CN100345631C - Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst - Google Patents

Catalyst for production of acrylic acid and process for production of acrylic acid using this catalyst Download PDF

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Publication number
CN100345631C
CN100345631C CNB2005100594689A CN200510059468A CN100345631C CN 100345631 C CN100345631 C CN 100345631C CN B2005100594689 A CNB2005100594689 A CN B2005100594689A CN 200510059468 A CN200510059468 A CN 200510059468A CN 100345631 C CN100345631 C CN 100345631C
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catalyst
aforementioned
acrylic acid
dry thing
producing
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CN1689700A (en
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柚木弘己
谷本道雄
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Abstract

A catalyst for production of acrylic acid is provided which is highly active or has a long-catalytic-life-time while lowering the temperature rise of the oxidation reaction. As a means of achieving this object, the catalyst comprises an oxide and/or a composite oxide having a metal element composition shown by general formula (1): Mo a V b W c Cu d O x (1) (wherein: when a = 12, then 1 |b |14, 0 |c |12, 0 |d |10, and 0<c + d; and x is a numerical value determined by oxidation states of the elements); with the catalyst being characterized in that any of the vanadium, tungsten, and copper is maldistributed in the surface side or core side of the catalyst. Processes for the production of acrylic acid using these catalysts are also provided.

Description

Acrylic acid catalyst for producing and use the production method for acrylic acid of this catalyst
Technical field
The present invention relates to the acrylic acid catalyst for producing, reach the method for producing acrylic acid that uses this catalyst.
Background technology
Make the catalyst (acrylic acid catalyst for producing) that acrylic acid is used expeditiously as the methacrylaldehyde catalytic gas phase oxidation, be extensive use of and contain molybdenum and the catalyst of vanadium, this manufacture method has been proposed various schemes for necessary catalyst component.
As these manufacture methods; for example; can enumerate (a) does in the dry thing that obtains admittedly in the evaporation of initiation material mixed liquor; add polyvinyl alcohol; resin and water that water absorbing capacity is arranged; after mixing; extrusion molding (for example; with reference to Patent Document 1); (b) with initiation material mixed liquor spray-drying; be fired into sintered body at 400 ℃ then; making water is binding agent; use rotary drum type load device etc.; sintered body (is for example loaded on the carrier; with reference to Patent Document 2); (c) it is solid to adopt evaporation to do at the initiation material mixed liquor; spray-drying; in the dry thing that any method drying of roller drying and pneumatic conveying drying obtains; add propyl alcohol and water; (for example mix the back extrusion molding; with reference to Patent Document 3); (d) with initiation material mixed liquor spray-drying; burn till at 400 ℃ then and make sintered body; the liquid adhesive that the organic compound that makes boiling point under water and the normal pressure or sublimation temperature be higher than 100 ℃ forms (for example loads to sintered body on the carrier; with reference to Patent Document 4); or (e) with after the initiation material mixed liquor drying; burn till at 250~500 ℃ and to make sintered body; using glycerine water solution etc. to use as binding agent rotates comminutor sintered body is loaded on the carrier (for example, with reference to Patent Document 5 and Patent Document 6) etc.
[Patent Document 1] spy opens flat 5-96183 communique
[Patent Document 2] spy opens flat 6-279030 communique
[Patent Document 3] spy opens flat 8-10621 communique
[Patent Document 4] spy opens flat 8-252464 communique
[Patent Document 5] spy opens flat 8-299797 communique
[Patent Document 6] spy opens the 2001-79408 communique
Summary of the invention
Yet, the acrylic acid catalyst for producing that above-mentioned all in the past method for makings make, with regard to any a kind of catalyst, also insufficient as acrylic acid selectivity of purpose product.In addition, it is abundant that all rerum natura long-term stabilities such as for example specific area, pore volume, pore distribute in the chemical property of catalyst or physical property, Acid-Base amount and soda acid intensity and can generating expeditiously can't be said aspect the acrylic acid, and room for improvement is still very big.
Therefore, the problem that the present invention will solve is to provide active acrylic acid catalyst for producing high, that therefore further improve as acrylic acid selectivity of purpose product, temperature rising that not only suppresses oxidation reaction but also the long acrylic acid catalyst for producing of catalyst life that can obtain high acrylic acid yield are provided in addition, the method for producing acrylic acid that uses these catalyst is provided simultaneously.
The present inventor studies with great concentration in order to solve above-mentioned problem.In research process, find except molybdenum and vanadium, also to use tungsten and/or copper, and, can solve aforesaid problem at one stroke by making specific metallic element be the face side and/or the core side of catalyst partially as the necessary metallic element that constitutes catalyst.More particularly, find, first, make tungsten be the face side of catalyst partially, and/or make copper be the core side of catalyst partially, activity of such catalysts height then, all rerum naturas of aforementioned catalyst are stable chronically, and the second, when making vanadium be the face side of catalyst partially, the activity of such catalysts height, all rerum naturas of aforementioned catalyst are stable chronically, and the 3rd, make copper be the face side of catalyst partially, and/or when making tungsten be the core side of catalyst partially, acrylic acid selectivity as the purpose product further improves, the 4th, when making vanadium be the core side of catalyst partially, further improve as acrylic acid selectivity of purpose product.Promptly, partially when first and second this metalloid element as described above, the temperature that not only suppresses oxidation reaction raises, and can obtain and equal or higher in the past acrylic acid selectivity, the result can keep life of catalyst chronically, obtains high acrylic acid yield, in addition, as the preceding the 3rd and the 4th this metalloid element the time, can obtain higher acrylic acid selectivity partially.So confirm to have finished the present invention after these.
Therefore, first acrylic acid catalyst for producing among the present invention, it is characterized in that at oxide of forming with the metallic element of following general formula (1) expression and/or composite oxides in the acrylic acid catalyst for producing for necessary catalyst component, tungsten is the face side of this catalyst partially, and/or copper is the core side of this catalyst partially.
Mo aV bW cCu dO x (1)
(in the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.=
Second acrylic acid catalyst for producing among the present invention, it is characterized in that at oxide of forming with the metallic element of following general formula (1) expression and/or composite oxides vanadium is the face side of this catalyst partially in the acrylic acid catalyst for producing for necessary catalyst component.
Mo aV bW cCu dO x (1)
(in the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.)
The 3rd acrylic acid catalyst for producing among the present invention, it is characterized in that at oxide of forming with the metallic element of following general formula (1) expression and/or composite oxides in the acrylic acid catalyst for producing for necessary catalyst component, copper is the face side of this catalyst partially, and/or tungsten is the core side of this catalyst partially.
Mo aV bW cCu dO x (1)
(in the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤b≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.)
The 4th acrylic acid catalyst for producing among the present invention, it is characterized in that at oxide of forming with the metallic element of following general formula (1) expression and/or composite oxides vanadium is the core side of this catalyst partially in the acrylic acid catalyst for producing for necessary catalyst component.
Mo aV bW cCu dO x (1)
(in the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤b≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.=
In addition, method for producing acrylic acid among the present invention, it is characterized in that in the presence of molecular oxygen, when methacrylaldehyde carries out catalytic vapor phase oxidation manufacturing acrylic acid, use the acrylic acid catalyst for producing (the first, second, third and the 4th acrylic acid catalyst for producing) of the invention described above.
According to the present invention, can be provided in the reaction of long acrolein oxidation as the higher acrylic acid catalyst for producing of acrylic acid selectivity of purpose product, also provide the temperature that not only suppresses oxidation reaction to rise but also can give the long acrylic acid catalyst for producing of catalyst life of high acrylic acid yield.More particularly, of the present invention first or second acrylic acid catalyst for producing, it is the long catalyst of catalyst life that not only suppresses the temperature rising of oxidation reaction but also can give high acrylic acid yield, the present invention the 3rd or the 4th acrylic acid catalyst for producing are as the higher catalyst of acrylic acid selectivity of purpose product.The method for producing acrylic acid that uses these catalyst can also be provided.
The specific embodiment
Below, to acrylic acid catalyst for producing of the present invention and use the method for producing acrylic acid of this catalyst at length to describe, but scope of the present invention is regardless of and is limited to these explanations, even the content beyond the following illustration also can suitably change enforcement in the scope of not destroying main idea of the present invention.
The first, second, third and the 4th acrylic acid catalyst for producing among the present invention (below, sometimes claim system " catalyst of the present invention "), all be that the oxide formed of metallic element shown in the aforementioned formula (1) and/or composite oxides are the catalyst of necessary catalyst component.And, as previously mentioned, first acrylic acid catalyst for producing (below, sometimes claim " first catalyst "), importantly tungsten be partially aforementioned catalyst face side (below, sometimes be called for short " face side "), and/or copper be partially aforementioned catalyst the core side (below, sometimes be called for short " core side "), second acrylic acid catalyst for producing (below, sometimes claim " second catalyst "), importantly vanadium is the face side of aforementioned catalyst partially, the 3rd acrylic acid catalyst for producing (below, sometimes claim " the 3rd catalyst "), importantly copper is the face side of aforementioned catalyst partially, and/or tungsten is the core side of aforementioned catalyst partially, the 4th acrylic acid catalyst for producing (below, sometimes claim " the 4th catalyst "), importantly vanadium is the core side of aforementioned catalyst partially.As first and second catalyst, make metallic element partially the time, the temperature that not only suppresses oxidation reaction rises, and can obtain and equal or higher in the past acrylic acid selectivity, the result can keep life of catalyst chronically, give high acrylic acid yield.And, as the 3rd and the 4th catalyst, make metallic element partially the time, can obtain higher (than aforementioned first and second catalyst height) acrylic acid selectivity.In addition, above-mentioned metallic element is formed among the present invention, except the metallic element (Mo, V, W and Cu) of expression in the general formula (1), also can contain niobium, chromium, manganese, iron, cobalt, nickel, zinc, bismuth, tin and antimony etc. as any composition.
