.Wherein, preferred telluric acid and salt, tellurous acid and salt thereof, tellurium oxide.In addition, because that the reduction of Te raw material is not necessarily is necessary, so the tellurium element that contains in the Te raw material, can be the state of oxidation, reducing condition, metallic state.

In addition, except using the method for above-claimed cpd, can also use the compound more than 2 kinds that contains in palladium element, antimony element and the tellurium element etc. as the raw material of catalyst.Specifically, for example can enumerate out palladium-tellurium complex PdX _n(TeRR ') _4-nDeng.In addition, at PdX _n(TeRR ') _4-nIn, Pd representes palladium, and X representes fluorine, chlorine, bromine or iodine, and Te representes tellurium, and R, R ' represent alkyl respectively independently, n representes 0～3 integer.In addition, also can use two sides' the compound etc. of the antimony element of the palladium element that contains the state of oxidation and the state of oxidation.

Suitably select above-mentioned Pd raw material, Sb raw material, use raw material as Preparation of Catalyst.Suitably select the use level of these compounds, so that Sb/Pd, the rate of supporting reach desired value.Contain in preparation under the situation of catalyst of tellurium element, suitably select above-mentioned Te raw material, use raw material as Preparation of Catalyst.Suitably select the use level of Te raw material, so that Te/Pd, the rate of supporting reach desired value.

In addition, except palladium element, antimony element, the tellurium element, also contain under the situation of catalyst of other metallic element in preparation, as raw material, can and with the compound that contains other metallic element (below be also referred to as " other raw material ").As other raw material, can enumerate out, contain metal, metal oxide, slaine, oxometallic acid, oxometallate of other metallic element etc.

Pd reduction operation, Sb reduction operation can be carried out simultaneously, also can carry out respectively.Under the situation of carrying out respectively, the order of Pd reduction operation, Sb reduction operation is arbitrarily.Under the situation of carrying out Te interpolation operation, this Te adds operation and can reduce operation and/or Sb reduction operation while with Pd, also can be according to carrying out in proper order arbitrarily.In addition; Contain in preparation under the situation of catalyst of the metallic element beyond the palladium element, antimony element, tellurium element; Under the situation of the operation of other raw material of the state of oxidation being reduced with reducing agent; This reduction operation can be reduced operation and/or Sb reduction operation and/or Te interpolation operation simultaneously with Pd, also can be according to carrying out in proper order arbitrarily.

Under the situation of preparation supported catalyst, preferably in the presence of carrier, carry out above-mentioned reduction operation.Method of reducing during as the preparation supported catalyst for example can be enumerated out,

After the raw material that (1) will contain the metallic element of the state of oxidation is supported on the carrier, contact, come the method for reducing metal element with reducing agent,

(2) make the solution or the slurry of the raw material of the metallic atom that contains the state of oxidation, with the carrier state of contact under, contact with reducing agent, in the reduction of the metallic element in solution or the slurry, the method that supports,

(3) after implementing the method for (2), and then the method etc. of adding other raw metal.The method of reducing of (1) of the catalyst that wherein, the decentralization of the preferred metallic element of acquisition easily is high.

Method of reducing as (1); Preferred being dissolved in the solvent more than a kind or 2 kinds with Pd raw material, Sb raw material, Te raw material and other raw material (following also be generically and collectively referred to as " raw metal "); In the lysate that is obtained, heat treated makes raw metal be changed to metal oxide then with carrier impregnation; The metal oxide that is supported on the carrier is contacted with reducing agent, come the method that metal oxide is reduced.In addition, in the method, also can be arranged on heat treated front evaporator solvent in addition, make raw metal be supported on the operation on the carrier.

Lysate is impregnated in the method for preparing catalyst in the carrier, is the filling perforation method in the method for evaporating solvent with the method for carrier impregnation back evaporating solvent in lysate or after making the lysate of pore volume amount of carrier absorption carrier preferably.The solvent of lysate so long as the solvent of dissolution of metals raw material just have no particular limits.As the solvent of raw metal, can be used alone or in combination for example water; The organic carboxyl acid class of acetic acid, valeric acid etc.; The inorganic acid of nitric acid, hydrochloric acid etc.; The alcohols of ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butanol, the tert-butyl alcohol etc.; The ketone of acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone etc.; The solvent of the hydro carbons of heptane, hexane, cyclohexane etc. etc.From the viewpoint of the dispersiveness of the dissolubility of raw metal and reducing agent or carrier, preferred water, organic carboxyl acid class.

Lysate is impregnated into the operation in the carrier, can uses the lysate that all contains raw metal only to carry out 1 time, also can repeatedly use lysate to carry out repeatedly.Under the situation of carrying out repeatedly, the 2nd later dip operation can be after previous solvent evaporation back, heat treated or carried out reduction arbitrary after handling the time.Order to the carrying metal element does not have special qualification.

The temperature of heat treated is preferably more than the decomposition temperature that raw metal becomes metal oxide.The time of heat treated is preferably 1～12 hour so long as at least a portion of raw metal becomes the time of metal oxide gets final product.

As the method for reducing of (2), for example can enumerate out, dissolving or disperse that raw metal obtains solution or slurry more than a kind or 2 kinds in solvent contacts with reducing agent, comes the method for reducing metal raw material in that this solution or slurry are impregnated under the state in the carrier; Make carrier be distributed in above-mentioned lysate or the slurry under the state method that contacts the reducing metal raw material with reducing agent etc.

The operation that contacts with reducing agent can use the lysate that all contains raw metal only to carry out 1 time, also can repeatedly use lysate to carry out repeatedly.Under the situation of carrying out repeatedly, during handling, the 2nd later reduction use the carrier after previous reduction is handled.Order to the carrying metal element does not have special qualification.

As the method for reducing of (3), preference as in the presence of carrier with solution or slurry behind the raw material of reducing agent reducing metal in, add separately in the solvent of water etc. dissolving or disperse other raw metal and the solution that obtains or the method for slurry.As the solution that adds or the solvent of slurry, preferred water, but also can use above-mentioned various organic solvents etc.After adding other raw metal, can add reducing agent once more and reduce.

Repeatedly reducing under the situation about handling, the kind of reducing agent, reduction temperature and time, the solvent types when in liquid phase, carrying out etc. can suitably be set separately when carrying out at every turn.

