CN101690900A - Method for preparing catalyst for acrolein and acrylic acid - Google Patents
Method for preparing catalyst for acrolein and acrylic acid Download PDFInfo
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- CN101690900A CN101690900A CN200910235354A CN200910235354A CN101690900A CN 101690900 A CN101690900 A CN 101690900A CN 200910235354 A CN200910235354 A CN 200910235354A CN 200910235354 A CN200910235354 A CN 200910235354A CN 101690900 A CN101690900 A CN 101690900A
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Abstract
The invention discloses a method for preparing a catalyst for acrolein and acrylic acid, which is characterized in that: the catalyst consists of an active component supporter and an inert alumina carrier; the main composition elements of the active component are selected from Mo, Bi, Co and/or Ni and Fe, and the active component also contains trace elements such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P and W; the active component supported on the carrier accounts for 5 to 70 percent of the total weight of the catalyst; and the active component supporter is not prepared by coprecipitation, instead, initial raw materials of the elements of the above expression formula containing the active component are precipitated in aqua ammonia of ammonium molybdate step by step to prepare an active component precursor with core-shell distribution, and the active component precursor is dried and baked to prepare the active component.
Description
Technical field:
The present invention relates to utilize the gas that contains molecular oxygen that propylene is carried out catalytic gas phase oxidation, what a kind of high activity, high life were provided is used to prepare methacrylaldehyde and acrylic acid Preparation of catalysts method.
Background of invention:
About propylene partial oxidation acrolein catalyst, in recent years, many patent reports are arranged both at home and abroad.With regard to catalyst is formed, almost be that molybdenum is a multicomponent catalyst entirely.Many producers are this type of catalyst of industrial production, in order to the preparation methacrylaldehyde, or and then oxidation prepare acrylic acid.Key component in the catalyst comprises Fe
2(MoO
4)
3, α-Bi
2(MoO
4)
3, CoMoO
4And NiMoO
4, α-Bi wherein
2(MoO
4)
3Be the surface-active center, play the selective oxidation effect; Fe
2(MoO
4)
3Play redox facilitation; CoMoO
4And NiMoO
4Play the Stability Analysis of Structures effect.Each component hight coordinate makes catalyst keep good reactivity worth.
The traditional preparation method (CN 87102247, CN 1697701) of catalyst will contain the nitrate aqueous solution of cobalt, nickel, iron at least, joins in the bismuth nitrate with the nitric acid acidifying to mix, and then mixed solution is joined co-precipitation in the ammonium molybdate.The suspension that obtains is carried out drying, this drying thing heat treated is obtained the precursor powder of catalyst, by extrusion molding, compression molding or load with methods such as moulding and give shape arbitrarily.At last, this article shaped is carried out the roasting of a few hours and obtain the equally distributed composite oxide catalysts of each component.
Yet the equally distributed composite oxide catalysts of each component of industrial use is produced in methacrylaldehyde and the acrylic acid process various problems can occur, and wherein a Tu Chu aspect is exactly catalyst inactivation is very fast.Cause the factor of many components Mo-Bi-Co-Fe-O catalysqt deactivation and stability decreases to have a lot, be reduced (Fe comprising the catalyst activity component
3+→ Fe
2+), the formation of different metal oxides, and cause the distillation of Mo component because of part abnormal high temperature (focus) and run off and irreversible crystalline phase variation etc.These factors all can cause the change of specificity of catalyst, cause the reduction of catalyst activity and have shortened service life of catalyst.
In order to improve the performance of catalyst, prolong its service life, multiple solution has been proposed.For example, patent CN 1210511 has mentioned a kind of method by the prepared by co-precipitation composite oxides, and in it was raw materials used, Co was or/and the shared ratio of Ni is higher, in order to Fe in the rugged catalyst
3+, avoid its too fast reduction; The MoO that has free state in addition in the composite oxide catalysts
3, the loss that can replenish the Mo that causes because of distillation.Yet evenly distribute by each active component in the composite oxides of coprecipitation preparation, as activated centre α-Bi
2(MoO
4)
3Do not concentrate and be distributed in catalyst coating; And deposit more α phase structure by the molybdate of cobalt in the catalyst of the method preparation, lack the effective more beta phase structure of reaction, make the synergy between the catalyst activity component be difficult to be brought into play largely, this has suppressed activity of such catalysts and stability.