Below, in the catalyst of the present invention, sometimes (promptly the metallic element that is face side partially, copper in vanadium in tungsten in first the catalyst, second the catalyst, the 3rd the catalyst) claim " metallic element (α) ", claim " metallic element (β) " metallic element that is the core side partially (that is the vanadium in the tungsten in the copper in first the catalyst, the 3rd the catalyst, the 4th the catalyst).
There is not particular determination as catalyst form of the present invention, for example,
1) can be that the catalyst material that will contain catalyst component carries out the catalyst that moulding such as extrusion molding make, promptly, carrier not as constituent material and catalyst component as the catalyst that must constituent material carries out moulding system (below, title " preformed catalyst " sometimes.)
2) can be to make the catalyst material that contains catalyst component load to the catalyst that makes on the carrier, promptly, catalyst component with carrier as necessary constituent material, above-mentioned catalyst component load on the surface of above-mentioned carrier and/or the catalyst of inner system (below, claim sometimes " carried catalyst ".)。
Wherein, as above-mentioned 2) the form of carried catalyst, for example, can enumerate
2-1) catalyst component load on carrier surface (area load) (in fact, catalyst component can load on the surface of carrier, also can be the inside that the part of catalyst component is present in carrier), characteristic at vpg connection between carrier that uses and the catalyst that makes has substantial variation (particularly, size ratio behind the supported catalyst composition is carrier Shi Da etc.), the catalyst of so-called eggshell type, or
But 2-2) use the carrier etc. of porous internal load as carrier, catalyst component loads on the catalyst of this carrier inside (inside of this carrier just for example, or inner and the equal load in surface) etc. at least.
In addition, as above-mentioned 2-2) the form of supported catalyst, can enumerate,
2-2-1) an internal load catalyst component (internal load) at carrier (can also can be that the part of catalyst component is present in carrier surface only at the internal load catalyst component of carrier in fact.), between carrier that uses and the catalyst that makes the characteristic of vpg connection do not have substantial variation (particularly, when being carrier with the supported catalyst composition after particle diameter mutually equal), the catalyst of so-called even type, or
2-2-2) above-mentioned 2-1) and two kinds of catalyst that form is compound 2-2-1), that is, equal compound catalyst of supported catalyst composition (the evenly composite catalyst of type and eggshell type) etc. on the inside of carrier and surface.
As the shape of catalyst of the present invention, for example, can enumerate spherical (except that just spherical, the ball that also contains the spherical grade of similar ellipse squeeze bad flat spherical, and be spherical shape basically.), (just) polyhedron shape of column (cylindric, oval column, flat column), dice shape etc., ring-type and amorphous etc. form arbitrarily.
The particle diameter of catalyst of the present invention (mean outside diameter) is unqualified, preferably 1~15mm, be more preferably 3~10mm.Moreover, so-called " mean outside diameter " means the longest part and the mean value of the length of short part in the catalyst particle diameter among the present invention, for example, diameter is identical with mean outside diameter during just spherical catalyst, rather than the longest external diameter is a mean outside diameter with the mean value of short external diameter during just spherical catalyst.
In addition, catalyst of the present invention is aforementioned 2-1) the occasion of egg-shell catalyst, load to the thickness of supported catalyst composition, preferred any part is more than the certain value.Particularly, more than the preferred 30 μ m of above-mentioned thickness, more preferably 60 μ m~5mm, preferred 100 μ m~3mm again.
In the catalyst of the present invention above-mentioned partially degree, if metallic element (α) to surperficial lateral deviation in that (tungsten in first the catalyst exists partially, vanadium in second the catalyst exists partially, or the copper in the 3rd the catalyst exists partially), metallic element (the α) (tungsten in first the catalyst (W elements) that contains in the then relevant catalyst component, vanadium in second the catalyst (v element), copper in the 3rd the catalyst (copper)), can be partial to face side exists greater than half amount of total content, and, metallic element (β) if to the core lateral deviation in that (copper in first the catalyst exists partially, tungsten in the 3rd the catalyst exists partially, or the vanadium in the 4th the catalyst exists partially) time, the metallic element that contains in the catalyst component (the β) (copper in first the catalyst (copper) then, tungsten in the 3rd the catalyst (W elements), vanadium in the 4th the catalyst (v element)), can be partial to the core side exists greater than half amount of its total content.Be face side or core side partially by the metallic element that makes regulation, can easily solve aforesaid problem.
Among the present invention, so-called metallic element (α) is face side partially, be that metallic element (α) in the various metallic elements that contain in the aforesaid catalyst component is face side partially, at length say, mean that above-mentioned metallic element (α) deflection is present near the skin section and/or this skin section of acrylic acid catalyst for producing, at length say again, mean that above-mentioned metallic element (α) mainly is present in above-mentioned skin section, and/or depth direction has wide range of distribution to a certain degree than above-mentioned skin section and mainly is present near this skin section.In addition, here said surperficial lateral deviation regulation, even type, aforementioned 2-2-2 with aforesaid various catalyst forms (for example, aforementioned 2-1) eggshell type, aforementioned 2-2-1)) compound, and aforementioned 1) moulding etc.) kind it doesn't matter, can fully similarly be suitable for.
Among the present invention, so-called metallic element (β) is the core side partially, is that the metallic element (β) in the various metallic elements that contain in the aforesaid catalyst component is the core side partially, at length says, can stipulate as follows according to the kind of aforesaid catalyst form.
Promptly, catalyst of the present invention, at aforementioned 2-1) the occasion of egg-shell catalyst, so-called metallic element (β) is the core side partially, mean that above-mentioned metallic element (β) deflection is present near part that the surface with this carrier in the catalyst component of the carrier institute load in the acrylic acid catalyst for producing joins and/or its, at length say again, mean that above-mentioned metallic element (β) mainly is present in above-mentioned part of joining, and/or the opposite direction of depth direction have wide range of distribution to a certain degree than above-mentioned joining part and mainly be present in this joining part near.
In addition, catalyst of the present invention is at aforementioned 2-2-1) even type, aforementioned 2-2-2) compound, and aforementioned 1) the occasion of moulding type etc., so-called metallic element (β) is the core side partially, mean above-mentioned metallic element (β) deflection be present in the central part of acrylic acid catalyst for producing and/or this central part near, at length say again, mean that above-mentioned metallic element (β) mainly is present in above-mentioned central part, and/or the above-mentioned central part of its peripheral distance has wide range of distribution to a certain degree and mainly is present near this central part.
Catalyst of the present invention, by using the mensuration of EPMA (electron probe microanalysis) device, to the metallic element (metallic element (α) or metallic element (β)) of the regulation that contains in the catalyst component to face side partially and to the existing partially of core side, can estimate according to the method and the standard of following (i)~(iii) expression.At length say, whether metallic element (α) is partially that face side (the surperficial lateral deviation of metallic element (α) is in rate) can adopt following (i) and (ii) estimate, whether metallic element (β) is partially that core side (the core lateral deviation of metallic element (β) is in rate) can adopt following (i) and (iii) estimate.In following (i)~(iii),, condition determination or evaluation method are described according to the kind of catalyst form.In addition, among the embodiment described later, in the evaluation of the core lateral deviation of rate and metallic element (β), adopt the method for the following stated to carry out in rate to the surperficial lateral deviation of metallic element (α).
(i), the metallic element (metallic element (α) or metallic element (β)) of every kind of regulation is carried out confirming analytically by using the mensuration of EPMA device.Particularly, cross section with the central part that contains catalyst is an object, the outer surface of one side's outer surface along the direction of passing through central part to the opposing party measured (line analysis mensuration) continuously to the metallic element (metallic element (α) or metallic element (β)) of regulation from this cross section.Then, the kind according to the catalyst form obtains following figure (curve map).
Promptly, catalyst of the present invention is aforementioned 2-1) the occasion of egg-shell catalyst, among the scope that locates from above-mentioned central part to above-mentioned outer surface, to be the position range of analytic target to above-mentioned outer surface, obtain representing that above-mentioned carrier surface (x=0) is to above-mentioned outer surface (x=r from carrier surface 1) apart from r 1(x axle), and the figure (curve map) of relation between the x transmitted intensity I (y axle) that measures corresponding to the amount of regulation metallic element.
In addition, catalyst of the present invention is aforementioned 2-2-1) even type, aforementioned 2-2-2) compound, and aforementioned 1) the occasion of moulding type etc., to the position range of above-mentioned outer surface, obtain representing that above-mentioned central part (x=0) is to above-mentioned outer surface (x=r with above-mentioned central part as analytic target 2) apart from r 2(x axle), and the figure (curve map) of relation between the x transmitted intensity I (y axle) that measures corresponding to the amount of regulation metallic element.
(ii) according to the kind of catalyst form regulation to surperficial lateral deviation evaluation method and evaluation criterion.
That is the occasion of egg-shell catalyst, aforementioned 2-1) to metallic element (α), asks above-mentioned carrier surface (x=0) to above-mentioned outer surface (x=r 1) be the integrated value N of the position range of the analytic target x transmitted intensity I in all 10, by above-mentioned carrier surface (x=0) towards above-mentioned outer surface (x=r 1) contain 1/2r 1Position (reference position), thus with the integrated value of the x transmitted intensity I of outer surface side position in all as N 11The time, by following formula (a):
Ma(%)=(N 11/N 10)×100 (a)
The surperficial lateral deviation of obtaining is preferably greater than 50% at rate Ma (%), more preferably more than 55%, more preferably more than 60%.In addition, this occasion, the said reference position is more preferably 3/5r 1, 2/3r preferably again 1When not satisfying above-mentioned metewand, might not can easily solve aforesaid problem.
