CN1917956A - Catalyst for producing alpha, beta-unsaturated carboxylic acid and method for preparation thereof and method for producing alpha, beta-unsaturated carboxylic acid - Google Patents
Catalyst for producing alpha, beta-unsaturated carboxylic acid and method for preparation thereof and method for producing alpha, beta-unsaturated carboxylic acid Download PDFInfo
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Abstract
A catalyst for producing an alpha, beta-unsaturated carboxylic acid which comprises a carrier having a total pore volume of 0.40 to 1.50 cc/g as measured by the nitrogen gas adsorption method and a metal carried thereon or which comprises a carrier and, carried thereon, palladium having an average particle diameter in the range of 1 to 8 nm; a method for preparing the catalyst; and a method for producing an alpha, beta-unsaturated carboxylic acid using the above catalyst. The above catalyst can be suitably used for producing an alpha, beta-unsaturated carboxylic acid from an olefin or an alpha, beta-unsaturated aldehyde through the liquid phase oxidation in good reaction performance.
Description
Technical field
The present invention relates to be used for alkene or α, beta-unsaturated aldehyde is made α by liquid phase oxidation, the catalyst of beta-unsaturated carboxylic acid, its manufacture method, and uses the α of this catalyst, the manufacture method of beta-unsaturated carboxylic acid.
Background technology
α, beta-unsaturated carboxylic acid, material useful in industry is a lot.Acrylic acid and methacrylic acid be the extremely a large amount of use of quilt in purposes such as synthetic resin raw material.For example, the manufacture method of methacrylic acid, though vapour phase oxidation process, the liquid phase oxidation of isobutene are arranged, and the method for process acetone cyanohydrin etc., not having particularly advantageous method, this several method wherein is applied in the industrial production.
For being used for from alkene or α, beta-unsaturated aldehyde is made α through the liquid phase oxidation of molecularity oxygen, and the catalyst of beta-unsaturated carboxylic acid and method are studied awfully hot always.Can enumerate, for example, the method (patent documentation 1) of in the presence of the catalyst that supports gold, carrying out, the method (patent documentation 2～6) of use palladium metal catalyst is used the method (patent documentation 7) of molybdenum compound and palladium catalyst etc.
The catalyst of being put down in writing in the patent documentation (2～7), though contain palladium as catalyst component, not about the record directly of palladium particle.And in the catalyst put down in writing of patent documentation (1～7), what have is supported on the carriers such as active carbon, aluminium oxide, silica.About the rerum natura of these carriers, have only and put down in writing " the common carrier that preferred hydrophobic carrier or hydrophobization were handled " in the patent documentation 1, in addition do not find the description of carrier rerum natura.
Patent documentation 1: the spy opens the 2001-172222 communique
Patent documentation 2: the spy opens clear 60-155148 communique
Patent documentation 3: the spy opens clear 60-139341 communique
Patent documentation 4: the spy opens clear 60-139643 communique
Patent documentation 5: No. 4435598 specification of United States Patent (USP)
Patent documentation 6: the international international publication text that discloses No. 02/083299
Patent documentation 7: the spy opens clear 56-59722 communique
Summary of the invention
The catalyst that the method that the present inventor puts down in writing in will the embodiment according to patent documentation 1～7 is made, be used for making acrylic acid from propylene, except in the patent documentation 1～7 record accessory substance (for example, acetaldehyde, acetone, methacrylaldehyde, acetate and carbon dioxide) in addition, find that also a large amount of pairs have given birth to multiple polymers, oligomer.In patent documentation 1～7, do not capture such polymer and oligomer, thereby can judge acrylic acid selection rate, the yield of the reality that comprises these accessory substances, that puts down in writing among the embodiment than patent documentation 1～7 is low.As mentioned above, at α, the reaction achievement in the manufacture method of beta-unsaturated carboxylic acid is also insufficient, wishes further to improve.
The objective of the invention is, provide can be good the reaction achievement come from alkene or α, beta-unsaturated aldehyde is made α through liquid phase oxidation, the catalyst of beta-unsaturated carboxylic acid, and manufacture method, and the α that uses this catalyst, the manufacture method of beta-unsaturated carboxylic acid.
Present inventors find that carrier rerum natura, particularly pore volume used when making catalyst are very big to the catalyst performance influence, thereby have finished the present invention.But also found that particularly with under the situation of palladium as catalyst component, palladium particle footpath is very big to the catalyst performance influence in the catalyst of manufacturing, thereby has finished the present invention.
α among the present invention, beta-unsaturated carboxylic acid catalyst for producing are used for by alkene or α, and beta-unsaturated aldehyde is made α by liquid phase oxidation, and the catalyst of beta-unsaturated carboxylic acid is specific as follows:
[1] α, the catalyst of beta-unsaturated carboxylic acid manufacturing usefulness is characterized in that, is in the carrier of 0.40～1.5cc/g in total pore volume of measuring according to the nitrogen adsorption method, has supported metal.
[2] α, the beta-unsaturated carboxylic acid catalyst for producing is characterized in that, supports the palladium of averaged particles footpath in 1～8nm scope in the carrier.
α of the present invention, the manufacture method of beta-unsaturated carboxylic acid catalyst for producing is the α of above-mentioned [1], the manufacture method of beta-unsaturated carboxylic acid catalyst for producing, be in the presence of above-mentioned carrier, to utilize reducing agent reducing metal compound to make α, the manufacture method of beta-unsaturated carboxylic acid catalyst for producing.
α of the present invention, the manufacture method of beta-unsaturated carboxylic acid catalyst for producing is the α of above-mentioned [2], the manufacture method of beta-unsaturated carboxylic acid catalyst for producing is to utilize reducing agent reduction palladium compound to make α, the method for beta-unsaturated carboxylic acid catalyst for producing in the presence of above-mentioned carrier.
α of the present invention, the manufacture method of beta-unsaturated carboxylic acid is the α in above-mentioned [1] or [2], under the existence of beta-unsaturated carboxylic acid catalyst for producing, by alkene or α, beta-unsaturated aldehyde utilizes molecularity oxygen to carry out oxidation in liquid phase and makes α, the method for beta-unsaturated carboxylic acid.
According to the present invention, can provide can be good the reaction achievement from or α, beta-unsaturated aldehyde is made α by liquid phase oxidation, the catalyst of beta-unsaturated carboxylic acid, and manufacture method, and the α that uses this catalyst, the manufacture method of beta-unsaturated carboxylic acid.