In addition, for fear of the generation of focus, the technical staff has proposed in reaction tube to arrange two or more reaction zones and has had the various reaction methods that the multiple catalyst of different activities reacts by filling.The example of these class methods of hitherto reported comprises following two kinds (CN 1314331, CN 1210511, JP 4-217932): a kind of is to load active more and more higher catalyst according to the inlet from unstripped gas to outlet, and wherein activity of such catalysts is controlled by the composition or the preparation condition of active component; Another kind method is to have the catalyst that difference occupies volume and be seated in a plurality of reaction zones multiple, and loads to the mode that outlet diminishes according to occupying the inlet of volume from reaction tube.By the type of feed of this class catalyst is set, can avoid the generation of beds focus in the course of reaction, thereby the distillation that suppresses molybdenum component is run off.But these class methods fundamentally do not solve catalysqt deactivation problem faster owing to still use the equally distributed catalyst of active component, by decaying catalyst is carried out phenetic analysis, find Fe
2(MoO
4)
3Be reduced into FeMoO
4, and α-Bi
2(MoO
4)
3Change γ-Bi into
2MoO
6
Summary of the invention;
The present invention is directed to problems of the prior art, a kind of new method for preparing catalyst is provided.Conventional method is to solve the relatively poor problem of catalyst stability by the type of feed that changes some components contents in the catalyst or change catalyst.Distinguishing feature of the present invention is, activity of such catalysts component (supporting thing) has specific crystal phase structure and distribution.Active component is inhomogeneous layer distributed, CoMoO
4, NiMoO
4Be positioned at the kernel of catalyst activity component Deng the molybdate of divalent metal; Fe
2(MoO
4)
3And the MoO of free state
3Invest the skin of kernel; And the outermost layer of active component is a bismuth molybdate.This surface and the inhomogenous active component of body phase composition are supported on the inertia aluminium oxide by proper proportion, can obtain propylene oxidation acrolein and acrylic acid catalyst of high activity, high stability.
The present invention is a kind of preparation methacrylaldehyde and acrylic acid Preparation of catalysts method; It is characterized in that;
Catalyst supports thing by active component and the inertia alumina support is formed; The main component of active component is selected from Mo, Bi, Co and/or Ni and Fe, also comprises trace elements such as K, Na, Rb, Cs, Mg, Ca, Zn, B, p, W; Wherein active component is represented with following statement formula:
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hO
i
In the formula, X represents that K, Na, Rb and Cs's is at least a, Y represents to be selected from least a among B, P and the W, Z represents to be selected from least a among Mg, Ca, the Zn, a～i represents each atoms of elements ratio, when a=12, b=0.5～7, c=0～10, d=0～10, c+d=1～10, e=0.05～3, f=0.0005～3, g=0～3, h=0～1, i are the values that satisfies other element states of oxidation.
According to method for making of the present invention, it is characterized in that; Above-mentioned active component is supported on the 5-70% that ratio on the carrier accounts for the catalyst gross weight.It is not to pass through prepared by co-precipitation that active component supports thing, but the initiation material fractional precipitation that will contain each element of the above-mentioned statement formula of active component is in the ammonia spirit of ammonium molybdate, preparation has the active component predecessor that nucleocapsid distributes, and makes by dry, roasting again:
The concrete preparation process of this catalyst may further comprise the steps:
(a) mixed solution that at first will contain elements such as Co, Ni joins in the ammonia spirit of ammonium molybdate, and under stirring condition, pH is 1～6 in control, 40～80 ℃ of temperature, and reaction generates precipitation, as the nucleus of next step reaction;
(b) mixed solution that will contain elements such as Fe, Bi, K joins in the system of step a gained, under stirring condition, pH is 1～6 in control, 40～80 ℃ of temperature, make on the nucleus that reacts the precipitation deposition step a gained that generates, generate the mixed solution that contains precipitation;
(c) step b gained system is carried out drying, obtain having the active component presoma that nucleocapsid distributes; Dry method adopts any in the conventional drying methods such as evaporation, flash distillation, vacuum drying, rotary evaporation, spray-drying;
(d) with the active component presoma of step c gained, under air atmosphere, be warming up to 300 ℃ and be incubated 1～4hr with 1～20 ℃/min speed, be warming up to 460 ℃ and be incubated 2～5hr with 1～10 ℃/min again, obtain the biscuit firing product;
(e) add adhesive in the biscuit firing product with the steps d gained, and in rotary drum granulator, apply with the inertia alumina balls of 1.5 times of weights; The adhesive kind is to be selected from starch, methylcellulose, glycerine, the acrylate typical binders one or more; Apply on the gained catalyst of back, active component content is 15～50wt%, preferred 25～40%.