In addition, catalyst of the present invention is at aforementioned 2-2-1) even type, aforementioned 2-2-2) compound, and aforementioned 1) the occasion of moulding type etc., to metallic element (α), ask above-mentioned central part (x=0) to above-mentioned outer surface (x=r 2) be the integrated value N of the x transmitted intensity I of position range in all of analytic target 10, by above-mentioned central part (x=0) towards above-mentioned outer surface (x=r 2) contain 1/2r 2Position (reference position), thus, the integrated value of the x transmitted intensity I of the position of outer surface side in all is N 21The time, by following formula (b):
Mb(%)=(N 21/N 20)×100 (b)
The surperficial lateral deviation of obtaining is preferably greater than 50% at rate Mb (%), more preferably more than 55%, more preferably more than 60%.In addition, this occasion said reference position is more preferably 3/5r 2, 2/3r preferably again 2, when not satisfying above-mentioned metewand, might not can easily solve aforesaid problem.
(iii) according to the kind of catalyst form regulation to the core lateral deviation evaluation method and evaluation criterion.
That is the occasion of egg-shell catalyst, aforementioned 2-1) asks above-mentioned carrier surface (x=0) to above-mentioned outer surface (x=r to metallic element (β) 1) be the integrated value N of the x transmitted intensity I of position range in all of analytic target 30, by above-mentioned carrier surface (x=0) towards above-mentioned outer surface (x=r 1) contain 1/2r 1Position (reference position), thus, the integrated value of the x transmitted intensity I of carrier surface side position in all is N 31The time, by following formula (c):
Mc(%)=(N 31/N 30)×100 (c)
The core lateral deviation of obtaining is preferably greater than 50% at rate Mc (%), and is more preferably more than 55%, preferred again more than 60%.In addition, this occasion said reference position is more preferably 2/5r 1, 1/3r preferably again 1When not satisfying above-mentioned metewand, might not can easily solve aforesaid problem.
In addition, catalyst of the present invention is aforementioned 2-2-1) even type, aforementioned 2-2-2) compound, and aforementioned 1) the occasion of moulding type etc., to metallic element (β), ask above-mentioned central part (x=0) to above-mentioned outer surface (x=r 2) be the integrated value N of the x transmitted intensity I of position range in all of analytic target 40, by above-mentioned central part (x=0) towards above-mentioned outer surface (x=r 2) contain 1/2r 2Position (reference position), so the integrated value of the x transmitted intensity I of the position of central part side in all is N 41The time, by following formula (d):
Md(%)=(N 41/N 40)×100 (d)
The core lateral deviation of obtaining is preferably greater than 50% at rate Md (%), more preferably more than 55%, more preferably more than 60%.In addition, this occasion, the said reference position is more preferably 2/5r 2, 1/3r preferably again 2When not satisfying above-mentioned metewand, might not can easily solve aforesaid problem.
Catalyst of the present invention, when using the EPMA device to carry out various mensuration and analyze as described above, shape as the determination object catalyst, for example, preferably spherical (especially, just spherical and just spherical etc. basically), column (especially cylindric etc.), ring-type (especially Huan cross section for the ring-type of circle etc.) etc., be more preferably spherical (especially just spherical and just spherical basically etc.).Moreover, about the shape of catalyst, though adopt to use analysis, the evaluation method of EPMA device may be difficult to confirm the distribution of the metallic element stipulated, so long as the shape of the acrylic acid catalyst for producing that general crowd knows then can be analyzed fully, estimate.In addition, catalyst cross section when relevant use EPMA device is analyzed, for example, can be considered the cross section (circular cross section) vertical during cylindrical catalyst with the center line of cylinder, during spherical catalyst, be face, be considered as and form the mutually perpendicular plane, plane of ring during the ring-type catalyst, and be the face by the ring center line, the wall thickness cross section partly that cutting forms ring by ball center.
Use the EPMA device, when carrying out the evaluation of the method benchmark shown in aforementioned (i)~(iii), catalyst particle size of the present invention (mean outside diameter) is 1~15mm preferably, is more preferably 3~10mm.If in the above-mentioned scope of particle diameter, then use the inclined to one side of regulation metallic element of the analytical method defined of EPMA device good dependency relation to be arranged at state and its effect.
In addition, occasion one catalyst of the present invention that carries out above-mentioned same evaluation is aforementioned 2-1) the occasion of egg-shell catalyst, load to the thickness of supported catalyst composition, preferred any part is more than the certain value.Particularly, above-mentioned thickness above, more preferably 60 μ m~5mm, preferred 100 μ m~3mm again of 30 μ m preferably.
Acrylic acid catalyst for producing of the present invention, general adopt comprise that operation, this drying thing use liquid adhesive etc. that molybdenum also has tungsten and/or copper to make dry thing for initiation material mixed liquor (aqueous solution or water-soluble serous attitude attitude) drying that must composition with vanadium, are simultaneously carried out the operation of moulding, the method for the operation of operation that the formed body that makes is burnt till etc. makes.
Obtain above-mentioned molybdenum and vanadium and tungsten and/or copper and be oxide that must metallic element and/or the initiation material that composite oxides are used, from ammonium salt, nitrate, carbonate, chloride, sulfate, hydroxide, acylate and the oxide of the general metallic element that uses of this kind catalyst, select, but preferably use ammonium salt and nitrate.
The mixed liquor of initiation material can adopt the general method preparation of using in this catalyst manufacturing, therefore, sequentially initiation material is mixed into and makes it to form the aqueous solution or water-based slurry in the water, and also these sequentially can be mixed according to the occasion that the kind of initiation material prepares the multiple aqueous solution or water-based slurry.The condition of above-mentioned mixing (order by merging, temperature, pressure, pH etc.) does not have particular restriction.
The mixed liquor of the initiation material that obtains like this adopts the whole bag of tricks to be dried to dry thing.For example, can enumerate the method for heat drying or the method for drying under reduced pressure.
About obtaining the heating means that dry thing uses and the form of dry thing, for example, can use spray dryer, roller drier etc. to obtain pulverous dry thing, also can use box drying machine, canal drier etc. in air-flow, to heat the dry thing that obtains bulk or sheet.
The dry thing that obtains through being used to obtain pulverizing process or the classification operation that suitable granularity powder is used, is delivered to molding procedure as required again.Moreover the granularity of above-mentioned dry powder is unqualified, below the preferred 500 μ m.
The dry thing that will obtain in the molding procedure can use liquid adhesive etc. when carrying out moulding.Particularly, can adopt the dry thing that obtains is added the method that moulding is carried out in the liquid adhesive mixing, perhaps, dry thing is loaded to when (obtaining carried catalyst) on the desired carrier, use liquid adhesive to make that this carrier is wetting to add the method etc. that dry thing carries out load again.
In addition, when obtaining catalyst of the present invention, except aforesaid general method for making, also can adopt moist initiation material mixed liquor and directly use this initiation material mixed liquor, make this mixed liquor of desired carrier absorption or be coated with or adhere to the method for burning till then.Therefore, as the form of carrier supported catalyst composition, except the form of the aforesaid dry thing of load, also can enumerate the form of load initiation material mixed liquor itself.
Unqualified as above-mentioned liquid adhesive, generally can use the employed binding agent of this shaping of catalyst or load.Particularly, outside dewatering, also can make the organic compound of spent glycol, glycerine, propionic acid, maleic acid, benzylalcohol, propyl alcohol, polyvinyl alcohol, phenol etc. or nitric acid, ammonium nitrate, ammonium carbonate, Ludox etc.In addition, these can only use a kind, also can will also use more than 2 kinds.
The use amount of above-mentioned liquid adhesive (addition) is unqualified, can according to the method for moulding of being adopted or load, and the rerum natura of dry thing powder etc. suit to stipulate.
Obtain the occasion of catalyst of the present invention, can use the shaping assistant that can improve mouldability or improve the reinforcing agent of catalyst strength, the pore that makes catalyst form appropriate pore to form the various materials that use for these effects in the general catalyst manufacturing such as agent.As these various materials, for example, can enumerate stearic acid, graphite, starch, cellulose, silica, alundum (Al, glass fibre, carborundum, silicon nitride etc., preferably catalyst performance (for example activity, purpose product selectivity etc.) not had dysgenic material because of interpolation.These various materials for example, can add to be mixed in above-mentioned liquid adhesive or the initiation material mixed liquor and use.The occasion of these various material addition surpluses owing to sometimes the mechanical strength of catalyst is reduced significantly, can not be used as industrial catalyst even, so preferred interpolation does not reduce the amount of the degree of catalyst mechanical strength.
As aforementioned bearer, can use the inert carrier arbitrarily of certain shape, particularly, for example, can use the carrier with definite shape of trioxygen-containingization two aluminium, silica, silica alundum (Al, titanium oxide, magnesia, talcum and carborundum etc.
The occasion of supported catalyst, the load factor of catalyst consider condition, activity of such catalysts and the intensity etc. of oxidation reaction and determine aptly, preferably 10~70 quality %, be more preferably 15~50 quality %.Load factor is the value that the calculation method described in the embodiment described later is tried to achieve.
As adoptable forming method in the molding procedure; can adopt known method means in the past; for example, can adopt extrusion moulding (extrusion shaping machine), comminution granulation (rotating comminutor, centrifugal flow coating unit), floating following formula spherical container shaping method, compression molding method, infusion process, evaporation to do the forming method of solid method and spray-on process etc.These methods can suitably be selected to be used in combination.