The specific embodiment
(1) α, the beta-unsaturated carboxylic acid catalyst for producing
α of the present invention, beta-unsaturated carboxylic acid catalyst for producing (the following catalyst that is called for short sometimes) is to be used for by alkene or α, and beta-unsaturated aldehyde is made α by liquid phase oxidation, and the catalyst of beta-unsaturated carboxylic acid is specific as follows:
[1] α, the beta-unsaturated carboxylic acid catalyst for producing is characterized in that, is in the carrier of 0.40～1.5cc/g in total pore volume of measuring according to the nitrogen adsorption method, has supported metal.
[2] α, the beta-unsaturated carboxylic acid catalyst for producing is characterized in that, supports the palladium of averaged particles footpath in 1～8nm scope in the carrier.
By using above-mentioned catalyst, reaction achievement that can be good is by alkene or α, and beta-unsaturated aldehyde is made α by liquid phase oxidation, beta-unsaturated carboxylic acid.Particularly propylene, the isobutene of catalyst of the present invention in alkene, α, effective in the particularly methacrylaldehyde in the beta-unsaturated aldehyde and the liquid phase oxidation of MAL.
Catalyst of the present invention is that metal is supported on catalyst-loaded on the carrier.Below to describing as operable carrier of catalyst of the present invention and metal.
(1-1) carrier
To the kind of carrier without limits, can use representational carriers such as active carbon, carbon black, silica, aluminium oxide, magnesia, calcium oxide, zirconia, titanium oxide.Wherein preferably use active carbon or silica.Usually, active carbon will pass through charing, whole grain, and activation, cleaning, drying reach the technology of pulverizing and make, but among the present invention its manufacturing process are not particularly limited.Also be not particularly limited for carbonaceous material, can use various raw materials such as palm shell, coal, timber and synthetic resin as the active carbon raw material.Activation method also is not particularly limited, and can use steam, carbon dioxide, and oxygen, phosphoric acid, phosphate and zinc chloride etc. activates.Active carbon after the activation as required, is used inorganic acid, hydrochloric acid, after the cleaning, drying such as water for using.In the impurity that contains in the active carbon goods, because the chlorine element can bring adverse effect to catalyst performance, so preferred few as far as possible.Therefore, the active carbon that uses zinc chloride, hydrochloric acid to make, preferred fully clean, remove the chlorine element that is contained as much as possible.Shape to active carbon is not particularly limited, can use Powdered, spherical, graininess, and various active carbons such as fibrous.The BET specific area of active carbon is preferably 300m
2More than/the g, be preferably 600m especially
2More than/the g, and be preferably 4000m
2Below/the g, be preferably 2500m especially
2Below/the g.
Here, as a kind of form of catalyst of the present invention, can enumerate total pore volume of selecting use to measure according to the nitrogen adsorption method is the carrier of 0.40～1.50cc/g.By utilizing such carrier, can make that by alkene or α beta-unsaturated aldehyde is made α, beta-unsaturated carboxylic acid in high selectivity, high production rate ground by liquid phase oxidation.Below its formation and manufacture method are described.
Particularly, for the target product that obtains of high selectivity, preferred total pore volume is the carrier of 0.40～0.80cc/g.More preferably more than the 0.47cc/g, and below the preferred 0.70cc/g, more preferably below the 0.67cc/g.By using the carrier that satisfies such condition, the accessory substance of generation is few, well obtains to selection rate target products such as acrylic acid, methacrylic acid.This can infer be because, by total pore volume being defined as in the above-mentioned scope little scope like that, suppressed the generation of accessory substances such as oligomer, thereby improved the selection rate of target product.In addition, at this moment, fine pore is preferably below 40% of total pore volume in the pore volume ratio of the mesopore of 2nm～50nm, more preferably below 35%, more preferably below 30%, is preferably below 20% especially.And the pore volume ratio of above-mentioned mesopore is preferably more than 5% of total pore volume, more preferably more than 7%, more preferably more than 9%.Particularly in this case, can think that if identical pore volume, because the ratio of mesopore is low more, it is difficult more then to generate accessory substance such as oligomer, so selection rate further improves.In addition, the BET specific area of carrier is preferably 600m
2More than/the g, 800m more preferably
2More than/the g, be preferably 2000m
2Below/the g, 1500m more preferably
2Below/the g.
Particularly, for high production rate obtains target product, preferably selecting total pore volume is the carrier of 0.70～1.50cc/g.More preferably more than the 0.80cc/g, more than the further preferred 0.90cc/g, more preferably below the 1.40cc/g, below the further preferred 1.30cc/g.By using the carrier that satisfies such condition, catalyst activity uprises, and can obtain target products such as acrylic acid, methacrylic acid with good productivity ratio.Can think that be in scope big as in the above-mentioned scope by making pore volume, reactant and product spread transfiguration in pore easy, thereby productivity ratio further improves.In addition, fine pore is preferably more than 10% of total pore volume in the pore volume ratio of the mesopore of 2nm～50nm, more preferably more than 20%, more preferably more than 30%, is preferably more than 40% especially; And be preferably below 65%, more preferably below 60%, more preferably below 55%.Particularly in this case, can think that if identical pore volume, because the ratio of mesopore is high more, the diffusion in the pore is just easy more, so production efficiency further improves.And then the BET specific area of carrier is preferably 100m
2More than/the g, 300m more preferably
2More than/the g, be preferably 5000m
2Below/the g, 4000m more preferably
2Below/the g.
In addition, total pore volume of carrier, fine pore are in the pore volume and the BET specific area of the mesopore of 2nm～50nm, can for example use, the automatic specific area of Micromeritics corporate system/pore measure of spread device TriStar3000 (commercial name) etc. is measured.
(1-2) metal
The metal that supports in the carrier is though so long as the material that has as the catalyst function of liquid phase oxidation just has no particular limits preferred noble metal, more preferably palladium or gold, preferred especially palladium.Metal can be a kind of, also can be two or more.In addition, also can contain the metal that does not have as the liquid-phase oxidation catalyst function in the catalyst.From the viewpoint of catalyst activity, preferably do not have to account for below the 50 atom % as the metal of liquid-phase oxidation catalyst function.