(f) with step e gained catalyst dry 10～20hr under 20～80 ℃, preferred 20～40 ℃ of drying 10～15hr;
(g) catalyst of step f gained is warming up to 500～550 ℃ with the speed of 5～30 ℃/min, roasting 3～8hr, preferred 4～5hr obtains the catalyst finished product.
According to method for making of the present invention, it is characterized in that; Active component is uneven distribution, CoMoO
4, NiMoO
4Be positioned at the kernel of catalyst activity component Deng the molybdate of divalent metal; Fe
2(MoO
4)
3And the MoO of free state
3Invest the skin of kernel; And the outermost layer of active component is a bismuth molybdate, forms nuclear---the state of shell layer distributed.
According to method for making of the present invention, it is characterized in that; The divalence molybdate is mainly beta phase structure in the active component, and α phase structure content in active component is very low or do not exist.
In the presence of composite oxide catalysts that preparation method of the present invention makes, utilize the gas that contains molecular oxygen that propylene is carried out catalytic gas phase oxidation and can prepare methacrylaldehyde and acrylic acid.
Optimum implementation of the present invention:
The best catalyst that uses is to be supported on the catalytic active component that having on the inert carrier formed shown in the following formula among the present invention:
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hO
i
In the formula, X represents that K, Na, Rb and Cs's is at least a, Y represents to be selected from least a among B, P and the W, Z represents to be selected from least a among Mg, Ca, the Zn, a～i represents each atoms of elements ratio, when a=12, b=0.5～7, c=0～10, d=0～10, c+d=1～10, e=0.05～3, f=0.0005～3, g=0～3, h=0～1, i are the values that satisfies other element states of oxidation.In above definition, it is desirable to a=12, b=0.5～3, c+d=2～10, e=0.5～3, f=0.005～1, g=0～1, h=0.05～0.5.
Here the state to the drying means of product and the dry products that obtains thus is not particularly limited.For example, the dry products with can obtain powder type as common spray dryer, slurry dried machine or whizzer perhaps can obtain bulk or sheet dry products with common box drier or tunnel type roaster.
After drying was handled, the powder that contains catalytic active component carried out biscuit firing usually under 200-600 ℃, preferred 300-500 ℃ temperature before being carried on the carrier, and the time of biscuit firing reaches 2-24 hour.Biscuit firing is preferably carried out under atmosphere.Be known as the biscuit firing powder hereinafter by the formed powder of biscuit firing.
When above-mentioned biscuit firing powder is supported on carrier, it is mixed with moulding additive and/or intensity improver.The moulding additive comprises analogs such as avicel cellulose, starch, and the intensity improver comprises graphite, ceramic fibre etc., and the consumption of moulding additive or intensity improver is based on the 30wt% of biscuit firing amount of powder or lower.Moulding additive or intensity improver can be before molding in advance with above-mentioned biscuit firing powder, perhaps they are joined in the mould machine when adding the biscuit firing powder.After the shaping of catalyst step in; the powder thing that will contain catalytic active component and moulding additive and/or intensity improver; join in the rotary drum granulator and acutely mix with the inertia aluminium oxide; and use and to comprise binding agents such as water, ethanol, glycerine, the consumption of binding agent is based on the 10-60wt% of biscuit firing powder.Use the method active component can be coated on the inertia alumina surface.
Sintering temperature after the powder that will contain catalytic active component is supported on the carrier is preferably at 450-600 ℃, more preferably 480-600 ℃.Roasting time generally is 3-30 hour, preferred 4-15 hour.Ratio between whole catalyst that catalyst activity component and roasting form can change in the 5-80wt% scope, and this ratio is 20-50wt% preferably.The average diameter of the composite oxide catalysts of the present invention preparation in the 3-15mm scope, preferred 3-8mm.And the specific area of catalyst, average pore diameter and pore pore volume do not have particular restriction, and preferred specific surface is 5-25m
2/ g, average pore diameter is 0.03-1 μ m, pore volume is 0.2-0.7ml/g.
Among the present invention, the gas that the propylene utilization is contained molecular oxygen with above-mentioned catalyst carries out catalytic gas phase oxidation and prepares corresponding methacrylaldehyde and acrylic acid, can adopt existing method to carry out.
The mist that will comprise inert gas 20-70 volume % such as propylene 1-20 volume %, molecular oxygen 3-40 volume %, steam 0-60 volume %, nitrogen, carbon dioxide is under 250-450 ℃, the pressure of 0.1-1Mpa, with space velocity (SV) 300-5000hr
-1, feed in the catalyst layer in the reaction tube that is filled in the preferred 15-50mm of internal diameter.In addition, because the prepared catalyst of the present invention has high activity and high stability,, or under the high space velocity condition, also can turn round even if at higher material concentration.