The method (being the method for catalyst surface side or catalyst core side (catalyst center side) usefulness partially) of suitably regulating and controlling at the abundance amount of catalyst surface side or catalyst core side (catalyst center side) as the metallic element as catalyst component (α) or the metallic element (β) of catalyst of the present invention, for example, can adopt (A) prepare in advance relevant as catalyst component metallic element (α) and/or the different multiple catalyst material of the composition component of metallic element (β) (for example, catalyst component mixed liquor or its dry thing), control various catalyst materials, the abundance of metallic element (α) and/or metallic element (β) is created a difference in catalyst surface side and catalyst core side, and after becoming the amount of regulation, carry out the method for moulding (containing load) etc.
(A) method, at length say, for example, prepare catalyst material X and catalyst material Y in advance respectively as above-mentioned multiple catalyst material, adopt following 1)~5) method, promptly 1) catalyst material X is played the sheet moulding, then, to beat the formed body that the sheet moulding makes is the method (having nuclear to beat the sheet method) that nuclear is beaten sheet preformed catalyst material Y again, 2) catalyst material X is carried out extrusion molding, then, the formed body that this extrusion molding is made is beaten the method (having nuclear to beat the sheet method) of sheet preformed catalyst material Y, 3) method loads on the carrier catalyst material X to adopt evaporation to do admittedly, then, adopting the method for the dried solid method supported catalyst agent material Y of evaporation, 4) method loads on the carrier, catalyst material X then to adopt evaporation to do admittedly, adopt the method for rotating comminution granulation supported catalyst agent material Y, 5) adopt evaporation to do solid method catalyst material X is loaded on the carrier, then, adopt the method for spray-on process supported catalyst agent material Y etc.In addition, above-mentioned 1) in the method~5), can be between each processing of moulding of repeatedly carrying out or load, the heat treatment of carrying out drying or burning till etc., in addition, above-mentioned 1) in the method~5), repeatedly the amount of the catalyst material that uses during respectively the handling of moulding of carrying out or load is unqualified, can suitably set, make it to realize aforementioned regulation catalyst component partially (promptly obtaining catalyst of the present invention).
When preparing catalyst of the present invention, when carrying out the burning till of formed body, preferred 350 ℃~450 ℃, more preferably 380 ℃~420 ℃ of firing temperatures, preferred about 1~10 hour of firing time.Before above-mentioned burning till, can under than the low temperature of above-mentioned firing temperature, carry out The pre-heat treatment.
Method for producing acrylic acid of the present invention is characterized in that, in the presence of molecular oxygen, catalytic gas phase oxidation of acrolein is made the acrylic acid catalyst for producing that uses the invention described above in the acrylic acid.The catalyst of the application of the invention can at one stroke and easily solve aforesaid problem.
Make acrylic acid as catalytic gas phase oxidation of acrolein, except use catalyst this point of the present invention as catalyst, do not have particular restriction, can under general device, method and the condition of using, implement.
Aforesaid propylene aldehyde, generally be to supply with catalytic vapor phase oxidation with the unstrpped gas state that contains methacrylaldehyde, as such unstrpped gas, the mist that yes methacrylaldehyde, oxygen and inert gas are formed, the mist that contains methacrylaldehyde that also can use direct oxidation of propylene to obtain also can add air or oxygen as required, add water vapour or other gas again and use.The acrylic acid that contains contained accessory substance in the methacrylaldehyde mist, acetic acid, carbonoxide, propane or the unreacting propylene etc. that make as direct oxidation of propylene, the acrylic acid catalyst for producing that the present invention is used is without any harm.
Catalytic vapor phase oxidation reaction of the present invention can adopt any method of sinolprocess or round-robin method, can use fixed bed reactors, fluidized-bed reactor, moving-burden bed reactor etc. as reactor.
With regard to the condition of above-mentioned reaction, the general condition of using in the time of can adopting catalytic vapor phase oxidation reaction to make acrylic acid, for example, the gaseous mixture that makes the water vapour of oxygen, the 0-30 volume % (preferred 0~25 volume %) of methacrylaldehyde, 0.5~25 volume % (preferred 2~20 volume %) of 1~15 volume % (preferred 4~12 volume %), forms with the inert gas of the nitrogen of 20~80 volume % (preferred 50~70 volume %) etc. etc., under the temperature range of 200~400 ℃ (preferred 220~380 ℃), pressure, adopted 300~10000 o'clock at 0.1~1MPa -1(STP) (preferred 500~5000 o'clock -1(STP)) air speed contacts with the acrylic acid catalyst for producing of the invention described above and to react.
Below, be described more specifically the present invention according to embodiment, but the present invention is not subjected to these any qualifications.At length saying, be that example describes with the carried catalyst (egg-shell catalyst) at the catalyst supported on surface composition of inert carrier only, the invention is not restricted to this catalyst, and the production method for acrylic acid of this catalyst of use.In addition, below for convenience's sake, sometimes " mass parts " is abbreviated as " part ", " liter " is abbreviated as " L ".
Various assay methods in following embodiment and the comparative example, the detailed content of computational methods are described below.
The computational methods of<load factor 〉
Load factor (quality %)
=[(the carrier quality of the catalyst quality-use that makes)/make catalyst quality] * 100
The conversion ratio of<methacrylaldehyde 〉
Acrolein conversion rate (mole %)
=(the methacrylaldehyde molal quantity of the methacrylaldehyde molal quantity/supply of reaction) * 100
<acrylic acid yield 〉
Acrylic acid yield (mole %)
=(the methacrylaldehyde molal quantity of the acrylic acid molal quantity/supply of generation) * 100
<acrylic acid selectivity 〉
Acrylic acid selectivity (mole %)
=(the methacrylaldehyde molal quantity of the acrylic acid molal quantity/reaction of generation) * 100
<EPMA section line is analyzed 〉
Analytical equipment: Shimadzu Seisakusho Ltd.'s system, goods name: EPMA-1610
X beam diameter: 1 μ m
Accelerating potential: 15kV
Electron beam current: 0.1 μ A
Minute: 20 milliseconds
Data point: 1024 * 1024
The step of x beam wide (mobile range): 5 μ m
[preparation example]
(preparation of dry thing)
20000 parts of heating of pure water are mixed on the limit, and the limit makes 3000 parts of ammonium molybdates, 663 parts of ammonium metavanadates, 268 parts of dissolvings of ammonium paratungstate.In addition, 2000 parts of heating of pure water are mixed on the limit, and the limit makes 1026 parts of dissolvings of copper nitrate trihydrate compound.With 2 kinds of aqueous solution that obtain, add antimony trioxide again and make the initiation material mixed liquor for 62 parts.After using roller drier with the initiation material mixed liquor drying that obtains, be ground into again and make dry thing (A) below the 500 μ m.
The dry thing (A) that makes like this is as follows except that the ratio of components of the metallic element of deoxidation.
Dry thing (A): Mo 12V 4.0W 0.7Cu 3.0Sb 0.3
Among the preparation method of above-mentioned dry thing (A), except the use amount that changes ammonium metavanadate, ammonium paratungstate, copper nitrate trihydrate compound respectively, the preparation method of other and dry thing (A) similarly makes dry thing (B)~(G).These dry things are as follows respectively except that the ratio of components of the metallic element of deoxidation.
Dry thing (B): Mo 12V 4.0W 1.3Cu 3.0Sb 0.3
Dry thing (C): Mo 12V 4.0W 0.7Cu 2.0Sb 0.3
Dry thing (D): Mo 12V 4.0W 1.3Cu 2.0Sb 0.3
Dry thing (E): Mo 12V 3.5W 1.3Cu 2.0Sb 0.3
Dry thing (F): Mo 12V 5.0W 1.3Cu 2.0Sb 0.3
Dry thing (G): Mo 12V 5.0W 0.7Cu 3.0Sb 0.3
[first catalyst]
[embodiment 1-1]
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of average diameter 5.0mm.Under rotating disc and horizontal plane tilt 30 ° state, adopt the rotation of rotation number 15rpm limit, the glycol water spraying of 10 quality % is carried out on the limit.Spray after 10 minutes, at first drop into dry thing (A), the dry thing (A) of load on carrier.Then drop into dry thing (B),, form load at the dry thing (B) of the outer lateral load of dry thing (A).
Then, take out this load, under air ambient atmosphere, 400 ℃ were burnt till 6 hours, made spherical catalyst (1-1).In addition, regulate dry thing (A) and the input amount of dry thing (B) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
Be cut into the catalyst that makes (1-1) hemispherical along face by this catalyst center.By the outer surface of central part, use the EPMA device that tungsten and copper are carried out line analysis from side's outer surface of the section of this hemispherical catalyst to the opposing party.According to analysis result, by aforementioned formula (a) tungsten being obtained the reference position is 1/2r 1The time surperficial lateral deviation at rate Ma (%).Simultaneously, by aforementioned formula (c), it is 1/2r that copper is obtained the reference position 1The time the core lateral deviation at rate Mc (%).These be the results are shown in table 1.
(oxidation reaction)
Using alkane to melt in the stainless steel reaction tube of internal diameter 25mm, length 800mm of nitrate heating, catalyst filling (1-1) 100ml is when adopting air speed 2500 -1(STP) mist of importing methacrylaldehyde 4 volume %, oxygen 4 volume %, water vapour 30 volume %, nitrogen 62 volume % carries out the acrolein oxidation reaction continuously.Conditioned reaction temperature makes acrolein conversion rate keep 98~99 moles of % during this.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
[comparative example 1-1]
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of diameter 4.5~5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate was sprayed.Spray after 10 minutes, drop into dry thing (A), the dry thing (A) of load on carrier.The load that taking-up makes, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (c1-1).In addition, regulate the input amount of dry thing (A) in rotating granulation, making the load factor after burning till is 20 quality %.