Here, as a kind of form of catalyst of the present invention, can be set forth in and support the catalyst of averaged particles footpath in the carrier at the palladium of 1～8nm scope.By selecting palladium as metal, and averaged particles directly is in the above-mentioned scope, become can high yield from α, beta-unsaturated aldehyde is made α, the catalyst of beta-unsaturated carboxylic acid.More than the above-mentioned preferred 1.2nm in averaged particles footpath, more preferably more than the 1.4nm.And averaged particles directly is preferably below the 7nm, more preferably below the 6nm.The averaged particles footpath of palladium is under the situation beyond the above-mentioned scope, and the catalyst activity that contains this palladium has the trend of reduction, α, and the productive rate of beta-unsaturated carboxylic acid also has the trend of reduction.At this moment, though can contain palladium metal in addition in the catalyst, from the viewpoint of catalyst activity, the metal beyond the preferred palladium accounts for below the 50 atom %.
Here, the averaged particles of above-mentioned palladium directly is meant, utilizes the infiltration type electron microscope to the particle footpath that the palladium in the catalyst measures, and specifically is the numerical value of calculating according to following method.
With the infiltration type electron microscope observation to portrait print with identical size, from the visual field, pick out 50 palladium zones arbitrarily, measure particle footpath respectively.Because the shape in palladium zone is circular basically, thereby all is approximately circle and measures.This operation is carried out in three visuals field, and the mean value of getting measured value is as the averaged particles footpath.In addition, the observation of infiltration type electron microscope will be carried out with the observation multiplying power that can measure palladium particle footpath.
In addition, the averaged particles of palladium footpath in the catalyst, be subjected to the kind of used carrier and BET specific area thereof, when making catalyst used solvent species and mixed solvent mixed proportion, change as various condition influence such as the temperature and time of the kind of the palladium compound of catalyst raw material and concentration, reduction palladium compound.In the present invention, be necessary suitably to select to set these conditions, make the averaged particles of the palladium in the catalyst that obtains directly be in above-mentioned scope.
(2) α, the manufacture method of beta-unsaturated carboxylic acid catalyst for producing
Below, to the α of the invention described above, the manufacture method of beta-unsaturated carboxylic acid catalyst for producing is illustrated.
Though the manufacture method of catalyst of the present invention is not particularly limited, preferably adopt carrier to have the method for using reducing agent reducing metal compound down.Specifically can modulate the metal compound solution that carrier is disperseed, to wherein adding the liquid phase reduction that reducing agent reduces by for example; Metal compound solution is contained be immersed in the carrier, dry then, the gas phase reduction process that reduces under the reducing gases atmosphere waits to be made.Wherein, the preferred liquid phase reducing process below describes the method for utilizing liquid phase reduction to make catalyst.
As the metallic compound that uses, preferably become catalyst metals, chloride, oxide, acetate, nitrate, sulfate, tetramine complex compound, perhaps acetylacetonate complex etc., the more preferably chloride of metal, oxide, acetate, nitrate and sulfate, chloride, acetate or the nitrate of special preferable alloy.These can use separately, also can multiplely be used in combination.
In addition, as these metallic compounds, preferably use as the not chloride in fact metallic compound of impurity.More particularly, the chlorine in the preferable alloy compound is below the 1000ppm.That is, preferably use not chloride metallic compounds such as acetate, nitrate, bis-acetylacetonate complex compound.When selecting palladium, can for example suitably use acid chloride, palladium nitrate, bis-acetylacetonate palladium as metal.
Solvent as the dissolution of metals compound, can be according to the dissolubility of metallic compound and reducing agent, the dispersiveness of carrier etc. is suitably selected, and can make water, alcohols, ketone, organic acid, hydro carbons, or the mixed solvent of the two or more solvents of selecting from the group of these compositions.As solvent, the mixed solvent of one or more that preferred use is selected from the group that alcohols, ketone, organic acid are formed is more preferably from C
2～C
6Organic acid, the tert-butyl alcohol, and C
3～C
6The group formed of ketone in select a kind of or these mixed solvent.
Owing to can make more high performance catalyst, the mixed solvent of therefore preferred organic solvent and water.Under the situation of mixed solvent that is organic solvent and water, preferably from alcohols, ketone, the organic solvent of one or more that select in the group that the organic carboxyl acid class is formed and the mixed solvent of water.Wherein, the mixed solvent of the solvent of one or more that preferably from the organic carboxyl acid class, select and water.As organic acid, that preferably selects from the group that acetate, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid are formed is at least a.Wherein preferred especially positive valeric acid or acetate.Though at this moment the use amount of water is not particularly limited, preferably the quality with respect to mixed solvent is more than the 5 quality %, more preferably more than the 8 quality %.And the amount of above-mentioned water is preferably below the 60 quality %, more preferably below the 50 quality %, more preferably below the 40 quality %.Under the situation of mixed solvent, though the homogeneous state is used in hope, non-homogeneous state does not hinder yet.
In above-mentioned solvent, with carrier and metallic compound according to the order of hope or add simultaneously, thereby the metal compound solution that modulation disperses carrier.The concentration of metallic compound is preferably more than the 0.1 quality %, more preferably more than the 0.2 quality %, is preferably especially more than the 0.5 quality %.And the concentration of above-mentioned metallic compound is preferably below the 20 quality %, more preferably below the 10 quality %, more preferably below the 7 quality %, is preferably especially below the 4 quality %.
Then, disperseed to add in the metal compound solution of carrier reducing agent at this and reduced, be supported on supported catalyst thereby obtain metal.
The reducing agent that uses is not particularly limited, and gets final product so long as possess the material of the reducing power of the metal of the state of oxidation in the compound of reducing metal.For example can use hydrazine, formaldehyde, sodium borohydride, hydrogen, formic acid, formates, alcohols and olefines etc.Wherein, preferably from formaldehyde, that selects in the group that propylene, isobutene, 1-butylene and 2-butylene are formed is at least a, more preferably formaldehyde, propylene, perhaps isobutene.
For example using under the situation of gas as reducing agent such as propylene, the metal compound solution that has disperseed carrier is joined in the pressue devices such as autoclave, preferably the method that the autoclave internal pressurization is reduced with reducing agent.This pressure is preferably 0.1～1.0MPa (pressure gauge pressure, pressure shown below is the pressure gauge pressure).
At reducing agent is under the situation of liquid or solid, reducing agent can be joined in the metal compound solution that has disperseed carrier to reduce.The use amount of reducing agent is preferably about 1～50 mole with respect to 1 mole metal compound at this moment.