In the present invention, preferably under the solution of Pd raw material and carrier state of contact, contact, after the reduction of Pd raw material, Sb raw material (with the Te raw material) is dissolved or is dispersed in the water, add the solution that obtained or the method for slurry with reducing agent.Then, as required, Sb raw material (with the Te raw material) is reduced.

The reducing agent that uses during to reduction does not have special qualification; For example can enumerate; Hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, formates, ethene, propylene, 1-butylene, 2-butylene, isobutene, 1,3-butadiene, 1-heptene, 1-hexene, 2-hexene, cyclohexene, allyl alcohol, methallyl alcohol, methacrylaldehyde and MAL etc.Wherein, preferred hydrazine, formaldehyde, formic acid, formates.In addition, also can be also with more than 2 kinds.

The solvent that uses during as the reduction in the liquid phase, preferred water still according to the dispersiveness of carrier, also can be used the alcohols that is used alone or in combination ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butanol, the tert-butyl alcohol etc.; The ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.; The organic acid of acetic acid, positive valeric acid, isovaleric acid etc.; The organic solvent of the hydro carbons of heptane, hexane, cyclohexane etc. etc.Also can use the mixed solvent of this organic solvent and water.

When reducing agent is gas,, preferably in the pressue device of autoclave etc., carry out in order to improve the solubility in solution.At this moment, preferably pressurize with reducing agent in the inside of pressue device.Its pressure is preferably 0.1～1MPa (gauge pressure, following surface pressure is put down in writing with gauge pressure).

In addition, when reducing agent is liquid,, can carry out through in solution, adding reducing agent to the not restriction of device of reducing.The use amount of the reducing agent of this moment does not have special qualification, still with respect to the palladium compound of 1 mole of state of oxidation, is preferably 1 mole～100 moles.

Reduction temperature and recovery time, and different, reduction temperature is preferably-5～150 ℃, more preferably 15～80 ℃ according to metallic element or metal oxide, the reducing agent etc. of reduction object.

Recovery time is preferably 0.1～4 hour, more preferably 0.25～3 hour, further is preferably 0.5～2 hour.

Using the raw metal that needn't reduce to prepare under the situation of supporting property catalyst, can on the carrier of above-mentioned reduction that is through with, support this raw metal.

The catalyst that is obtained can water, organic solvent etc. washs.Wash through water, organic solvent etc., remove raw metal of for example deriving from chloride, acetate, nitrate anion, sulfate radical etc. etc. impurity, derive from the impurity of reducing agent etc.Method and number of times to washing do not have special qualification, still according to the difference of impurity, hinder liquid phase oxidation reaction sometimes, and therefore preferred washing is to the degree that can fully remove impurity.Catalyst after the washing can directly be used for reaction after reclaiming through filter or centrifugation etc.In addition, in other process, carry out also preferably during this process, washing under the situation of Pd reduction operation and Sb reduction operation.

In addition, can carry out drying to the catalyst that reclaims.Drying means is not had special qualification, but the preferred drying machine that uses carries out drying in air or in the inert gas.Dry catalyst as required, also can carry out activation before being used for reaction.Method to activation does not have special qualification, for example can enumerate out the method for heat-treating under the reducing atmosphere in hydrogen stream.According to this method, can remove oxide film thereon and the impurity that is in the suds and does not remove on the surface of palladium element, antimony element.

< second embodiment of palladium-containing catalyst >

Palladium-containing catalyst of the present invention is the catalyst that contains palladium element, tellurium element and bismuth element, and said palladium element constitutes metal.Through forming the catalyst that contains palladium of such composition, can be with high selectivity by alkene or α, beta-unsaturated aldehyde prepares α, beta-unsaturated carboxylic acid.

Palladium-containing catalyst contains this situation of the palladium element that constitutes metal, can wait and measure through XRD determining, XPS (x-ray photoelectron spectrum analysis method).In XRD determining, in the x-ray diffractogram of powder that Cu-K α line produces, near x-ray diffraction angle (2 θ) 40 degree, there is the peak of (111) face that is equivalent to palladium metal.This peak can be observed at 40.11 degree usually, but the alloying of the palladium element of metallic state and tellurium element and/or bismuth element or the formation of intermetallic compound make this peak position move on to the low angle side sometimes.In the present invention, be under the situation at peak of 39.0 degree～40.11 degree observing as x-ray diffraction angle (2 θ), be defined as and contain the palladium element that constitutes metal.Wherein, constitute the palladium element of metal, preferably as above such and tellurium element and/or bismuth element alloying or formation intermetallic compound, the x-ray diffraction angle (2 θ) that more preferably contains the peak is the above palladium elements of 39.2 degree.In addition, the x-ray diffraction angle (2 θ) that preferably contains the peak is the palladium element below 40.0 degree, more preferably contains the palladium element below 39.9 degree.

Tellurium element in the palladium-containing catalyst needs to surpass 0 with respect to the mol ratio (Te/Pd) of palladium element, is preferably more than 0.002, and more preferably more than 0.003, Te/Pd is preferably below 0.30, more preferably below 0.25.Te/Pd can through after the match ratio of each raw material of the palladium element that uses in the preparation of the palladium-containing catalyst stated and tellurium element wait and adjust.

Chemical state to the tellurium element that contains in the palladium-containing catalyst; Do not have special qualification, can be metallic state, can be the state of oxidation yet; But tellurium element is preferably metallic state, because the electronic state of the palladium element that constitutes metal is further changed.In addition, tellurium element is more preferably element alloyed or form intermetallic compound with palladium, therefore can make like this and tellurium element increases in abutting connection with the ratio of the altered greatly palladium element of electronic state that causes.

Bismuth element in the palladium-containing catalyst needs to surpass 0 with respect to the mol ratio (Bi/Pd) of palladium element, is preferably more than 0.002, and more preferably more than 0.003, Bi/Pd is preferably below 0.26, more preferably below 0.10, is preferably below 0.06 especially.Bi/Pd can through after the match ratio of each raw material of the palladium element that uses in the preparation of the palladium-containing catalyst stated and bismuth element wait and adjust.

The chemical state of the bismuth element that contains in the palladium-containing catalyst; Do not have special qualification, can be metallic state, can be the state of oxidation yet; But bismuth element is preferably metallic state, because the electronic state of the palladium element that constitutes metallic state is further changed.In addition, bismuth element is more preferably element alloyed or form intermetallic compound with palladium, because can make like this and bismuth element increases in abutting connection with the ratio of the altered greatly palladium element of electronic state that causes.