The catalyst that makes (c1-1) and embodiment 1-1 similarly, the surperficial lateral deviation of asking tungsten in the core lateral deviation of rate Ma (%) and copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Except use catalyst (c1-1) alternative catalysts (1-1) in the oxidation reaction of embodiment 1-1, other and embodiment 1-1 similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction with the acrylic acid selectivity, reach oxidation reaction and begin after reaction temperature and acrylic acid selectivity during through 2000 hours be shown in table 2.
(comparative example 1-2)
(catalyst manufacturing)
Except use the alternative dry thing (A) of dry thing (B) in the catalyst autofrettage of comparative example 1-1, other and comparative example 1-1 similarly make spherical catalyst (c1-2).
The catalyst that makes (c1-2) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), with the core lateral deviation of copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Use in the oxidation reaction of embodiment 1-1 catalyst (c1-2) alternative catalysts (1-1), other carry out oxidation reaction similarly to Example 1.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
(comparative example 1-3)
(catalyst manufacturing)
Except the mixed-powder that uses dry thing (A) and dry thing (B) equivalent to mix equably in the catalyst autofrettage of comparative example 1-1 substituted dry thing (A), other and comparative example 1-1 similarly made spherical catalyst (c1-3).In addition, regulate dry thing (A) and the input amount of dry thing (B) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
The catalyst that makes (c1-3), with embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), and the core lateral deviation of copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Use in the oxidation reaction of embodiment 1-1 catalyst (c1-3) alternative catalysts (1-1), other and embodiment 1-1 similarly carry out oxidation reaction.After the beginning oxidation reaction through 100 hours reaction temperature and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
(embodiment 1-2)
(catalyst manufacturing)
Use dry thing (C) to substitute the dry thing (B) in the catalyst autofrettage of embodiment 1-1, other and embodiment 1-1 similarly make spherical catalyst (1-2).
The catalyst that makes (1-2) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), with the core lateral deviation of copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Use in the oxidation reaction of embodiment 1-1 catalyst (1-2) alternative catalysts (1-1), other and embodiment 1-1 similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
(comparative example 1-4)
(catalyst manufacturing)
Use dry thing (C) to substitute the dry thing (A) in the catalyst autofrettage of comparative example 1-1, other and comparative example 1-1 similarly make spherical catalyst (c1-4).
The catalyst that makes (c1-4) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), with the core lateral deviation of copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Use in the oxidation reaction of embodiment 1-1 catalyst (c1-4) alternative catalysts (1-1), other and embodiment 1-1 similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
[reference example 1-1]
(catalyst manufacturing)
Use dry thing (A) to substitute dry thing (B) in the catalyst autofrettage of embodiment 1-1, use dry thing (C) to substitute the dry thing (A), other and embodiment 1-1 similarly make spherical catalyst (r1-1).
The catalyst that makes (r1-1) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), with the core lateral deviation of copper at rate Mc (%).Such table 1 that the results are shown in.
(oxidation reaction)
Use in the oxidation reaction of embodiment 1-1 catalyst (r1-1) alternative catalysts (1-1), other and embodiment 1-1 similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
[embodiment 1-3~1-5]
(catalyst manufacturing)
Use dry thing (D), (E), (F) to substitute the dry thing (B) in the catalyst autofrettage of embodiment 1-1 respectively, other and embodiment 1-1 similarly make spherical catalyst (1-3), (1-4), (1-5) respectively.
The catalyst that makes (1-3), (1-4), (1-5) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten rate Ma (%), and the core lateral deviation of copper at rate Mc (%).These the table 1 that the results are shown in.
(oxidation reaction)
Use respectively in the oxidation reaction of embodiment 1 catalyst (1-3), (1-4), (1-5) alternative catalysts (1-1), other and embodiment 1-1 similarly carry out oxidation reaction respectively.The reaction temperature during through 100 hours after the beginning oxidation reaction with the acrylic acid selectivity and after beginning oxidation reaction reaction temperature and the acrylic acid selectivity during through 2000 hours be shown in table 2.
[embodiment 1-6~1-9]
(catalyst manufacturing)
In the catalyst autofrettage of embodiment 1-1, use respectively dry thing (B) or (C) substitute dry thing (A), use dry thing (E) or (F) substitute the dry thing (B), other and embodiment 1-1 similarly make spherical catalyst (1-6), (1-7), (1-8), (1-9) (the concrete combination of the dry thing of use is with reference to table 1 or table 2) respectively.
The catalyst that makes (1-6), (1-7), (1-8), (1-9) and embodiment 1-1 similarly, the surperficial lateral deviation of obtaining tungsten in the core lateral deviation of rate Ma (%) and copper at rate Mc (%).These be the results are shown in table 1.
(oxidation reaction)
Use respectively in the oxidation reaction of embodiment 1-1 catalyst (1-6), (1-7), (1-8), (1-9) alternative catalysts (1-1), other similarly carry out oxidation reaction with embodiment 1-1 respectively.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 2.
[embodiment 1-10]
(oxidation reaction)
Catalyst filling (1-2) 1000ml in the stainless steel reaction tube of the internal diameter 25mm, the length 3000mm that use the molten nitrate heating is when adopting air speed 1600 -1(STP) gaseous mixture that imports the inert gas 40 volume % of methacrylaldehyde 5 volume %, air 25 volume %, water vapour 30 volume %, nitrogen etc. carries out oxidation reaction.Beginning through the oxidation reaction result after 100 hours from oxidation reaction, is that 99.1 moles of %, acrylic acid selectivity are that 95.1 moles of %, acrylic acid yield are 94.2 moles of % in 260 ℃ of following acrolein conversion rate of reaction temperature.
[table 1]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle Partially at rate (%)
The surperficial lateral deviation of W is at rate (Ma) The core lateral deviation of Cu is at rate (Mc)
Embodiment 1-1 Catalyst (1-1) Dry thing (A)/dry thing (B) 64 50
Comparative example 1-1 Catalyst (c1-1) Only dry thing (A) 50 50
Comparative example 1-2 Catalyst (c1-2) Only dry thing (B) 50 50
Comparative example 1-3 Catalyst (c1-3) The even mixing of dry thing (A) and dry thing (B) 50 50
Embodiment 1-2 Catalyst (1-2) Dry thing (A)/dry thing (C) 50 62
Comparative example 1-4 Catalyst (c1-4) Only dry thing (C) 50 50
Reference example 1-1 Catalyst (r1-1) Dry thing (C)/dry thing (A) 47 43
Embodiment 1-3 Catalyst (1-3) Dry thing (A)/dry thing (D) 65 60
Embodiment 1-4 Catalyst (1-4) Dry thing (A)/dry thing (E) 65 59
Embodiment 1-5 Catalyst (1-5) Dry thing (A)/dry thing (F) 63 62
Embodiment 1-6 Catalyst (1-6) Dry thing (C)/dry thing (E) 64 50
Embodiment 1-7 Catalyst (1-7) Dry thing (C)/dry thing (F) 62 52
Embodiment 1-8 Catalyst (1-8) Dry thing (B)/dry thing (E) 50 58
Embodiment 1-9 Catalyst (1-9) Dry thing (B)/dry thing (F) 50 60
[table 2]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle After oxidation reaction begins during through 100 hours After oxidation reaction begins during through 2000 hours
Reaction temperature (℃) Acrylic acid selectivity (mole %) Reaction temperature (℃) Acrylic acid selectivity (mole %)
Embodiment 1-1 Catalyst (1-1) Dry thing (A)/dry thing (B) 271 94.0 303 92.9
Comparative example 1-1 Catalyst (c1-1) Only dry thing (A) 275 93.7 321 91.3
Comparative example 1-2 Catalyst (c1-2) Only dry thing (B) 270 93.4 308 91.1
Comparative example 1-3 Catalyst (c1-3) The even mixing of dry thing (A) and dry thing (B) 273 93.5 310 91.8
Embodiment 1-2 Catalyst (1-2) Dry thing (A)/dry thing (C) 272 94.1 304 93.0
Comparative example 1-4 Catalyst (c1-4) Only dry thing (C) 268 93.4 305 91.3
Reference example 1-1 Catalyst (r1-1) Dry thing (C)/dry thing (A) 275 94.8 319 92.3
Embodiment 1-3 Catalyst (1-3) Dry thing (A)/dry thing (D) 269 94.0 295 93.2
Embodiment 1-4 Catalyst (1-4) Dry thing (A)/dry thing (E) 272 94.5 301 93.4
Embodiment 1-5 Catalyst (1-5) Dry thing (A)/dry thing (F) 266 93.8 290 93.2
Embodiment 1-6 Catalyst (1-6) Dry thing (C)/dry thing (E) 271 94.5 302 93.3
Embodiment 1-7 Catalyst (1-7) Dry thing (C)/dry thing (F) 266 94.0 291 93.0
Embodiment 1-8 Catalyst (1-8) Dry thing (B)/dry thing (E) 270 94.3 299 93.1
Embodiment 1-9 Catalyst (1-9) Dry thing (B)/dry thing (F) 266 93.8 290 92.8
[second catalyst]
[embodiment 2-1]
(catalyst manufacturing)
In the rotating disc of disc type rotation comminutor, place the silica alumina carrier of average diameter 5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 weight % while rotate was sprayed.Spray after 10 minutes, at first drop into dry thing (A), the dry thing (A) of load on carrier.Then drop into dry thing (G),, make load at the dry thing (G) of the outer lateral load of dry thing (A).
Then, take out this load, under air ambient atmosphere, 400 ℃ burnt till 6 hours, make spherical catalyst (2-1).In addition, regulate dry thing (A) and the input amount of dry thing (G) in rotating comminutor, make the load factor after burning till be respectively 10 weight %.
Be cut into the catalyst that makes (2-1) hemispherical along face by this catalyst center.At the section of this hemispheric catalyst from a side outer surface by the outer surface of central part to the opposing party, use the EPMA device that vanadium is carried out line analysis.By aforesaid formula (a) vanadium being obtained the reference position according to analysis result is 1/2r 1The time surperficial lateral deviation at rate Ma (%).This be the results are shown in table 3.