The specific embodiment:
Embodiment 1
(preparation of composite oxide catalysts)
Ammonium paramolybdate 339g is dissolved in the 2400ml pure water, and adding 520ml concentration is 25% ammonia spirit; 242g cobalt nitrate and 130g nickel nitrate are dissolved in the 300ml pure water; The 132g bismuth nitrate is dissolved in the 160ml pure water of using the acidifying of 20ml nitric acid, in addition, the 116g ferric nitrate is dissolved in the 300ml water, bismuth nitrate solution and iron nitrate solution are mixed.In the time of 50 ℃, the mixed solution of cobalt nitrate and nickel nitrate is added in the ammonia spirit of ammonium molybdate of vigorous stirring, the mixed solution that adds bismuth nitrate and ferric nitrate afterwards again, adding ammoniacal liquor or nitric acid make the pH value of system remain between the 1-6 in adition process, so can obtain suspension recited above.Behind this suspension heat drying, under air atmosphere, be warming up to 300 ℃ and carry out the heat treatment of 1hr with 2 ℃/min, be warming up to 460 ℃ of heat treatments of carrying out 3hr with 4 ℃/min again, obtain above-mentioned biscuit firing powder.Add avicel cellulose in first powders calcined, and mix with the inertia alumina balls of 1.5 times of weights in rotary drum granulator, the glycerine water solution of adding 33% applies.Make at room temperature dry 12 hours of the particle that supports active component, roasting 5 hours in 520 ℃ air stream then obtains to support the catalyst of 40% active component.
The catalyst that is calculated by the raw material that adds is the composite oxides with following atomic ratio.
Mo∶Bi∶Co∶Ni∶Fe∶K＝12∶1.7∶5.2∶2.8∶1.6∶0.1
(oxidation reaction)
The catalyst that 30ml is the such internal diameter of packing into is in the stainless steel reaction pipe of 20ml, leads in the unstripped gas that the air by the steam of the propylene of 10% concentration, 17% concentration and 73% concentration constitutes, and under atmospheric pressure carries out the propylene oxidation reaction.Obtain reaction result as shown in table 1 for 300 ℃ in reaction temperature.
Comparative example 1
Except not adding the ammoniacal liquor in ammonium molybdate solution, other are all identical with embodiment 1, and preparation is formed identical catalyst with embodiment 1, and the reaction structure that obtains is as shown in table 1.
Comparative example 2
Other preparation methods are identical with embodiment 1, and just cobalt nitrate, nickel nitrate, ferric nitrate, bismuth nitrate add in the ammonia spirit of ammonium molybdate simultaneously, and preparation is formed identical catalyst with embodiment 1, and the reaction structure that obtains is as shown in table 1.
Embodiment 2
(preparation of composite oxide catalysts)
Ammonium paramolybdate 339g is dissolved in the 2400ml pure water, and adding 520ml concentration is 25% ammonia spirit; 242g cobalt nitrate and 130g nickel nitrate are dissolved in the 300ml pure water; The 132g bismuth nitrate is dissolved in the 160ml pure water of using the acidifying of 20ml nitric acid, in addition, the 116g ferric nitrate is dissolved in the 300ml water, bismuth nitrate solution and iron nitrate solution are mixed.In the time of 50 ℃, the mixed solution of cobalt nitrate and nickel nitrate is added in the ammonia spirit of ammonium molybdate of vigorous stirring, the mixed solution that adds bismuth nitrate and ferric nitrate afterwards, adding ammoniacal liquor or nitric acid make the pH value of system remain between the 1-6 in adition process, so can obtain suspension recited above.Behind this suspension heat drying, under air atmosphere, be warming up to 300 ℃ and carry out the heat treatment of 1hr with 2 ℃/min, be warming up to 460 ℃ of heat treatments of carrying out 3hr with 4 ℃/min again, obtain above-mentioned biscuit firing powder.Add avicel cellulose in first calcined powder, and mix with the inertia alumina balls of 1.5 times of weights in rotary drum granulator, the glycerine water solution of adding 33% applies.Make at room temperature dry 12 hours of the particle that supports active component, roasting 5 hours in 560 ℃ air stream then obtains to support the catalyst of 40% active component.
The catalyst that is calculated by the raw material that adds is the composite oxides with following atomic ratio.