Te/Pd in the palladium-containing catalyst and Bi/Pd sum ((Te+Bi)/Pd) needs to surpass 0, but in order to improve α; The selection rate of beta-unsaturated carboxylic acid further reduces carbon dioxide by-product, is preferably more than 0.004; More preferably more than 0.006; Be preferably below 0.4, more preferably below 0.10, be preferably below 0.3 especially.

In addition, Te/Pd, Bi/Pd and (Te+Bi)/Pd can calculate according to the quality and the atomic weight of the palladium element, tellurium element and the bismuth element that contain in the palladium-containing catalyst after the modulation.The quality of palladium element, tellurium element and bismuth element in the palladium-containing catalyst can use following method to measure.

The modulation of A treatment fluid: contain at carrier under the situation of silica, the hydrofluoric acid of palladium-containing catalyst, red fuming nitric acid (RFNA), 48 quality % is taken to テ Off ロ Application (registration mark) system decomposes pipe, carry out dissolution process with the heating using microwave decomposer.Do not contain at carrier under the situation of silica, palladium-containing catalyst, red fuming nitric acid (RFNA), hydrogen peroxide solution are taken to テ Off ロ Application (registration mark) system decompose pipe, carry out dissolution process with the heating using microwave decomposer.After with sample filtering, merging filtrate and washings, constant volume are in volumetric flask, as the A treatment fluid.

The modulation of B treatment fluid: not dissolving under the situation of portion, the filter paper of having collected the portion of not dissolving is transferred in the crucible of platinum system, after the heating ashing, added lithium metaborate, use the gas arc lamp fusion with above-mentioned processing existence.After cooling, in crucible, add hydrochloric acid and low amounts of water, dissolving back constant volume is in volumetric flask, as the B treatment fluid.

With the ICP apparatus for analyzing luminosity quality of the palladium element, tellurium element and the bismuth element that contain in the A treatment fluid that obtains and the B treatment fluid is carried out quantitatively, with the aggregate value of the quality in two treatment fluids quality as palladium element, tellurium element and bismuth element in the palladium-containing catalyst.

Palladium-containing catalyst of the present invention can contain other metallic element.For example can enumerate out the precious metal element of platinum, rhodium, ruthenium, iridium, gold, silver, osmium etc.; The base metal element of antimony, thallium, lead etc.Can contain other metallic element more than 2 kinds.From realizing the viewpoint of high catalytic activity, in the metallic element that contains in the palladium-containing catalyst, the total amount of palladium element, tellurium element and bismuth element is preferably more than the 50 quality %.

In addition, palladium-containing catalyst of the present invention can be non-supported, on carrier, supports the loaded of palladium element, tellurium element and bismuth element but be preferably.As carrier, for example can enumerate out active carbon, carbon black, silica, aluminium oxide, magnesia, calcium oxide, titanium oxide and zirconia etc.Wherein, preferred silica, titanium oxide and zirconia.Can not decide without exception by difference along with the difference of the kind of carrier etc. for the specific area of preferred carrier, and still under the situation of silica, specific area is for being preferably 50m ²/ g is above, 100m more preferably ²More than/the g.In addition, be preferably 1500m ²Below/the g, 1000m more preferably ²Below/the g.The specific area of carrier is more little, can prepare useful component (palladium element, tellurium element and bismuth element) more and be supported on more near the catalyst on surface, and the specific area of carrier is big more in above-mentioned scope, can prepare the catalyst that supports more useful components more.

Under the situation of supported catalyst, the total of palladium element, tellurium element and bismuth element supports rate, with respect to the carrier quality before supporting; Be preferably more than the 0.1 quality %, more preferably more than the 1 quality %, further more preferably more than the 2 quality %; Be preferably especially more than the 4 quality %, be preferably below the 40 quality %, more preferably below the 30 quality %; Further be preferably below the 20 quality %, be preferably especially below the 15 quality %.

Palladium-containing catalyst of the present invention, each elemental metals of palladium element, tellurium element and bismuth element can be that raw material prepares with the alloy of these elements, the compound that contains these elements.Wherein, from being prepared in the viewpoint that carrier is dispersed with the highly active catalyst of a large amount of useful components easily,, preferably contain the compound of these elements as raw material.

Raw material to the palladium element does not have special qualification, can enumerate out, and palladium metal, palladium salt, palladium oxide etc., wherein, preferred palladium salt.As palladium salt, for example can enumerate out, palladium bichloride, palladium, palladium nitrate, palladium sulfate, chlorination four ammino palladiums and two (acetylacetone,2,4-pentanedione) palladium etc., wherein, preferred palladium bichloride, palladium, palladium nitrate, chlorination four ammino palladiums, preferred especially palladium nitrate.

Raw material to tellurium element does not have special qualification, for example can enumerate out tellurium metal, tellurium salt, telluric acid and salt, tellurous acid and salt, tellurium oxide etc.As tellurium salt, for example can enumerate out hydrotelluric acid, telluric chloride, tellurium chloride, tellurium hexafluoride, telluric iodide, telluric bromide, tellurium bromide etc.As tellurate, for example can enumerate out llurate, potassium tellurate etc.As tellurite, for example can enumerate out sodium tellurite, potassium tellurite etc.Wherein, preferred telluric acid and salt, tellurous acid and salt thereof, tellurium oxide.

Raw material to bismuth element does not have special qualification, can enumerate out bismuth metal, bismuth salt, bismuth organic compound, bismuth oxide etc.As bismuth salt, for example can enumerate out bismuth acetate (III), bismuth acetate oxide (III), bismuth bromide (III), alkaline carbonic acid bismuth (III), bismuth chloride (III), fluoridize bismuth (III), bismuth iodide (III), alkaline bismuth nitrate (III), bismuth nitrate (III), bismuthyl chloride (III), bismuth phosphate (III), bismuth sulfate (III) etc.As bismuth organic compound, can enumerate out for example triphenyl bismuth etc.Wherein, preferred bismuth oxide and bismuth nitrate.

Suitably select the raw material of above-mentioned palladium element, tellurium element and bismuth element, be used to prepare palladium-containing catalyst.The match ratio of these raw materials becomes the desired value that kind according to the mol ratio that makes palladium element, tellurium element and bismuth element in the palladium-containing catalyst and suitably selects.