(oxidation reaction)
Catalyst filling (2-1) 100ml in the stainless steel reaction tube of the internal diameter 25mm, the length 800mm that heat with molten nitrate is when adopting air speed 2500 -1(STP) gaseous mixture of importing methacrylaldehyde 4 volume %, oxygen 4 volume %, water vapour 30 volume %, nitrogen 62 volume % carries out the acrolein oxidation reaction continuously.Conditioned reaction temperature makes acrolein conversion rate keep 98~99 moles of % during this.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 4.
(comparative example 2-1)
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of diameter 4.5~5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate was sprayed.Spray after 10 minutes, drop into dry thing (A), the dry thing (A) of load on carrier.The load that taking-up makes, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (c2-1).In addition, regulate the input amount of dry thing (A) in rotating comminutor, making the load factor after burning till is 20 quality %.
The catalyst that makes (c2-1) and embodiment 2-1 similarly, the surperficial lateral deviation of obtaining vanadium is at rate Ma (%).The results are shown in table 3.
(oxidation reaction)
Use in the oxidation reaction of embodiment 2-1 catalyst (c2-1) alternative catalysts (2-1), other similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 4.
[comparative example 2-2]
(catalyst manufacturing)
Use dry thing (G) to substitute the dry thing (A) in the catalyst autofrettage of comparative example 2-1, other and comparative example 2-1 similarly make spherical catalyst (c2-2).
The catalyst that makes (c2-2) and embodiment 2-1 similarly, the surperficial lateral deviation of obtaining vanadium is at rate Ma (%).This be the results are shown in table 3.
(oxidation reaction)
Use in the oxidation reaction of embodiment 2-1 catalyst (c2-2) alternative catalysts (2-1), other similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 4.
[comparative example 2-3]
(catalyst manufacturing)
The mixed-powder that uses dry thing (A) and dry thing (G) equivalent to mix equably in the catalyst autofrettage of comparative example 2-1 substitutes the dry thing (A), and other similarly make spherical catalyst (C2-3).In addition, regulate dry thing (A) and the input amount of dry thing (G) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
The catalyst that makes (C2-3) and embodiment 2-1 similarly, the surperficial lateral deviation of obtaining vanadium is at rate Ma (%).This be the results are shown in table 3.
(oxidation reaction)
Use in the oxidation reaction of embodiment 2-1 catalyst (C2-3) alternative catalysts (2-1), other similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 4.
[reference example 2-1]
(catalyst manufacturing)
Use dry thing (G) to substitute dry thing (A) in the catalyst autofrettage of embodiment 2-1, use dry thing (A) to substitute the dry thing (G), other similarly make spherical catalyst (r2-1).
The catalyst that makes (r2-1) and embodiment 2-1 similarly, the surperficial lateral deviation of obtaining vanadium is at rate Ma (%).This be the results are shown in table 3.
(oxidation reaction)
Use in the oxidation reaction of embodiment 2-1 catalyst (r2-1) alternative catalysts (2-1), other similarly carry out oxidation reaction.The reaction temperature during through 100 hours after the beginning oxidation reaction and acrylic acid selectivity, and reaction temperature and acrylic acid selectivity when beginning after the oxidation reaction through 2000 hours be shown in table 4.
[embodiment 2-2]
(oxidation reaction)
Catalyst filling (2-1) 1000ml in the stainless steel reaction tube of the internal diameter 25mm, the length 3000mm that heat with molten nitrate is when adopting air speed 1600 -1(STP) gaseous mixture of the inert gas 40 volume % of input methacrylaldehyde 5 volume %, air 25 volume %, water vapour 30 volume %, nitrogen etc. carries out oxidation reaction.Beginning through the oxidation reaction result after 100 hours from oxidation reaction, is 93.9 moles of % at 99.3 moles of % of 262 ℃ of following acrolein conversion rate of reaction temperature, 94.6 moles of % of acrylic acid selectivity, acrylic acid yield.
[table 3]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle Partially at rate (%)
The surperficial lateral deviation of V is at rate (Ma)
Embodiment 2-1 Catalyst (2-1) Dry thing (A)/dry thing (G) 54
Comparative example 2-1 Catalyst (c2-1) Only dry thing (A) 50
Comparative example 2-2 Catalyst (c2-2) Only dry thing (G) 50
Comparative example 2-3 Catalyst (c2-3) The even mixing of dry thing (A) and dry thing (G) 50
Reference example 2-1 Catalyst (r2-1) Dry thing (G)/dry thing (A) 45
[table 4]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle After oxidation reaction begins during through 100 hours After oxidation reaction begins during through 2000 hours
Reaction temperature (℃) Acrylic acid selectivity (mole %) Reaction temperature (℃) Acrylic acid selectivity (mole %)
Embodiment 2-1 Catalyst (2-1) Dry thing (A)/dry thing (G) 271 93.7 303 92.6
Comparative example 2-1 Catalyst (c2-1) Only dry thing (A) 275 93.7 321 91.3
Comparative example 2-2 Catalyst (c2-2) Only dry thing (G) 268 92.9 302 90.7
Comparative example 2-3 Catalyst (c2-3) The even mixing of dry thing (A) and dry thing (G) 272 93.2 311 90.9
Reference example 2-1 Catalyst (r2-1) Dry thing (G)/dry thing (A) 273 94.4 314 91.8
[the 3rd catalyst]
[embodiment 3-1]
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of average diameter 5.0mm.The glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate under rotating disc and horizontal plane tilt 30 ° state is sprayed.Spray after 10 minutes, at first drop into dry thing (B), the dry thing (B) of load on carrier.Then drop into dry thing (A),, make load at the dry thing (A) of the outer lateral load of dry thing (B).
Then, take out this load, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (3-1).In addition, regulate dry thing (A) and the input amount of dry thing (B) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
Be cut into the catalyst that makes (3-1) hemispherical along face by this catalyst center.At the section of this hemispheric catalyst, by the outer surface of central part, use the EPMA device that copper and tungsten are carried out line analysis to the opposing party from a side outer surface.According to analysis result, by aforementioned formula (a) copper being obtained the reference position is 1/2r 1The time surperficial lateral deviation at rate Ma (%).Simultaneously, by aforesaid formula (c) tungsten being obtained the reference position is 1/2r 1The time the core lateral deviation at rate Mc (%).These the table 5 that the results are shown in.
(oxidation reaction)
Catalyst filling (3-1) 100ml in the stainless steel reaction tube of the internal diameter 25mm, the length 800mm that heat with molten nitrate is when adopting air speed 2500 -1(STP) gaseous mixture of importing methacrylaldehyde 4 volume %, oxygen 4 volume %, water vapour 30 volume %, nitrogen 62 volume % carries out the acrolein oxidation reaction continuously.The conditioned reaction temperature makes acrolein conversion rate keep 98~99 moles of % during this period.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[comparative example 3-1]
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of diameter 4.5~5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate was sprayed.Spray after 10 minutes, drop into dry thing (A), the dry thing (A) of load on carrier.The load that taking-up makes, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (c3-1).In addition, regulate the input amount of dry thing (A) in rotating comminutor, making the load factor after burning till is 20 quality %.
The catalyst that makes (c3-1) and embodiment 3-1 similarly, the surperficial lateral deviation of obtaining copper in the core lateral deviation of rate Ma (%) and tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (c3-1) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[comparative example 3-2]
(catalyst manufacturing)
Use dry thing (B) to substitute the dry thing (A) in the catalyst autofrettage of comparative example 3-1, other and comparative example 3-1 similarly make spherical catalyst (c3-2).
The catalyst that makes (c3-2) and embodiment 3-1 similarly, the surperficial lateral deviation of obtaining copper rate Ma (%), with the core lateral deviation of tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (c3-2) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[comparative example 3-3]
(catalyst manufacturing)
The mixed-powder that uses dry thing (A) and dry thing (B) equivalent to mix equably in the catalyst autofrettage of comparative example 3-1 substitutes the dry thing (A), and other and comparative example 3-1 similarly make spherical catalyst (c3-3).In addition, regulate dry thing (A) and the input amount of dry thing (B) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
The surperficial lateral deviation that the catalyst that makes (c3-3) and embodiment 3-1 similarly obtain copper in the core lateral deviation of rate Ma (%) and tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (c3-3) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[embodiment 3-2]
(catalyst manufacturing)
Use dry thing (C) to substitute the dry thing (B) in the catalyst autofrettage of embodiment 3-1, other and embodiment 3-1 similarly make spherical catalyst (3-2).
The surperficial lateral deviation that the catalyst that makes (3-2) and embodiment 3-1 similarly obtain copper rate Ma (%), with the core lateral deviation of tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (3-2) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[comparative example 3-4]
(catalyst manufacturing)
Use dry thing (C) to substitute the dry thing (A) in the catalyst autofrettage of comparative example 3-1, other and comparative example 3-1 similarly make spherical catalyst (c3-4).
The surperficial lateral deviation that the catalyst that makes (c3-4) and embodiment 3-1 similarly obtain copper in the core lateral deviation of rate Ma (%) and tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (c3-4) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[reference example 3-1]
(catalyst manufacturing)
Use dry thing (A) to substitute dry thing (B) in the catalyst autofrettage of embodiment 3-1, use dry thing (C) to substitute the dry thing (A), other and embodiment 3-1 similarly make spherical catalyst (r3-1).