The temperature of system and recovery time during reduction, different and different according to method of reducing, used carrier, metallic compound, solvent, reducing agent etc., cannot treat different things as the same, but the situation of liquid-phase reduction, reduction temperature is preferably more than-5 ℃, more preferably more than 0 ℃, more preferably more than 15 ℃.And reduction temperature is preferably below 150 ℃, more preferably below 100 ℃, more preferably below 80 ℃.Recovery time was preferably more than 0.1 hour, more preferably more than 0.25 hour, more preferably more than 0.5 hour; And the recovery time was preferably below 24 hours, more preferably below 4 hours, more preferably below 3 hours, was preferably especially below 2 hours.
To from dispersion liquid, support the catalyst of metal after the reduction in the carrier of separating.Separation method is not particularly limited, and for example can use methods such as filtration, centrifugation.Catalyst after the separation will be through suitably dry.Drying means is not particularly limited, and can in all sorts of ways.
In addition, having separated concentration of metal contained in the solution of catalyst after the preferred reduction is below the 10mg/l.The concentration of metallic compound and reducing condition etc. were regulated before this amount can be reduced by change.What GOLD FROM PLATING SOLUTION belonged to has or not reducing agents such as can passing through to add hydrazine and affirmation simply.In addition, the amount of GOLD FROM PLATING SOLUTION genus can be undertaken quantitatively by elementary analyses such as ICP.
The metal of catalyst supports rate, is preferably more than the 0.1 quality % with respect to carrier before supporting, and more preferably more than the 0.5 quality %, more preferably more than the 1 quality %, is preferably especially more than the 4 quality %.In addition, it is below the 40 quality % that the metal of catalyst supports rate with respect to carrier quality optimization before supporting, and more preferably below the 30 quality %, more preferably below the 20 quality %, is preferably especially below the 15 quality %.Support rate, metal quality contained in the solution after the quality of metal in the quality of the carrier that can use when making catalyst, the metallic compound, reduction back and the catalyst separation is tried to achieve.
The catalyst that makes like this after can cleaning with solvent, is applied in the reaction with the state of dispersion liquid, also can be applied in the reaction and go through after centrifugation or the isolated by filtration.
Catalyst can activate before being applied to liquid phase oxidation reaction.The method of activation is not particularly limited, can variety of methods.As the method for activation, the preferably method that heats under the reduction atmosphere gas in hydrogen stream.
(3) α, the manufacturing of beta-unsaturated carboxylic acid
Below, to using the α of the present invention that obtains like this, the beta-unsaturated carboxylic acid catalyst for producing, from alkene or α, beta-unsaturated aldehyde is made α by liquid phase oxidation, and the manufacture method of beta-unsaturated carboxylic acid describes.
As the raw material olefin of liquid phase oxidation, for example can enumerate propylene, isobutene, 2-butylene etc.In addition, as raw material α, beta-unsaturated aldehyde for example can be enumerated, methacrylaldehyde, MAL, crotonaldehyde (Beta-methyl methacrylaldehyde), cinnamic acid (beta-phenyl methacrylaldehyde) etc.Raw material olefin or α in the beta-unsaturated aldehyde, can contain a spot of saturated hydrocarbons and/or rudimentary saturated aldehyde etc. as impurity.
With the α that liquid phase oxidation makes, beta-unsaturated carboxylic acid, raw material are under the situation of alkene, are the α that has identical carbon skeleton with alkene, beta-unsaturated carboxylic acid.In addition, raw material is α, under the situation of beta-unsaturated aldehyde, is α, and the aldehyde radical of beta-unsaturated aldehyde changes into the α after the carboxyl, beta-unsaturated carboxylic acid.
Catalyst of the present invention is suitable for the liquid phase oxidation of being made acrylic acid, being made methacrylic acid by isobutene or MAL by propylene or methacrylaldehyde.
Used molecularity oxygen source in the reaction, air is economical, but also available pure oxygen or pure oxygen and Air mixing gas as required, also can use air or the pure oxygen mist through dilutions such as nitrogen, carbon dioxide, steam.
Though solvent used in the liquid phase oxidation reaction is not particularly limited, for example can use water; Alcohols such as the tert-butyl alcohol, cyclohexanol; Ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Organic acids such as acetate, propionic acid, n-butyric acie, isobutyric acid, positive valeric acid, isovaleric acid; Organic acid ester such as ethyl acetate, methyl propionate; Hydro carbons such as hexane, cyclohexane, toluene, or use two or more mixed solvent in the group be selected from these compositions.Wherein preferred alcohols, ketone, organic acid, and the group formed of organic acid ester in one or more the solvent selected, more preferably from C
2～C
6Organic acid, the tert-butyl alcohol, C
3～C
6The group formed of ketone in the mixture of a kind of or these solvents of selecting, especially preferably contain any in the tert-butyl alcohol, acetate and the positive valeric acid.In addition, by use be selected from the group that alcohols, ketone, organic acid and organic acid ester form one or more solvent and the mixed solvent of water, can further improve the achievement of liquid phase oxidation reaction, thereby be preferred.Though this moment, the use amount of water was not particularly limited, and with respect to the quality of mixed solvent, was preferably more than the 2 quality %, more preferably more than the 5 quality %; Be preferably below the 70 quality %, more preferably below the 50 quality %.Though solvent is contemplated to be the homogeneous state, use also not hindering of non-homogeneous state.
Liquid phase oxidation reaction can adopt any form in continous way and the batch type, if but consider productivity ratio, then industrial better with continous way.
As the alkene or the α of raw material, the use amount of beta-unsaturated aldehyde with respect to 100 mass parts solvents, is generally more than 0.1 mass parts, more than preferred 0.5 mass parts, and, be generally below 20 mass parts, be preferably below 10 mass parts.
The use amount of molecularity oxygen, with respect to 1 mole of raw material olefin or α, beta-unsaturated aldehyde is preferably more than 0.1 mole, more preferably more than 0.3 mole, is preferably especially more than 0.5 mole.And the use amount of above-mentioned molecularity oxygen is preferably below 30 moles, more preferably below 25 moles, and then is preferably below 20 moles, is preferably especially below 15 moles, most preferably is below 10 moles.
Usually, catalyst uses with suspended state in the reactant liquor that carries out liquid phase oxidation, but also can use on fixed bed.The catalyst use amount with respect to the solution that exists in the 100 mass parts reactors, in the catalyst that exists in the reactor, is preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts, is preferably especially more than 1 mass parts.And the use amount of above-mentioned catalyst is preferably below 30 mass parts, more preferably below 20 mass parts, is preferably especially below 15 mass parts.