Palladium-containing catalyst; Preferably through suitable selection have the palladium element of the state of oxidation compound, have the tellurium element of the state of oxidation compound, have the state of oxidation the compound of bismuth element respectively as the raw material of palladium element, tellurium element and bismuth element; Mix; With these raw materials of reducing agent reduction, prepare.

In addition, under the situation of the loaded palladium-containing catalyst of preparation, can above-mentioned raw materials be supported on the carrier.The use amount of carrier can suitably be selected according to obtaining the catalyst that kind that target supports rate.

Raw material is supported on the method on the carrier, does not have special qualification, can enumerate out the precipitation method, ion-exchange, infusion process, the precipitation method etc.Under situation with immersion process for preparing, can flood the raw material of loaded palladium element, tellurium element and bismuth element simultaneously, also can be after dipping support arbitrary raw material, dipping supports remaining raw material.

In addition, also can support on the carrier at raw material with palladium element, tellurium element and bismuth element after, heat-treat, form palladium oxide, tellurium oxide and bismuth oxide and be supported on the state on the carrier.As the scope of heat treated temperature, be preferably more than 200 ℃, more preferably more than 300 ℃, be preferably below 800 ℃, more preferably below 700 ℃.Heat treatment time is not had special qualification, be preferably 1～12 hour scope.

In addition, make the palladium element of the state of oxidation, the tellurium element of the state of oxidation and the bismuth element of the state of oxidation, under the state that is supported on the carrier, reduce, prepare palladium-containing catalyst with reducing agent.

Reducing agent to using does not have special qualification; For example can enumerate; Hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, formates, ethene, propylene, 1-butylene, 2-butylene, isobutene, 1,3-butadiene, 1-heptene, 2-heptene, 1-hexene, 2-hexene, cyclohexene, allyl alcohol, methallyl alcohol, methacrylaldehyde and MAL etc.Can be also with the reducing agent more than 2 kinds.In addition, under the situation of in liquid phase, reducing, as reducing agent, preferred hydrazine, formaldehyde, formic acid, formates.

The solvent that uses during as the reduction in the liquid phase, preferred water, but under loaded situation,, also can use the alcohols that is used alone or in combination ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butanol, the tert-butyl alcohol etc. according to the dispersiveness of carrier; The ketone of acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.; The organic acid of acetic acid, positive valeric acid, isovaleric acid etc.; The organic solvent of the hydro carbons of heptane, hexane, cyclohexane etc. etc.Also can use the mixed solvent of this organic solvent and water.

When reducing agent is gas,, preferably in the pressue device of autoclave etc., carry out in order to improve the solubility in solution.At this moment, preferably pressurize with reducing agent in the inside of pressue device.Its pressure is preferably more than the 0.1MPa, is preferably below the 1.0MPa.

In addition, when reducing agent is liquid,, can carry out through in solution, adding reducing agent to the not restriction of device of reducing.The use amount of the reducing agent of this moment does not have special qualification, still with respect to the palladium element of 1 mole of state of oxidation, is preferably more than 1 mole, is preferably below 100 moles.

Reduction temperature and recovery time, and different, reduction temperature is preferably more than-5 ℃, more preferably more than 15 ℃, is preferably below 150 ℃, more preferably below 80 ℃ according to reducing agent etc.Recovery time was preferably more than 0.1 hour, more preferably more than 0.25 hour, further was preferably more than 0.5 hour, was preferably below 4 hours, more preferably below 3 hours, further was preferably below 2 hours.

Through the palladium-containing catalyst of also modulating originally, preferred water, solvent etc. wash.Wash through water, solvent etc., can remove raw material of for example deriving from chloride, acetate, nitrate anion, sulfate radical etc. etc. impurity, derive from the impurity of reducing agent etc.Method and number of times to washing do not have special qualification, still according to the difference of impurity, hinder alkene or α sometimes, the liquid phase oxidation reaction of beta-unsaturated aldehyde, and therefore preferred washing is to the degree that can fully remove impurity.Catalyst after the washing can directly be used for reaction after reclaiming through filtration or centrifugation.

In addition, can carry out drying to the catalyst that reclaims.Drying means is not had special qualification, but the preferred drying machine that uses carries out drying in air or in the inert gas.Dry catalyst as required, also can carry out activation before being used for liquid phase oxidation reaction.Method to activation does not have special qualification, for example can enumerate out the method for heat-treating under the reducing atmosphere in hydrogen stream.According to this method, can remove the oxide film thereon and the impurity that is in the suds and does not remove on palladium metal surface.The rerum natura of the catalyst that modulates can be measured to wait and confirm through BET specific area measuring, XRD determining, CO pulse absorption method, TEM mensuration, XPS.

In addition, Metal Palladium self shows the activity as oxidation catalyst, but when using this Metal Palladium separately, with alkene or α, the beta-unsaturated aldehyde oxidation generates α, and the reactive activity of beta-unsaturated carboxylic acid is insufficient, and carbon dioxide by-product is also many.But, if there be the electronegativity degree bismuth element different, then because the effect of bismuth element can make the electronic state of palladium element change with the palladium element.And then, if having electronegativity degree and palladium element and all different tellurium element of bismuth element, then because the effect of tellurium element further changes the electronic state of palladium element.Its result improves by alkene or α, and the beta-unsaturated aldehyde oxidation generates α, and the activity of the main reaction of beta-unsaturated carboxylic acid on the other hand, suppresses to generate the side reaction of carbon dioxide.

< α, the preparation method of beta-unsaturated carboxylic acid >

Below, to using palladium-containing catalyst of the present invention, with alkene or α, beta-unsaturated aldehyde carries out liquid phase oxidation through molecularity oxygen and prepares α, and the method for beta-unsaturated carboxylic acid describes.

As the alkene of raw material, for example can enumerate out, propylene, isobutene, 2-butylene etc., wherein, preferred propylene and isobutene.Also can be also with the alkene more than 2 kinds.The alkene of raw material can contain a spot of saturated hydrocarbons and/or rudimentary saturated aldehyde as impurity etc.