The surperficial lateral deviation that the catalyst that makes (r3-1) and embodiment 3-1 similarly obtain copper in the core lateral deviation of rate Ma (%) and tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (r3-1) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[reference example 3-2]
(catalyst manufacturing)
Use dry thing (C) to substitute dry thing (B) in the catalyst autofrettage of embodiment 3-1, use dry thing (F) to substitute the dry thing (A), other and embodiment 3-1 similarly make spherical catalyst (r3-2).
The surperficial lateral deviation that the catalyst that makes (r3-2) and embodiment 3-1 similarly obtain copper in the core lateral deviation of rate Ma (%) and tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use in the oxidation reaction of embodiment 3-1 catalyst (r3-2) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[embodiment 3-3,3-4]
(catalyst manufacturing)
Use dry thing (E), (F) to substitute the dry thing (B) in the catalyst autofrettage of embodiment 3-1 respectively, other and embodiment 3-1 similarly make spherical catalyst (3-3), (3-4) respectively.
The surperficial lateral deviation that the catalyst that makes (3-3), (3-4) and embodiment 3-1 similarly obtain copper rate Ma (%), with the core lateral deviation of tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use respectively in the oxidation reaction of embodiment 3-1 catalyst (3-3), (3-4) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[embodiment 3-5~3-8]
(catalyst manufacturing)
In the catalyst autofrettage of embodiment 3-1, use dry thing (E) and (F) any alternative dry thing (B), use dry thing (B) and (C) any alternative dry thing (A), other and embodiment 3-1 similarly make spherical catalyst (3-5), (3-6), (3-7), (3-8) (the concrete combination of the dry thing of use is with reference to table 5 and table 6) respectively.
The surperficial lateral deviation that the catalyst that makes (3-5), (3-6), (3-7), (3-8) and embodiment 3-1 similarly obtain copper rate Ma (%), with the core lateral deviation of tungsten at rate Mc (%).These be the results are shown in table 5.
(oxidation reaction)
Use respectively in the oxidation reaction of embodiment 3-1 catalyst (3-5), (3-6), (3-7), (3-8) alternative catalysts (3-1), other and embodiment 3-1 similarly carry out oxidation reaction respectively.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 6.
[embodiment 3-9]
(oxidation reaction)
Catalyst filling (3-2) 1000ml in the stainless steel reaction tube of the internal diameter 25mm, the length 3000mm that heat with molten nitrate is when adopting air speed 1600 -1(STP) gaseous mixture that imports the inert gas 40 volume % of methacrylaldehyde 5 volume %, air 25 volume %, water vapour 30 volume %, nitrogen etc. carries out oxidation reaction.Beginning through the oxidation reaction result after 100 hours from oxidation reaction, is that 99.0 moles of %, acrylic acid selectivity are that 95.9 moles of %, acrylic acid yield are 94.9 moles of % in 264 ℃ of following acrolein conversion rate of reaction temperature.
[table 5]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle Partially at rate (%)
The surperficial lateral deviation of Cu is at rate (Ma) The core lateral deviation of W is at rate (Mc)
Embodiment 3-1 Catalyst (3-1) Dry thing (B)/dry thing (A) 50 64
Comparative example 3-1 Catalyst (c3-1) Only dry thing (A) 50 50
Comparative example 3-2 Catalyst (c3-2) Only dry thing (B) 50 50
Comparative example 3-3 Catalyst (c3-3) The even mixing of dry thing (A) and dry thing (B) 50 50
Embodiment 3-2 Catalyst (3-2) Dry thing (C)/dry thing (A) 60 50
Comparative example 3-4 Catalyst (c3-4) Only dry thing (C) 50 50
Reference example 3-1 Catalyst (r3-1) Dry thing (A)/dry thing (C) 42 50
Reference example 3-2 Catalyst (r3-2) Dry thing (C)/dry thing (F) 50 40
Embodiment 3-3 Catalyst (3-3) Dry thing (E)/dry thing (A) 58 66
Embodiment 3-4 Catalyst (3-4) Dry thing (F)/dry thing (A) 60 64
Embodiment 3-5 Catalyst (3-5) Dry thing (E)/dry thing (C) 50 65
Embodiment 3-6 Catalyst (3-6) Dry thing (F)/dry thing (C) 50 64
Embodiment 3-7 Catalyst (3-7) Dry thing (E)/dry thing (B) 58 50
Embodiment 3-8 Catalyst (3-8) Dry thing (F)/dry thing (B) 60 50
[table 6]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle After oxidation reaction begins during through 100 hours
Reaction temperature (℃) Acrylic acid selectivity (mole %)
Embodiment 3-1 Catalyst (3-1) Dry thing (B)/dry thing (A) 274 94.8
Comparative example 3-1 Catalyst (c3-1) Only dry thing (A) 275 93.7
Comparative example 3-2 Catalyst (c3-2) Only dry thing (B) 270 93.4
Comparative example 3-3 Catalyst (c3-3) The even mixing of dry thing (A) and dry thing (B) 273 93.5
Embodiment 3-2 Catalyst (3-2) Dry thing (C)/dry thing (A) 275 94.8
Comparative example 3-4 Catalyst (c3-4) Only dry thing (C) 268 93.4
Reference example 3-1 Catalyst (r3-1) Dry thing (A)/dry thing (C) 272 94.1
Reference example 3-2 Catalyst (r3-2) Dry thing (C)/dry thing (F) 266 94.0
Embodiment 3-3 Catalyst (3-3) Dry thing (E)/dry thing (A) 273 95.2
Embodiment 3-4 Catalyst (3-4) Dry thing (F)/dry thing (A) 270 94.7
Embodiment 3-5 Catalyst (3-5) Dry thing (E)/dry thing (C) 274 95.2
Embodiment 3-6 Catalyst (3-6) Dry thing (F)/dry thing (C) 271 94.9
Embodiment 3-7 Catalyst (3-7) Dry thing (E)/dry thing (B) 273 95.1
Embodiment 3-8 Catalyst (3-8) Dry thing (F)/dry thing (B) 272 94.8
[the 4th catalyst]
[embodiment 4-1]
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of average diameter 5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate was sprayed.Spray after 10 minutes, at first drop into dry thing (G), the dry thing (G) of load on carrier.Then drop into dry thing (A),, form load at the dry thing (A) of the outer lateral load of dry thing (G).
Then, take out this load, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (4-1).In addition, regulate dry thing (A) and the input amount of dry thing (G) in rotating comminutor, make the load factor after burning till be respectively 10 quality %.
Be cut into the catalyst that makes (4-1) hemispherical along face by this catalyst center.At the section of this hemispheric catalyst, use the EPMA device that vanadium is carried out line analysis by central part to the opposing party's outer surface from a side outer surface.According to analysis result, by aforesaid formula (c) vanadium being obtained the reference position is 1/2r 1The time the core lateral deviation at rate Mc (%).This be the results are shown in table 7.
(oxidation reaction)
Catalyst filling (4-1) 100ml in the stainless steel reaction tube of the internal diameter 25mm, the length 800mm that heat with molten nitrate is when adopting air speed 2500 -1(STP) gaseous mixture of importing methacrylaldehyde 4 volume %, oxygen 4 volume %, water vapour 30 volume %, nitrogen 62 volume % carries out the acrolein oxidation reaction continuously.Conditioned reaction temperature makes acrolein conversion rate keep 98~99 moles of % during this.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 8.
(comparative example 4-1)
(catalyst manufacturing)
On the rotating disc of disc type rotation comminutor, place the silica alumina carrier of diameter 4.5~5.0mm.Under rotating disc and horizontal plane tilted 30 ° state, the glycol water that adopts rotation number 15rpm to carry out 10 quality % while rotate was sprayed.Spray after 10 minutes, drop into dry thing (A), the dry thing (A) of load on carrier.The load that taking-up makes, 400 ℃ were burnt till 6 hours under air ambient atmosphere, made spherical catalyst (c4-1).In addition, regulate the input amount of dry thing (A) in rotating comminutor, making the load factor after burning till is 20 quality %.
The catalyst that makes (c4-1) is similarly obtained the core lateral deviation of vanadium at rate Mc (%) with embodiment 4-1.This be the results are shown in table 7.
(oxidation reaction)
Except use catalyst (c4-1) alternative catalysts (4-1) in the oxidation reaction of embodiment 4-1, other similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 8.
[comparative example 4-2]
(catalyst manufacturing)
Use dry thing (G) to substitute the dry thing (A) in the catalyst autofrettage of comparative example 4-1, other and comparative example 4-1 similarly make spherical catalyst (c4-2).
The catalyst that makes (c4-2) is similarly obtained the core lateral deviation of vanadium at rate Mc (%) with embodiment 4-1.This be the results are shown in table 7.
(oxidation reaction)
Use in the oxidation reaction of embodiment 4-1 catalyst (c4-2) alternative catalysts (4-1), other similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 8.
[comparative example 4-3]
(catalyst manufacturing)
The mixed-powder that uses dry thing (A) and dry thing (G) equivalent to mix equably in the catalyst autofrettage of comparative example 4-1 substitutes the dry thing (A), and other similarly make spherical catalyst (c4-3).In addition, regulate dry thing (A) and the input amount of dry thing (G), make the load factor after burning till be respectively 10 quality % to the rotation comminutor.
The catalyst that makes (c4-3) is similarly obtained the core lateral deviation of vanadium at rate Mc (%) with embodiment 4-1.This be the results are shown in table 7.
(oxidation reaction)
Use in the oxidation reaction of embodiment 4-1 catalyst (c4-3) alternative catalysts (4-1), other similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 8.
[reference example 4-1]
(catalyst manufacturing)
Use dry thing (A) to substitute dry thing (G) in the catalyst autofrettage of embodiment 4-1, use dry thing (G) to substitute the dry thing (A), other similarly make spherical catalyst (r4-1).
The catalyst that makes (r4-1) is similarly obtained the core lateral deviation of vanadium at rate Mc (%) with embodiment 4-1.This be the results are shown in table 7.