Reaction temperature and reaction pressure can suitably be selected according to reaction dissolvent and reaction raw materials.Reaction temperature is preferably more than 30 ℃, more preferably more than 50 ℃, more preferably more than 60 ℃, is preferably especially more than 70 ℃.And reaction temperature is preferably below 200 ℃, more preferably below 150 ℃.Reaction pressure is preferably more than the atmospheric pressure (0MPa), more preferably more than the 0.5MPa, more preferably more than the 2MPa, is preferably below the 10MPa, more preferably below the 7MPa, more preferably below the 5MPa.
Add and depress when reacting, the preferred autoclave of being furnished with agitating function that uses.
Embodiment
Below, enumerate embodiment and comparative example further specifies the present invention, but the present invention is not limited to embodiment." part " in following embodiment and the comparative example refers to mass parts.
(analysis of raw material and product)
Using gas-chromatography analyzes raw material and product.In addition, alkene or α, the conversion ratio of beta-unsaturated aldehyde, the α of generation, the selection rate of beta-unsaturated aldehyde, the selection rate of the polymer oligomer of generation, the α of generation, the selection rate of beta-unsaturated carboxylic acid, productive rate, productivity ratio are as to give a definition:
Alkene or α, the conversion ratio of beta-unsaturated aldehyde (%)=(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 polymer oligomer (%)=(E/B) * 100
α, the productive rate of beta-unsaturated carboxylic acid (%)=(D/A) * 100
α, and the productivity ratio of beta-unsaturated carboxylic acid (g/ (gh))=F/ (G * H)
Here, alkene or the α of A for supplying with, the molal quantity of beta-unsaturated aldehyde, B is alkene or the α that has reacted, the molal quantity of beta-unsaturated aldehyde, 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 be polymer and oligomer gross mass (unit: g) divided by the alkene or the α that supply with, the molecular weight of beta-unsaturated aldehyde and the alkene or the α that calculate, the molal quantity of the polymer oligomer that beta-unsaturated aldehyde converts, the α of F for generating, (unit: g), (unit: g), H is reaction time (h of unit) to the quality of the metal that contains in the catalyst of G for use to the quality of beta-unsaturated carboxylic acid.Here, at α, under the situation of the liquid phase oxidation reaction of beta-unsaturated aldehyde, C/B=0.
[physical property measurement of carrier]
It is to utilize the automatic specific area of Micromeritics corporate system/pore measure of spread device TriStar3000 (commercial name) that the pore volume of carrier, pore distribute, and measures with constant volume method based on the nitrogen adsorption method.The fine pore that can measure is greatly about the scope of 1～100nm in this way, and all pore volume of putting down in writing among the present invention, pore distribution are to calculate with the variation (adsorption isotherm) based on the nitrogen adsorption amount on the direction that relative pressure (adsorption equilibrium pressure/saturated vapour pressure) is raise.
In said determination, used the total pore volume of t-plot method, and the BET specific area is measured to the per unit mass of carrier.And, with the BJH method fine pore is calculated in the pore volume of the pore (mesopore) of 2～50nm, and has been calculated its ratio with respect to total pore volume.
[supporting the averaged particles footpath of palladium in the catalyst of palladium]
Utilize the infiltration type determination of electron microscopy to support the average grain diameter of palladium in the catalyst of palladium.Specifically be to measure and calculate as following.The observation portrait of infiltration type electron microscope etc. is doubly printed, from the visual field, pick out 50 palladium particles arbitrarily, measure the particle footpath respectively.Because the shape of palladium particle is circular basically, thereby all is approximately circle and comes instrumentation.This operation is carried out in three visuals field, with the mean value measured as the averaged particles footpath.
[embodiment 1]
(catalyst manufacturing)
1 part of acid chloride (N.E. ケ system キ ヤ Star ト system) is dissolved in 55 parts the positive valeric acid aqueous solution of 88 quality %.This solution is transferred in the autoclave, and (total pore volume is 0.64cc/g, and the BET specific area is 1313m to add 5 parts of synthesis material active carbons of Network ラ レ ケ ミ カ Le society system again
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 7.8%), and stir.Import propylene to 0.5MPa, be warming up to 50 ℃ with 30 minutes, restore 30 minutes.After reduction finishes, the carried palladium catalyst that obtains is filtered, cleans with the acetic acid aqueous solution of 88 quality %, filtration after the displacement, obtain loading and be 10 quality % to contain palladium catalyst-loaded.
(reaction evaluating)
In autoclave, add 135 parts of 88 quality % acetic acid aqueous solutions that contain 200ppm p methoxy phenol (polymerization inhibitor), and 5.5 parts of above-mentioned rates that support are that the palladium of 10 quality % is catalyst-loaded.Add 4.5 parts of MALs again, closed container is warming up to 90 ℃ under stirring afterwards.Import air to 3.2MPa, make MAL carry out 20 minutes oxidation reaction.The use amount of molecularity oxygen is 0.76 mole with respect to 1 mole of MAL in the oxidation reaction.Reaction after finishing is chilled to reactor near room temperature, takes out reactant liquor.Analyze with the reactant liquor of gas-chromatography after separating catalyst.
At this moment, the conversion ratio of MAL is 84.0%, and the methacrylic acid selection rate is 83.2%, and methacrylic acid productivity ratio is 23.1g/ (gh).
[embodiment 2]
Removing carrier uses the active carbon that obtains from the palm shell manufacturing of Network ラ レ ケ ミ カ Le society system (always pore volume is 0.49cc/g, and the BET specific area is 988m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 10%) outside, use the method identical to carry out the manufacturing and the reaction evaluating of catalyst with embodiment 1.
At this moment, the conversion ratio of MAL is 89.7%, and the selection rate of methacrylic acid is 84.7%, and methacrylic acid productivity ratio is 25.2g/ (gh).
[embodiment 3]
Removing carrier uses the active carbon that obtains from the coal manufacturing of グ イ ネ Application society system (always pore volume is 0.46cc/g, and the BET specific area is 753m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 33%) outside, carry out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 84.4%, and the selection rate of methacrylic acid is 80.1%, and methacrylic acid productivity ratio is 22.4g/ (gh).
[embodiment 4]
(always pore volume is 0.75cc/g, and the BET specific area is 1613m to remove the synthesis material active carbon that carrier uses Network ラ レ ケ ミ カ Le society system
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 4.0%) outside, carry out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 78.3%, and the selection rate of methacrylic acid is 80.1%, and the productivity ratio of methacrylic acid is 20.8g/ (gh).