By the α of olefin production, beta-unsaturated carboxylic acid is the α that has same skeleton with alkene, beta-unsaturated carboxylic acid.Specifically, be under the situation of propylene at raw material, obtain acrylic acid; At raw material is under the situation of isobutene, obtains methacrylic acid.In addition, can obtain α, beta-unsaturated aldehyde simultaneously by alkene usually.This α, beta-unsaturated aldehyde is the α that has same carbon skeleton with alkene, beta-unsaturated aldehyde.For example, be under the situation of propylene at raw material, can obtain methacrylaldehyde, be under the situation of isobutene at raw material, can obtain MAL.

As the α of raw material, beta-unsaturated aldehyde for example can be enumerated out, methacrylaldehyde, MAL, crotonaldehyde (Beta-methyl methacrylaldehyde), cinnamic acid (beta-phenyl methacrylaldehyde) etc.Wherein, preferred methacrylaldehyde and MAL.Wherein, α, beta-unsaturated aldehyde also can be also with more than 2 kinds.The α of raw material, beta-unsaturated aldehyde can contain a spot of saturated hydrocarbons and/or rudimentary saturated aldehyde as impurity etc.

By α, the α of beta-unsaturated aldehyde preparation, beta-unsaturated carboxylic acid is α, the aldehyde radical of beta-unsaturated aldehyde becomes the α that carboxyl forms, beta-unsaturated carboxylic acid.Specifically, be under the situation of methacrylaldehyde at raw material, obtain acrylic acid; At raw material is under the situation of MAL, obtains methacrylic acid.

As the raw material of liquid phase oxidation, can only use alkene and α, a side of beta-unsaturated aldehyde also can use both mixture.

Liquid phase oxidation reaction can carry out with continous way, step arbitrary form, if but consider productivity ratio, preferred continous way in industry then.

The raw material of the molecularity oxygen that uses in the liquid phase oxidation reaction; Preferred economic air; But also can use purity oxygen or purity oxygen and Air mixing gas etc.; If be necessary, can also use the mist after air or purity oxygen diluted with nitrogen, carbon dioxide, steam etc.The gas that contains molecularity oxygen is so preferably supplied with pressurized state in the reaction vessel of autoclave etc.

As the solvent that uses in the liquid phase oxidation reaction, preferred at least a kind the organic solvent that is selected from the for example tert-butyl alcohol, cyclohexanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid, ethyl acetate and the methyl propionate etc. that uses.Wherein, more preferably be selected from least a kind of organic solvent in the tert-butyl alcohol, methyl iso-butyl ketone (MIBK), acetic acid, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid and the isovaleric acid.In addition, in order to prepare α with higher selection rate, beta-unsaturated carboxylic acid, water preferably coexists in these organic solvents.The amount of water to coexistence does not have special qualification, still, with respect to the total quality of organic solvent and water, is preferably more than the 2 quality %, more preferably more than the 5 quality %, is preferably below the 70 quality %, more preferably below the 50 quality %.Under the situation of the mixed solvent more than 2 kinds, this solvent is preferably the state of homogeneous, but also has no relations for inhomogenous state.

As the alkene and the α of the raw material of liquid phase oxidation reaction, the total concentration of beta-unsaturated aldehyde is with respect to the solvent that exists in the reactor; Be preferably more than the 0.1 quality %; More preferably more than the 0.5 quality %, be preferably below the 30 quality %, more preferably below the 20 quality %.

The use amount of molecularity oxygen is with respect to 1 mole of alkene and α as the raw material of liquid phase oxidation reaction, the total amount of beta-unsaturated aldehyde; Be preferably more than 0.1 mole; More preferably more than 0.2 mole, further be preferably more than 0.3 mole, be preferably below 20 moles; More preferably below 15 moles, further be preferably below 10 moles.

Catalyst preferably uses with the state that suspends in the reactant liquor that carries out liquid phase oxidation, but also can in fixed bed, use.The use amount of catalyst with respect to the solution that exists in the reactor, is preferably more than the 0.1 quality %; More preferably more than the 0.5 quality %, further be preferably more than the 1 quality %, be preferably below the 30 quality %; More preferably below the 20 quality %, further be preferably below the 15 quality %.

Reaction temperature and reaction pressure are suitably to select according to the solvent and the raw material that use.Reaction temperature is preferably more than 30 ℃, more preferably more than 50 ℃, is preferably below 200 ℃, more preferably below 150 ℃.In addition, reaction pressure is preferably more than the atmospheric pressure (0MPa), more preferably more than the 0.5MPa, is preferably below the 10MPa, more preferably below the 5MPa.

Embodiment

Below, enumerate embodiment, comparative example comes the present invention is more specifically explained, but the present invention not only is defined in embodiment.Following embodiment and " part " in the comparative example are mass parts.

(XRD determining)

Utilize the RU-200A (trade name) of the リガ of Co., Ltd. Network system to measure.Condition determination is an X ray: Cu-K α/40kV/100mA, sweep speed: 4 °/min).

(α, the analysis of the raw material in the preparation of beta-unsaturated carboxylic acid, product and accessory substance)

α, the analysis of the raw material in the preparation of beta-unsaturated carboxylic acid, product and accessory substance is carried out through using gas-chromatography.In addition, the reactivity of alkene, the α of generation, beta-unsaturated aldehyde and α, the selection rate of the selection rate of beta-unsaturated carboxylic acid and secondary carbon dioxide of giving birth to, definition is as follows.

The reactivity of alkene (%)=(B/A) * 100

α, the selection rate of beta-unsaturated aldehyde (%)=(C/B) * 100

α, the selection rate of beta-unsaturated carboxylic acid (%)=(D/B) * 100

The selection rate of carbon dioxide (%)=(E/B) * 100

Here; A is the molal quantity of the alkene supplied with, and B is the molal quantity of the alkene that reacted, the α of C for generating; The molal quantity of beta-unsaturated aldehyde; The α of D for generating, the molal quantity of beta-unsaturated carboxylic acid, E is (molal quantity of secondary carbon dioxide of giving birth to)/(carbon number of raw material olefin (being 4 under the situation of isobutene)).

[embodiment 1]

(modulation of catalyst)

Make 0.05 part of antimony oxide, be distributed to and in 2.3 parts of pure water, be dissolved with in 0.26 part of tartaric aqueous solution, stirred 30 minutes at 60 ℃.In this uniform solution, add 3.3 parts of palladium nitrate salpeter solutions (Tanaka's noble metal system, palladium element containing ratios: 22.65 quality %); In the aqueous solution that is obtained, further append pure water, the solution that full dose is adjusted into 10.2 parts adds 15.0 parts of pelletized silica carrier (specific area 450m gradually on a small quantity to ²/ g, pore volume 0.68cc/g, average diameter 53.58 μ m) in, repeated oscillation is added complete soln.To use such filling perforation method to flood the carrier of solution, in air, keep 3 hours, in air, burn till 3 hours then, obtain to have supported the silica supports of palladium element and antimony element at 450 ℃ at 100 ℃.