(oxidation reaction)
Use in the oxidation reaction of embodiment 4-1 catalyst (r4-1) alternative catalysts (4-1), other similarly carry out oxidation reaction.Reaction temperature and acrylic acid selectivity during through 100 hours after the beginning oxidation reaction is shown in table 8.
[embodiment 4-2]
(oxidation reaction)
Catalyst filling (4-1) 1000ml in the stainless steel reaction tube of the internal diameter 25mm, the length 3000mm that melt the nitrate heating with alkane is when adopting air speed 1600 -1(STP) gaseous mixture that imports the inert gas 40 volume % of methacrylaldehyde 5 volume %, air 25 volume %, water vapour 30 volume %, nitrogen etc. carries out oxidation reaction.Beginning through the oxidation reaction result after 100 hours from oxidation reaction, is that 98.8 moles of %, acrylic acid selectivity are that 96.0 moles of %, acrylic acid yield are 94.8 moles of % in 263 ℃ of following acrolein conversion rate of reaction temperature.
[table 7]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle Partially at rate (%)
The core lateral deviation of V is at rate (Mc)
Embodiment 4-1 Catalyst (4-1) Dry thing (G)/dry thing (A) 55
Comparative example 4-1 Catalyst (c4-1) Only dry thing (A) 50
Comparative example 4-2 Catalyst (c4-2) Only dry thing (G) 50
Comparative example 4-3 Catalyst (c4-3) The even mixing of dry thing (A) and dry thing (G) 50
Reference example 4-1 Catalyst (r4-1) Dry thing (A)/dry thing (G) 46
[table 8]
Catalyst Composition distribution (particle inside/particle external surface) in the catalyst particle After oxidation reaction begins through 100 hours
Reaction temperature (℃) Acrylic acid selectivity (mole %)
Embodiment 4-1 Catalyst (4-1) Dry thing (G)/dry thing (A) 273 94.4
Comparative example 4-1 Catalyst (c4-1) Only dry thing (A) 275 93.7
Comparative example 4-2 Catalyst (c4-2) Only dry thing (G) 268 92.9
Comparative example 4-3 Catalyst (c4-3) The even mixing of dry thing (A) and dry thing (G) 272 93.2
Reference example 4-1 Catalyst (r4-1) Dry thing (A)/dry thing (G) 271 93.7
Catalyst of the present invention is suitable as the acrylic acid catalyst for producing.
Manufacture method of the present invention is applicable to acrylic acid manufacturing.

Claims (13)

1. fixed bed acrylic acid catalyst for producing, it is characterized in that, oxide that the metallic element of following general formula (1) expression is formed and/or composite oxides be must the fixed bed usefulness acrylic acid catalyst for producing of catalyst component in, tungsten is the face side of this catalyst partially, and/or copper is the core side of this catalyst partially, and the particle diameter of catalyst is that mean outside diameter is 1~15mm
Mo aV bW cCu dO x (1)
In the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.
2. the described fixed bed of claim 1 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the surface of aforementioned bearer, the face side of aforementioned catalyst is near the skin section and/or this skin section of catalyst, and the core side of aforementioned catalyst be the surface of the catalyst component of aforementioned load and the aforementioned bearer part of joining and/or this joining part near.
3. the described fixed bed of claim 1 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the inside of aforementioned bearer at least, perhaps, aforementioned catalyst component carries out moulding as necessary constituent material and forms, the face side of aforementioned catalyst be the skin section of catalyst and/or this skin section near, and the core side of aforementioned catalyst be the central part of catalyst and/or this central part near.
4. fixed bed acrylic acid catalyst for producing, it is characterized in that, oxide that the metallic element of following general formula (1) expression is formed and/or composite oxides be the fixed bed of necessary catalyst component with the acrylic acid catalyst for producing in, vanadium is the face side of this catalyst partially, and the particle diameter of catalyst is that mean outside diameter is 1~15mm
Mo aV bW cCu dO x (1)
In the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.
5. the described fixed bed of claim 4 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the surface of aforementioned bearer, the face side of aforementioned catalyst be the skin section of catalyst and/or this skin section near.
6. the described fixed bed of claim 4 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the inside of aforementioned bearer at least, perhaps, aforementioned catalyst component carries out moulding as necessary constituent material and forms, the face side of aforementioned catalyst be the skin section of catalyst and/or this skin section near.
7. fixed bed acrylic acid catalyst for producing, it is characterized in that, use in the acrylic acid catalyst for producing as the fixed bed of necessary catalyst component at oxide and/or composite oxides that the metallic element of following general formula (1) expression is formed, copper is the face side of this catalyst partially, and/or tungsten is the core side of this catalyst partially, and the particle diameter of catalyst is that mean outside diameter is 1~15mm
Mo aV bW cCu dO x (1)
In the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.
8. the described fixed bed of claim 7 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the surface of aforementioned bearer, the face side of aforementioned catalyst be the skin section of catalyst and/or this skin section near, and the core side of aforementioned catalyst be the surface of the catalyst component of aforementioned load and the aforementioned bearer part of joining and/or this joining part near.
9. the described fixed bed of claim 7 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the inside of aforementioned bearer at least, perhaps, aforementioned catalyst component carries out moulding as necessary constituent material to be made, the face side of aforementioned catalyst be the skin section of catalyst and/or this skin section near, and the core side of aforementioned catalyst be the central part of catalyst and/or this central part near.
10. fixed bed acrylic acid catalyst for producing, it is characterized in that, oxide that the metallic element of following general formula (1) expression is formed and/or composite oxides be must the fixed bed usefulness acrylic acid catalyst for producing of catalyst component in, vanadium is the core side of this catalyst partially, and the particle diameter of catalyst is that mean outside diameter is 1~15mm
Mo aV bW cCu dO x (1)
In the formula, Mo-molybdenum, V-vanadium, W-tungsten, Cu-copper, and O-oxygen, a, b, c, d and x represent the atomic ratio of Mo, V, W, Cu and O respectively, during a=12,1≤b≤14,0≤c≤12,0≤d≤10, and 0<c+d, x is by the determined numerical value of the state of oxidation of each element.
11. the described fixed bed of claim 10 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the surface of aforementioned bearer, the core side of aforementioned catalyst be the surface of the catalyst component of aforementioned load and the aforementioned bearer part of joining and/or this joining part near.
12. the described fixed bed of claim 10 acrylic acid catalyst for producing, it is characterized in that, aforementioned catalyst component with carrier as necessary constituent material, aforementioned catalyst component loads on the inside of aforementioned bearer at least, perhaps, aforementioned catalyst component carries out moulding as necessary constituent material to be made, the core side of aforementioned catalyst be the central part of catalyst and/or this central part near.
13. method for producing acrylic acid is characterized in that, when catalytic gas phase oxidation of acrolein is made acrylic acid in the presence of molecular oxygen, uses each described fixed bed acrylic acid catalyst for producing of claim 1~12.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105612141A (en) * 2013-10-10 2016-05-25 日本化药株式会社 Method for producing unsaturated carboxylic acid, and supported catalyst

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012207811A1 (en) * 2012-05-10 2012-07-12 Basf Se Heterogeneously catalyzed gas phase partial oxidation of (meth)acrolein to (meth)acrylic acid using a catalytically active multimetal oxide mass
CN107321371A (en) * 2017-05-27 2017-11-07 镇江四联机电科技有限公司 A kind of preparation method of acrylic acid catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025549A (en) * 1973-11-28 1977-05-24 Societa' Italiana Resine S.I.R. S.P.A. Process for preparing methyl acrylate or mixtures thereof with acrylic acid
US4289654A (en) * 1978-12-12 1981-09-15 Euteco Impianti S.P.A. Supported catalyst for the oxidation of acrolein into acrylic acid
US5153162A (en) * 1989-08-29 1992-10-06 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalyst for the production of methacrylic acid
DE19736105A1 (en) * 1997-08-20 1999-02-25 Basf Ag Multi-metal oxide catalyst for gas-phase oxidation of acrolein
US6084126A (en) * 1995-11-16 2000-07-04 Basf Aktiengesellshaft Oxidation using multimetal molybdenum and vanadium oxides
CN1472008A (en) * 2002-06-25 2004-02-04 ��������ķ������ Mixed metallic oxide catalyst with physical weather salation load

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4025549A (en) * 1973-11-28 1977-05-24 Societa' Italiana Resine S.I.R. S.P.A. Process for preparing methyl acrylate or mixtures thereof with acrylic acid
US4289654A (en) * 1978-12-12 1981-09-15 Euteco Impianti S.P.A. Supported catalyst for the oxidation of acrolein into acrylic acid
US5153162A (en) * 1989-08-29 1992-10-06 Nippon Shokubai Kagaku Kogyo Co., Ltd. Catalyst for the production of methacrylic acid
US6084126A (en) * 1995-11-16 2000-07-04 Basf Aktiengesellshaft Oxidation using multimetal molybdenum and vanadium oxides
DE19736105A1 (en) * 1997-08-20 1999-02-25 Basf Ag Multi-metal oxide catalyst for gas-phase oxidation of acrolein
CN1472008A (en) * 2002-06-25 2004-02-04 ��������ķ������ Mixed metallic oxide catalyst with physical weather salation load

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105612141A (en) * 2013-10-10 2016-05-25 日本化药株式会社 Method for producing unsaturated carboxylic acid, and supported catalyst
US9751822B2 (en) 2013-10-10 2017-09-05 Nippon Kayaku Kabushiki Kaisha Method for producing unsaturated carboxylic acid and supported catalyst
CN105612141B (en) * 2013-10-10 2018-01-19 日本化药株式会社 The manufacture method and supported catalyst of unsaturated carboxylic acid

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