[embodiment 5]
Removing carrier uses the active carbon that obtains from the coal manufacturing of ダ イ ネ Application society system (always pore volume is 0.92cc/g, and the BET specific area is 1345m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 52%), the reaction time is outside 11 minutes, carries out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 90.3%, and the selection rate of methacrylic acid is 77.3%, and methacrylic acid productivity ratio is 42.1g/ (gh).
[embodiment 6]
(always pore volume is 1.27cc/g, and the BET specific area is 2587m to remove the synthesis material active carbon that carrier uses Network ラ レ ケ ミ カ Le society system
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 26%), the reaction time is outside 11 minutes, carries out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 89.5%, and the selection rate of methacrylic acid is 78.3%, and the productivity ratio of methacrylic acid is 42.3g/ (gh).
[embodiment 7]
Removing carrier uses the active carbon that obtains from the charcoal manufacturing of ノ リ Star ト society system (always pore volume is 1.30cc/g, and the BET specific area is 1692m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 58%), the reaction time is outside 15 minutes, carries out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 86.9%, and the selection rate of methacrylic acid is 76.2%, and methacrylic acid productivity ratio is 29.3g/ (gh).
[comparative example 1]
Removing carrier uses the active carbon that obtains from the coal manufacturing of Northwest heat chemistry society system (always pore volume is 1.61cc/g, and the BET specific area is 3174m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 35%) outside, carry out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 35.0%, and the selection rate of methacrylic acid is 24.3%, and methacrylic acid productivity ratio is 2.8g/ (gh).
[comparative example 2]
Removing carrier uses the active carbon that obtains from the timber manufacturing of ノ リ Star ト society system (always pore volume is 1.61cc/g, and the BET specific area is 1680m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 68%) outside, carry out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 83.1%, and the selection rate of methacrylic acid is 54.5%, and methacrylic acid productivity ratio is 15.0g/ (gh).
[comparative example 3]
(always pore volume is 0.37cc/g, and the BET specific area is 690m to remove the synthesis material active carbon that carrier uses Network ラ レ ケ ミ カ Le society system
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 2.7%) outside, carry out the manufacturing and the reaction evaluating of catalyst with method similarly to Example 1.
At this moment, the conversion ratio of MAL is 50.5%, and the selection rate of methacrylic acid is 65.2%, and methacrylic acid productivity ratio is 10.9g/ (gh).
The rerum natura of the carrier that uses in embodiment 1～7 and the comparative example 1～3 and reaction achievement are shown in table 1 in the lump.As can be seen, using among the embodiment 1～7 of total pore volume at the carrier of 0.40～1.50cc/g, the selection rate of methacrylic acid and productivity ratio are all good.And in the embodiment 1～4 that has used the carrier with less total pore volume, the selection rate of methacrylic acid is good especially.In addition, in the embodiment 5～7 of the carrier that has used big total pore volume, the productivity ratio of methacrylic acid is good especially.
Table 1
| The rerum natura of carrier | Reaction time (min) | MAL conversion ratio (%) | Methacrylic acid selection rate (%) | Methacrylic acid productivity ratio (g/ (gh)) | ||
| Total pore volume (cc/g) | The ratio of fine pore 2～50nm (%) | |||||
| Embodiment 1 | 0.64 | 7.8 | 20 | 84.0 | 83.2 | 23.1 |
| Embodiment 2 | 0.49 | 10 | 20 | 89.7 | 84.7 | 25.2 |
| Embodiment 3 | 0.46 | 33 | 20 | 84.4 | 80.1 | 22.4 |
| Embodiment 4 | 0.75 | 4.0 | 20 | 78.3 | 80.1 | 20.8 |
| Embodiment 5 | 0.92 | 52 | 11 | 90.3 | 77.3 | 42.1 |
| Embodiment 6 | 1.27 | 26 | 11 | 89.5 | 78.3 | 42.3 |
| Embodiment 7 | 1.30 | 58 | 15 | 86.9 | 76.2 | 29.3 |
| Comparative example 1 | 1.61 | 35 | 20 | 35.0 | 24.3 | 2.8 |
| Comparative example 2 | 1.61 | 68 | 20 | 83.1 | 54.5 | 15.0 |
| Comparative example 3 | 0.37 | 2.7 | 20 | 50.5 | 65.2 | 10.9 |
[embodiment 8]
(Preparation of catalysts)
1.05 parts of acid chlorides (N.E. ケ system キ ヤ Star ト system) are dissolved in 20 parts of acetate.Acetic acid solution is added 10 parts of silica supports, and (total pore volume is 0.68cc/g, and the BET specific area is 450m
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 100%) in after the vibration, evaporate.In air, burnt till under 450 ℃ 3 hours then.The catalyst precarsor that obtains added in 13 parts the 37 quality % formalins, be heated to 70 ℃ and stirred 2 hours, after the suction strainer, the tert-butyl alcohol aqueous solution of water and 75% quality filters to be cleaned, obtained palladium support rate be 5 quality % to contain palladium catalyst-loaded.
(reaction evaluating)
In autoclave, add the catalyst made from top method (10.5 parts of total amounts), 100 parts of 75 quality % tert-butyl alcohol aqueous solution, and 0.02 part of p methoxy phenol, airtight then autoclave respectively as reaction dissolvent.Import 2.75 parts of isobutenes, begin to stir (revolution 1000rpm), be warming up to 90 ℃.After intensification is finished, import nitrogen and press to the autoclave and be 2.3MPa, importing compressed air to interior pressure again is 4.6MPa.In reaction, when 0.1MPa is hanged down in internal drop, import oxygen and make the interior high 0.1MPa of voltage rise, repeat this operation 10 times.Import for the 10th time after the oxygen, when interior pressure has reduced 0.1MPa once more, cessation reaction.At this moment coreaction 56 minutes.The use amount of molecularity oxygen is 3.48 moles with respect to 1 mole of isobutene in the oxidation reaction.
Behind the reaction terminating, make in the autoclave ice-cold with ice bath.Gas outlet at autoclave is installed the gas collecting bag, opens the gas vent valve, and the gas limit is reclaimed on the limit makes the pressure in the reactor open.From autoclave, take out the reactant liquor that contains catalyst, use the molecular filter separating catalyst, and reclaim reactant liquor.With gas-chromatography the reactant liquor of recovery and the gas of capture are analyzed, calculated reaction yield and selection rate.
At this moment, conversion for isobutene is 90.7%, and the selection rate of MAL is 28.2%, and the selection rate of methacrylic acid is 28.6%, and the productivity ratio of methacrylic acid is 2.2g/ (gh)
[embodiment 9]
Except using silica/alumina (SiO
2/ Al
2O
3) mol ratio is that (total pore volume is 0.50cc/g, and the BET specific area is 629m for 200 y-type zeolite
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 42%) as carrier outside, with method similarly to Example 8, obtained supporting the loaded palladium-containing catalyst of y-type zeolite of palladium metal.