The carbon dioxide carrier that is obtained is added in 40.0 parts of the 37 quality % formalins.Be heated to 70 ℃, stirred 2 hours, reduce processing.Then, aspirate, use 1000 parts of warm water filtration washings then.And then down 100 ℃ of dryings 2 hours, palladium element and antimony element that acquisition is reduced are supported on the loaded palladium-containing catalyst on the silica supports in nitrogen circulation.The Sb/Pd of this catalyst is 0.05.The rate that supports of the palladium element of this catalyst is 5.0 quality %, and the rate that supports of antimony element is 0.26 quality %.In addition, supporting rate is the ratio of the quality of each element in the catalyst with respect to the carrier quality.In the XRD determining of this catalyst, near 2 θ=39.880 degree, detect the peak.

In addition; In embodiment 1～4 and comparative example 2; The quality of palladium element, antimony element and the tellurium element that uses in the calculating of the rate that supports of Sb/Pd, Te/Pd and each element is calculated according to the tellurium element containing ratio and the use level of the tellurium raw material of the antimony element containing ratio of the Sb raw material of the palladium element containing ratio of the Pd raw material that uses and use level, use and use level, use.Carrier quality in the catalyst is following such quantitative.At first, catalyst is taken in the platinum alloy crucible, adds sodium carbonate, carry out fusion.Add distilled water, form uniform solution, with the Si atom in the quantitative sample solution of ICP.

(reaction evaluating)

In autoclave, add in the catalyst that obtains with said method 10.5 parts and as 75 parts of the tert-butyl alcohol aqueous solution of 75 quality % of reaction dissolvent, airtight autoclave.Import 2.0 parts of isobutenes then, begin to stir (rotation number 1000rpm), be warming up to 90 ℃.After the end that heats up, in autoclave, importing nitrogen is 2.4MPa until interior pressure, and importing air then is 4.8MPa until interior pressure, begins reaction.Whenever internal drop in reaction low during 0.15MPa (interior pressure 4.65MPa), import the oxygen of 0.15MPa, press in making for 4.8MPa (below be also referred to as the operation that imports oxygen), repeatedly should operation 4 times.In addition, begin from reaction that the required time is 4 minutes till the oxygen to importing for the first time.After the 4th imported oxygen, internal drop finished reaction to the moment of 4.65MPa.

Reaction is put into ice bath with autoclave after finishing, and content is cooled off.Gas outlet at autoclave is installed the gas trapping bag, opens the gas vent valve and reclaims the gas of discharging, the pressure in the open simultaneously reactor.From autoclave, take out the reactant liquor that contains catalyst, come separating catalyst, reclaim reactant liquor through molecular filter.Analyze the reactant liquor of recovery and the gas of capture with gas chromatograph, calculate reactivity and selection rate.The result is as shown in table 1.

[embodiment 2]

(modulation of catalyst)

Operation 1: at palladium nitrate salpeter solution (Tanaka's noble metal system, palladium element containing ratio: 22.65 quality %) further append pure water in 3.3 parts; With full dose be adjusted into 10.2 parts solution add on a small quantity gradually with embodiment 1 in 15.0 parts of the same silica supports that use; Repeated oscillation is added complete soln.To use such filling perforation method to flood the silica supports of solution, in air, burn till 3 hours, obtain to have supported the silica supports of palladium oxide at 450 ℃.

Operation 2: make 0.10 part of antimony oxide, be distributed to and in 2.3 parts of pure water, be dissolved with in 0.52 part of tartaric aqueous solution, stirred 30 minutes at 60 ℃.The uniform solution that is obtained is added in the carbon dioxide carrier that has supported palladium oxide that in operation 1, obtains gradually on a small quantity, and repeated oscillation is added complete soln.Filling perforation method with such is flooded in solution, obtains to contain the silica supports of palladium element and antimony element.

The silica supports that is obtained is joined in 40.0 parts of the 37 quality % formalins.Be heated to 70 ℃, stirred 2 hours, reduce processing.Then, aspirate, use 1000 parts of warm water filtration washings then.And then down 100 ℃ of dryings 2 hours, palladium element and antimony element that acquisition is reduced are supported on the loaded palladium-containing catalyst on the silica supports in nitrogen circulation.The Sb/Pd of this catalyst is 0.10.The rate that supports of the palladium element in this catalyst is 5.0 quality %, and the rate that supports of antimony element is 0.53 quality %.In addition, in the XRD determining of this element, near 2 θ=39.700 degree, detect the peak.

(reaction evaluating)

Except in the catalyst that uses above-mentioned acquisition more than 10.6 parts, operate equally with embodiment 1, carry out reaction evaluating.In addition, from reaction begin to the time that imports for the 1st time till the oxygen be 3 minutes.The result is shown in table 1.

[embodiment 3]

(modulation of catalyst)

Make the use amount of antimony oxide become 0.15 part, tartaric use amount becomes 0.78 part, in addition, uses the method same with embodiment 1, has obtained palladium-containing catalyst.The Sb/Pd of this catalyst is 0.15.The rate that supports of the palladium element in this catalyst is 5.0 quality %, and the rate that supports of antimony element is 0.79 quality %.In the XRD determining of this catalyst, near 2 θ=39.600 degree, detect the peak.

(reaction evaluating)

The catalyst that uses aforesaid operations to obtain is used with embodiment 1 same method and is carried out.In addition, from reaction begin to the time that imports for the 1st time till the oxygen be 6 minutes.The result is shown in table 1.

[embodiment 4]

(modulation of catalyst)

Make 0.07 part of antimony oxide, be distributed to and in 2.3 parts of pure water, be dissolved with in 0.30 part of tartaric aqueous solution, stirred 30 minutes at 60 ℃.4.5 parts of palladium nitrate salpeter solutions of adding in this uniform solution (Tanaka's noble metal system, palladium element containing ratio: 22.65 quality %), with adding 5.0 parts of pelletized silica carrier (specific area 450m in the aqueous solution that is obtained gradually on a small quantity to ²/ g, pore volume 0.68cc/g, average diameter 53.58 μ m) in, repeated oscillation is added complete soln.To use such filling perforation method to flood the carrier of solution, in air, burn till 3 hours, obtain to have supported the silica supports of palladium element and antimony element at 450 ℃.

The carbon dioxide carrier that is obtained is added in 70 parts of the 37 quality % formalins.Be heated to 70 ℃ then, stirred 2 hours, reduce processing, aspirate, use 1000 parts of warm water filtration washings then.After the washing, obtain to support and carried out reducing the palladium element of processing and the silica supports of antimony element.And then, this silica supports is dispersed in 50.0 parts of the pure water, in this dispersion soln, drip the telluric acid aqueous solution that in 5.0 parts of pure water, is dissolved with 0.06 part of telluric acid.This solution is heated to 70 ℃, stirred 2 hours, handle.Then, after aspirating, with 1000 parts of warm water filtration washings.And then 100 ℃ of dryings 2 hours, palladium element, antimony element and the tellurium element that has obtained to be reduced was supported on the loaded palladium-containing catalyst on the silica supports under nitrogen circulation.The Sb/Pd of this catalyst is 0.05, and Te/Pd is 0.05.The rate that supports of the palladium element in this catalyst is 20.0 quality %, and the rate that supports of antimony element is 1.14 quality %, and the rate that supports of tellurium element is 1.20 quality %.In the XRD determining of this catalyst, near 2 θ=39.870 degree, detect the peak.

(reaction evaluating)

In autoclave, add in the catalyst that obtains with said method 3.0 parts and as 75 parts of the tert-butyl alcohol aqueous solution of 75 quality % of reaction dissolvent, airtight autoclave.Import 2.0 parts of isobutenes then, begin to stir (rotation number 1000rpm), be warming up to 90 ℃.After the end that heats up, in autoclave, importing nitrogen is 2.4MPa until interior pressure, and importing air then is 4.8MPa until interior pressure, begins reaction.Whenever internal drop in reaction low during 0.10MPa (interior pressure 4.70MPa), import the oxygen of 0.10MPa, press in making for 4.8MPa (below be also referred to as the operation that imports oxygen), repeatedly should operation 8 times.In addition, begin from reaction that the required time is 2 minutes till the oxygen to importing for the first time.Behind the 8th importing oxygen, internal drop finishes reaction to the moment of 4.70MPa.

[comparative example 1]

(modulation of catalyst)

To 2.16 parts of palladium nitrate solutions (N.E. ケ system キヤ Star ト system: the nitric acid acidic aqueous solution that contains 23.2 quality % palladium nitrates) and then append pure water, total amount is adjusted in 6.8 parts the solution and adds 10.0 parts of emboliform silica supports (specific area 450m gradually on a small quantity to ²/ g, pore volume 0.68cc/g) in, repeated oscillation is added complete soln.After with such filling perforation method dipping solution, evaporate.Then, in air, carry out burning till in 3 hours at 450 ℃.The catalyst precarsor that obtains joined in 20 parts the formalin of 37 quality %.Be heated to 70 ℃, stir maintenance 2 hours, with 1000 parts of warm water filtration washings, obtain silica supported type palladium-containing catalyst behind the suction filtration.In addition, the rate that supports of palladium element is 5 quality % in this catalyst.In addition, supporting rate is the ratio of the quality of each element in the catalyst with respect to the carrier quality.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.48 degree.

In addition, in embodiment 5～8 and comparative example 1, comparative example 3～5, the rate that supports of Te/Pd, Bi/Pd and each element is calculated according to the quality of the palladium element, tellurium element and the bismuth element that contain in the catalyst after the modulation and the quality of atomic weight and carrier.The quality of palladium element, tellurium element and bismuth element in the catalyst is measured according to following method.

The modulation of treatment fluid: 1 part of catalyst, 50 parts of 62 quality % aqueous solution of nitric acid and 48 quality % hydrofluoric acid aqueous solutions are taken to テ Off ロ Application (registration mark) system for 50 parts decompose in the pipe, (CEM society system, MARS5 (trade name)) carries out dissolution process with the heating using microwave decomposer.

With ICP apparatus for analyzing luminosity (サ one モエレメ Application タ Le system, IRIS-Advantage (trade name)); Quality to the palladium element, tellurium element and the bismuth element that contain in the uniform solution that is obtained is carried out quantitatively, obtains the quality of palladium element, tellurium element and bismuth element in the catalyst.Carrier quality in the catalyst, following such quantitative.At first, catalyst is taken in the platinum alloy crucible, adds sodium carbonate, carry out fusion.Add distilled water, form uniform solution, with the Si atom in the quantitative sample solution of ICP.

(reaction evaluating)

In autoclave, add whole catalyst (0.5 part of palladium element) of obtaining with said method and as 75 parts of the tert-butyl alcohol aqueous solution of 75 quality % of reaction dissolvent, airtight autoclave.Import 2.0 parts of isobutenes then, begin to stir (rotation number 1000rpm), be warming up to 90 ℃.After the end that heats up, in autoclave, importing nitrogen is 2.4MPa until interior pressure, and importing compressed air then is 4.8MPa until interior pressure.Whenever internal drop in reaction low during 0.15MPa (interior pressure 4.65MPa), import the oxygen of 0.15MPa, repeatable operation.Reaction time is 60 minutes, finishes reaction.

Reaction is carried out ice-cooled with ice bath to autoclave after finishing.Gas outlet at autoclave is installed the gas trapping bag, opens the gas vent valve and reclaims the gas of discharging, the pressure in the open simultaneously reactor.From autoclave, take out the reactant liquor that contains catalyst, come separating catalyst, reclaim reactant liquor through molecular filter.Analyze the reactant liquor of recovery and the gas of capture with gas chromatograph, calculate reactivity and selection rate.The result is shown in table 1 and table 2.

[comparative example 2]

(modulation of catalyst)

Make the use amount of antimony oxide become 0.31 part, tartaric use amount becomes 1.55 parts, in addition, uses the method same with embodiment 1, has obtained palladium-containing catalyst.The Sb/Pd of this catalyst is 0.30.The rate that supports of the palladium element in this catalyst is 5.0 quality %, and the rate that supports of antimony element is 1.62 quality %.In the XRD determining of this catalyst, near 2 θ=39.500 degree, detect the peak.