With the catalyst that obtains above,, react with method similarly to Example 8 except the reaction time is 38 minutes.At this moment, conversion for isobutene is 75.2%, and the selection rate of MAL is 49.9%, and the selection rate of methacrylic acid is 19.0%, and the productivity ratio of methacrylic acid is 1.9g/ (gh)
[comparative example 4]
Except using silica gel/aluminium oxide (SiO
2/ Al
2O
3) mol ratio is that (total pore volume is 0.20cc/g, and the BET specific area is 343m for 485 H-ZSM-5 type zeolite
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 29%) as carrier outside, with method similarly to Example 8, make the loaded palladium-containing catalyst of H-ZSM-5 type zeolite that supports palladium metal
With the catalyst that obtains above,, react with method similarly to Example 8 except the reaction time is 107 minutes.At this moment, conversion for isobutene is 67.4%, and the selection rate of MAL is 59.1%, and the selection rate of methacrylic acid is 15.4%, and the productivity ratio of methacrylic acid is 0.5g/ (gh).
The rerum natura of the carrier that uses in embodiment 8～9 and the comparative example 4 and reaction achievement are shown in table 2 in the lump.As can be seen, be that the selection rate of methacrylic acid and productivity are all good among the embodiment 8 and 9 of carrier of 0.40～1.50cc/g using total pore volume.
Table 2
| The rerum natura of carrier | Reaction time (min) | Isobutene conversion (%) | MAL selection rate (%) | Methacrylic acid selection rate (%) | Methacrylic acid productivity ratio (g/ (gh)) | ||
| Total pore volume (cc/g) | The ratio of fine pore 2～50nm (%) | ||||||
| Embodiment 8 | 0.68 | 100 | 56 | 90.7 | 28.2 | 28.6 | 2.2 |
| Embodiment 9 | 0.50 | 42 | 38 | 75.2 | 49.9 | 19.0 | 1.9 |
| Comparative example 4 | 0.20 | 29 | 107 | 67.4 | 59.1 | 15.4 | 0.5 |
[embodiment 10]
(Preparation of catalysts)
1.16 parts of acid chlorides are joined in the positive valeric acid aqueous solution of 60 part of 88 quality %, under 80 ℃, add thermal agitation and made its dissolving in 1 hour.The solution that obtains is moved in the autoclave, and to add 5.4 parts be that (total pore volume is 0.43cc/g to the active carbon made of raw material, and the BET specific area is 840m with coal
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 26%), begin to stir with the rotating speed of 400rpm, import nitrogen and emit then, for several times, carry out nitrogen replacement so repeatedly to installing inside.Import propylene gas then, make pressure rise to 0.5MPa, be warming up to 50 ℃ (reduction temperatures) and keep 1 hour (recovery time) afterwards.Reaction is cooled to 20 ℃ after finishing, and emits after the internal gas, opens autoclave.Filtering suspension liquid, obtain palladium support rate be 10 quality % (with respect to the quality of the palladium of carrier quality) to contain palladium catalyst-loaded.
The palladium averaged particles of palladium in catalyst-loaded that contain that obtains directly is 1.5nm (the observation multiplying power of infiltration type electron microscope is 1,000,000 times).
(reaction evaluating)
In the autoclave that has been equipped with agitating device, add 69 parts of 88 quality % acetic acid aqueous solutions that contain the 200ppm p methoxy phenol, and 3 parts above-mentioned to contain palladium catalyst-loaded.Add 2.5 parts of MALs again.After the airtight autoclave, begin to stir, with heater heat temperature raising to 90 ℃ with the rotating speed of 820rpm.When arriving 90 ℃, import air to 3.2MPa, keep 20 minutes (reaction time) like this.The use amount of molecularity oxygen is 0.77 mole with respect to 1 mole of MAL in the oxidation reaction.Reaction is cooled to 20 ℃ after finishing.In addition, at the gas discharge outlet of autoclave absorption tube and the gas trapping bag that contains cold water is installed successively.Open gas vent, gas is collected on the limit, the pressure in the open reactor in limit.Reactant liquor is transferred in the centrifuge tube, and centrifugation makes catalyst precipitation.0.5 μ m) and reclaim make supernatant make film filter (aperture: by PTFE.
The result of this reaction is, the conversion ratio of MAL is 93.6%, and the methacrylic acid selection rate is 79.9%, polymer oligomer selection rate 8.5%, and the methacrylic acid yield is 74.8%.
[embodiment 11]
(total pore volume is 0.49cc/g, and the BET specific area is 988m except using the active carbon of making as raw material from palm shell
2/ g, fine pore the pore volume ratio of the mesopore of 2～50nm be total pore volume 10%) as carrier outside, with method similarly to Example 10, make catalyst.The palladium averaged particles that obtains containing in the palladium catalyst-loaded (it is 10 quality % that palladium supports rate) directly is 2.6nm (the observation multiplying power of infiltration type electron microscope is 300,000 times).
Carry out reaction evaluating similarly to Example 10, the result who obtains is, the conversion ratio of MAL is 89.7%, and the methacrylic acid selection rate is 84.7%, polymer oligomer selection rate 4.3%, and the methacrylic acid yield is 76.0%.
[comparative example 5]
Except using 96 quality % acetic acid aqueous solutions, make catalyst similarly to Example 10 as the solvent of making catalyst.The palladium averaged particles that contains in the palladium catalyst-loaded (it is 10 quality % that palladium supports rate) that obtains directly is 8.4nm (the observation multiplying power of infiltration type electron microscope is 300,000 times).
Carry out reaction evaluating similarly to Example 10, the result who obtains is, the conversion ratio of MAL is 46.4%, and the methacrylic acid selection rate is 71.5%, polymer oligomer selection rate 15.4%, and the methacrylic acid yield is 33.2%.
[comparative example 6]
Except using positive valeric acid, make catalyst similarly to Example 10 as the solvent of making catalyst.The palladium averaged particles that contains in the palladium catalyst-loaded (it is 10 quality % that palladium supports rate) that obtains directly is 10.1nm (the observation multiplying power of infiltration type electron microscope is 300,000 times).