(reaction evaluating)

Use 10.7 parts in the catalyst that aforesaid operations obtains, in addition, use with embodiment 1 same method to begin reaction, internal drop as a result is more late than embodiment 1 to the moment of 4.65MPa, needs 45 minutes till importing oxygen to the 1st time.The catalyst that can judge its specific activity embodiment 1 thus is low, therefore in the moment (only carrying out the oxygen import operation 1 time) of convincing by patient analysis from reaction through 60 minutes, finishes reaction.The result is shown in table 1.

Table 1

As stated, the palladium-containing catalyst of the application of the invention can prepare α, beta-unsaturated carboxylic acid with high selectivity more.

[embodiment 5]

(modulation of catalyst)

In 0.0228 part of bismuth nitrate pentahydrate, add the aqueous solution of nitric acid of 62 quality % of 10 times of quality, form uniform solution.To the distilled water that wherein adds 0.151 part of telluric acid and its 10 times of quality, form uniform solution.The adding palladium nitrate solution (N.E. ケ system キヤ Star ト system: the nitric acid acidic aqueous solution that contains 23.2 quality % palladium nitrates) 2.16 parts, and then append pure water, the adjustment total amount is 6.8 parts.This solution is added emboliform silica supports (specific area 450m gradually on a small quantity ²/ g, pore volume 0.68cc/g), repeated oscillation is added complete soln.After with such filling perforation method dipping solution, evaporate.Then, in air, carry out burning till in 3 hours at 450 ℃.Two catalyst precarsors that obtain are joined in 20 parts the formalin of 37 quality %.Be heated to 70 ℃, stir maintenance 2 hours, with 1000 parts of warm water filtration washings, obtain silica supported type palladium-containing catalyst behind the suction filtration.In addition, Te/Pd is 0.14 in this catalyst, and Bi/Pd is 0.01.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of tellurium element is 0.84 quality %, and the rate that supports of bismuth element is 0.1 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.66 degree.

(reaction evaluating)

After reaction finishes, ice-cooled to carrying out in the autoclave with ice bath.Gas outlet at autoclave is installed the gas trapping bag, opens the gas vent valve and reclaims the gas of discharging, the pressure in the open simultaneously reactor.From autoclave, take out the reactant liquor that contains catalyst, come separating catalyst, reclaim reactant liquor through molecular filter.Analyze the reactant liquor of recovery and the gas of capture with gas chromatograph, calculate reactivity and selection rate.The result is as shown in table 2.

[embodiment 6]

(modulation of catalyst)

Make the use amount of bismuth nitrate pentahydrate become 0.0570 part, the use amount of telluric acid becomes 0.135 part, in addition, uses the method same with embodiment 5, has obtained palladium-containing catalyst.The Te/Pd of this catalyst is 0.125, and Bi/Pd is 0.025.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of tellurium element is 0.75 quality %, and the rate that supports of bismuth element is 0.25 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.50 degree.

(reaction evaluating)

Use the catalyst of above-mentioned acquisition, use with embodiment 5 same methods and carry out reaction evaluating.The result is shown in table 2.

[embodiment 7]

(modulation of catalyst)

Make the use amount of bismuth nitrate pentahydrate become 0.0912 part, the use amount of telluric acid becomes 0.119 part, in addition, uses the method same with embodiment 5, has obtained palladium-containing catalyst.The Te/Pd of this catalyst is 0.11, and Bi/Pd is 0.04.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of tellurium element is 0.66 quality %, and the rate that supports of bismuth element is 0.39 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.54 degree.

(reaction evaluating)

[embodiment 8]

(modulation of catalyst)

Make the use amount of bismuth nitrate pentahydrate become 0.114 part, the use amount of telluric acid becomes 0.108 part, in addition, uses the method same with embodiment 5, has obtained palladium-containing catalyst.The Te/Pd of this catalyst is 0.10, and Bi/Pd is 0.05.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of tellurium element is 0.6 quality %, and the rate that supports of bismuth element is 0.49 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.48 degree.

(reaction evaluating)

[comparative example 3]

(modulation of catalyst)

Make the use amount of bismuth nitrate pentahydrate become 0.114 part, do not use telluric acid, in addition, use the method same, obtained palladium-containing catalyst with embodiment 5.The Bi/Pd of this catalyst is 0.05.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of bismuth element is 0.49 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.70 degree.

(reaction evaluating)

[comparative example 4]

(modulation of catalyst)

In 0.752 part of bismuth nitrate pentahydrate, add the aqueous solution of nitric acid of 62 quality % of 4 times of quality, form uniform solution.Use this uniform solution, and then do not use telluric acid, in addition, use the method same, obtained palladium-containing catalyst with embodiment 5.The Bi/Pd of this catalyst is 0.33.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of bismuth element is 3.24 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.00 degree.

(reaction evaluating)

[comparative example 5]

Do not use the bismuth nitrate pentahydrate, make the use amount of telluric acid become 0.162 part, in addition, use the method same, obtained palladium-containing catalyst with embodiment 5.The Te/Pd of this catalyst is 0.15.The rate that supports of the palladium element in this catalyst is 5 quality %, and the rate that supports of tellurium element is 0.9 quality %.In the XRD determining of this catalyst, detect the peak, confirm to contain the palladium element that constitutes metal at 2 θ=39.20 degree.

(reaction evaluating)

Table 2

Show that more than the palladium-containing catalyst of the application of the invention can prepare α with high selectivity more, beta-unsaturated carboxylic acid, carbon dioxide by-product is few.

Claims

1. a palladium-containing catalyst is to be used for by alkene or α, and beta-unsaturated aldehyde prepares α, and the palladium-containing catalyst of beta-unsaturated carboxylic acid contains palladium element and tellurium element and bismuth element, and said palladium element constitutes metal.

2. the preparation method of a palladium-containing catalyst; It is the method for preparing the described palladium-containing catalyst of claim 1; Comprise the palladium element that will contain the state of oxidation compound, contain the state of oxidation tellurium element compound and contain the compound of the bismuth element of the state of oxidation, the operation of reducing with reducing agent.

3. α, the preparation method of beta-unsaturated carboxylic acid uses the described palladium-containing catalyst of claim 1, and with alkene or α, beta-unsaturated aldehyde carries out liquid phase oxidation with molecularity oxygen.