Carry out reaction evaluating similarly to Example 10, the result who obtains is, the conversion ratio of MAL is 45.4%, and the methacrylic acid selection rate is 65.2%, polymer oligomer selection rate 21.3%, and the methacrylic acid yield is 30.0%.
[comparative example 7]
Except the acid chloride use amount is 0.11 one, reduction temperature is 25 ℃, and the recovery time is beyond 18 hours, to make catalyst similarly to Example 10.The palladium averaged particles that contains in the palladium catalyst-loaded (it is 10 quality % that palladium supports rate) that obtains directly is 0.8nm (the observation multiplying power of infiltration type electron microscope is 1,000,000 times).
Except that the MAL reaction time is 3 hours, carry out reaction evaluating similarly to Example 10, the result who obtains is, the MAL conversion ratio is 42.5%, the methacrylic acid selection rate is 59.8%, polymer oligomer selection rate 29.6%, and the methacrylic acid yield is 25.4%.
Show the palladium averaged particles footpath and the reaction achievement of the catalyst that uses in embodiment 10～11 and the comparative example 5～7 in the table 3 in the lump.Can find out that the averaged particles of palladium directly is among the embodiment 10 and 11 of 1～8nm in using catalyst, the yield height of methacrylic acid.
Table 3
| Palladium averaged particles footpath (nm) | MAL conversion ratio (%) | Methacrylic acid selection rate (%) | Polymer oligomer selection rate (%) | Methacrylic acid yield (%) | |
| Embodiment 10 | 1.5 | 93.6 | 79.9 | 8.5 | 74.8 |
| Embodiment 11 | 2.6 | 89.7 | 84.7 | 4.3 | 76.0 |
| Comparative example 5 | 8.4 | 46.4 | 71.5 | 15.4 | 33.2 |
| Comparative example 6 | 10.1 | 45.4 | 65.2 | 21.3 | 30.0 |
| Comparative example 7 | 0.8 | 42.5 | 59.8 | 29.6 | 25.4 |
As implied above, the catalyst of the application of the invention, reaction achievement that can be good is from alkene or α, and beta-unsaturated aldehyde is made α by liquid phase oxidation, beta-unsaturated carboxylic acid.
Claims (9)
1. make α for one kind, the beta-unsaturated carboxylic acid catalyst, be to be used for by alkene or α, beta-unsaturated aldehyde is made α by liquid phase oxidation, the catalyst of beta-unsaturated carboxylic acid, it is characterized in that, in total pore volume of measuring according to the nitrogen adsorption method is the carrier of 0.40～1.50cc/g, supported metal.
2. manufacturing α as claimed in claim 1, the beta-unsaturated carboxylic acid catalyst, total pore volume of measuring according to the nitrogen adsorption method of above-mentioned carrier is 0.40～0.80cc/g.
3. manufacturing α as claimed in claim 2, the beta-unsaturated carboxylic acid catalyst, the pore volume ratio of the mesopore of above-mentioned carrier accounts for below 40% of total pore volume, and described mesopore is the fine pore measured according to the nitrogen adsorption method pore at 2～50nm.
4. manufacturing α as claimed in claim 1, the beta-unsaturated carboxylic acid catalyst, total pore volume of measuring according to the nitrogen adsorption method of above-mentioned carrier is 0.80～1.50cc/g.
5. manufacturing α as claimed in claim 4, the beta-unsaturated carboxylic acid catalyst, the pore volume ratio of the mesopore of above-mentioned carrier accounts for more than 10% of total pore volume, and described mesopore is the fine pore measured according to the nitrogen adsorption method pore at 2～50nm.
6. make α for one kind, the beta-unsaturated carboxylic acid catalyst is to be used for by alkene or α, and beta-unsaturated aldehyde is made α by liquid phase oxidation, and the catalyst of beta-unsaturated carboxylic acid is characterized in that, supports the palladium of averaged particles footpath in 1～8nm scope in carrier.
7. as each described manufacturing α of claim 1～5, beta-unsaturated carboxylic acid is characterized in that with the manufacture method of catalyst, in the presence of above-mentioned carrier, with reducing agent reducing metal compound.
8. manufacturing α as claimed in claim 6, beta-unsaturated carboxylic acid be with the manufacture method of catalyst, in the presence of above-mentioned carrier, reduces palladium compound with reducing agent.
9. make α for one kind, the method for beta-unsaturated carboxylic acid is characterized in that, at each described manufacturing α of claim 1～6, beta-unsaturated carboxylic acid is with under the existence of catalyst, and with alkene or α, beta-unsaturated aldehyde utilizes molecularity oxygen to carry out oxidation in liquid phase.
Applications Claiming Priority (7)
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| JP2004033276A JP4204491B2 (en) | 2004-02-10 | 2004-02-10 | Palladium-containing supported catalyst, method for producing the same, and method for producing α, β-unsaturated carboxylic acid |
| JP2004033256 | 2004-02-10 | ||
| JP033276/2004 | 2004-02-10 | ||
| JP033256/2004 | 2004-02-10 | ||
| JP2004233287 | 2004-08-10 | ||
| JP233287/2004 | 2004-08-10 | ||
| PCT/JP2005/001804 WO2005075072A1 (en) | 2004-02-10 | 2005-02-08 | CATALYST FOR PRODUCING α, β-UNSATURATED CARBOXYLIC ACID AND METHOD FOR PREPARATION THEREOF, AND METHOD FOR PRODUCING α, β-UNSATURATED CARBOXYLIC ACID |
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| CN200580004222XA Active CN1917956B (en) | 2004-02-10 | 2005-02-08 | Catalyst for producing alpha, beta-unsaturated carboxylic acid and method for preparation thereof and method for producing alpha, beta-unsaturated carboxylic acid |
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| US3969274A (en) * | 1974-03-14 | 1976-07-13 | National Distillers And Chemical Corporation | Fixed bed catalyst |
| US4435598A (en) * | 1977-10-28 | 1984-03-06 | National Distillers And Chemical Corporation | Process for the catalytic oxidation of propylene to acrylic acid |
| EP0415347B2 (en) * | 1989-08-29 | 2002-06-05 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for the production of methacrylic acid |
| DE3930533C1 (en) * | 1989-09-13 | 1991-05-08 | Degussa Ag, 6000 Frankfurt, De | |
| EP1129764B1 (en) * | 2000-03-01 | 2005-10-26 | Umicore AG & Co. KG | Catalyst for purifying diesel engines exhaust gases and process for its preparation |
| CN100445204C (en) * | 2001-11-27 | 2008-12-24 | 三菱化学株式会社 | Silica and producing method thereof |
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