Mo∶Bi∶Co∶Ni∶Fe∶K＝12∶1.7∶5.2∶2.8∶1.6∶0.1
(oxidation reaction)
The catalyst that 30ml is the such internal diameter of packing into is in the stainless steel reaction pipe of 20ml, leads in the unstripped gas that the air by the steam of the propylene of 10% concentration, 17% concentration and 73% concentration constitutes, and under atmospheric pressure carries out the propylene oxidation reaction.Obtain reaction result as shown in table 1 for 300 ℃ in reaction temperature:
Embodiment 3
(preparation of composite oxide catalysts)
Ammonium paramolybdate 339g is dissolved in the 2400ml pure water, and adding 520ml concentration is 25% ammonia spirit; 242g cobalt nitrate and 130g nickel nitrate are dissolved in the 300ml pure water; The 132g bismuth nitrate is dissolved in the 160ml pure water of using the acidifying of 20ml nitric acid, in addition, the 116g ferric nitrate is dissolved in the 300ml water, bismuth nitrate solution and iron nitrate solution are mixed.In the time of 50 ℃, the mixed solution of cobalt nitrate and nickel nitrate is added in the ammonia spirit of ammonium molybdate of vigorous stirring, the mixed solution that adds bismuth nitrate and ferric nitrate afterwards, adding ammoniacal liquor or nitric acid make the pH value of system remain between the 1-6 in adition process, so can obtain suspension recited above.Behind this suspension heat drying, under air atmosphere, be warming up to 300 ℃ and carry out the heat treatment of 1hr with 2 ℃/min, be warming up to 460 ℃ of heat treatments of carrying out 3hr with 4 ℃/min again, obtain above-mentioned biscuit firing powder.Add avicel cellulose in first calcined powder, and mix with the inertia alumina balls of 1.5 times of weights in rotary drum granulator, the glycerine water solution of adding 33% applies.Make at room temperature dry 12 hours of the particle that supports active component, roasting 5 hours in 560 ℃ air stream then obtains to support the catalyst of 40% active component.
The catalyst that is calculated by the raw material that adds is the composite oxides with following atomic ratio.
Mo∶Bi∶Co∶Ni∶Fe∶K＝12∶1.7∶5.2∶2.8∶1.6∶0.1
(oxidation reaction)
The catalyst that 30ml is the such internal diameter of packing into is in the stainless steel reaction pipe of 20ml, leads in the unstripped gas that the air by the steam of the propylene of 10% concentration, 17% concentration and 73% concentration constitutes, and under atmospheric pressure carries out the propylene oxidation reaction.Obtain reaction result as shown in table 1 for 330 ℃ in reaction temperature.
Propylene conversion (mole %): (the propylene molal quantity of the propylene molal quantity/supply of reaction) * 100
Selectivity (mole %): (generating the propylene molal quantity of methacrylaldehyde and acrylic acid total mole number/reaction) * 100
Gross production rate (mole %): (the propylene molal quantity of the methacrylaldehyde of generation and acrylic acid molal quantity/supply) * 100
Table 1
| Project | Reaction time (hour) | Reaction temperature (℃) | Hot(test)-spot temperature (℃) | Propylene conversion (%) | Selectivity (%) | Gross production rate (%) |
| Embodiment 1 | 2000 | 300 | 364 | 96.7 | 95.2 | 92.1 |
| Comparative example 1 | 2000 | 300 | 372 | 92.4 | 94.3 | 87.1 |
| Comparative example 2 | 2000 | 300 | 376 | 91.8 | 94.8 | 87 |
| Embodiment 2 | 2000 | 300 | 358 | 98.8 | 94.6 | 93.5 |
| Embodiment 3 | 2000 | 330 | 391 | 99.2 | 94.3 | 93.5. |
Claims (4)
1. one kind prepares methacrylaldehyde and acrylic acid Preparation of catalysts method; It is characterized in that;
Catalyst supports thing by active component and the inertia alumina support is formed; The main component of active component is selected from Mo, Bi, Co and/or Ni and Fe, also comprises trace elements such as K, Na, Rb, Cs, Mg, Ca, Zn, B, P, W; Wherein active component is represented with following statement formula:
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hO
i
In the formula, X represents that K, Na, Rb and Cs's is at least a, Y represents to be selected from least a among B, P and the W, Z represents to be selected from least a among Mg, Ca, the Zn, a～i represents each atoms of elements ratio, when a=12, b=0.5～7, c=0～10, d=0～10, c+d=1～10, e=0.05～3, f=0.0005～3, g=0～3, h=0～1, i are the values that satisfies other element states of oxidation;
Active component is supported on the 5-70% that ratio on the carrier accounts for the catalyst gross weight; It is not to pass through prepared by co-precipitation that active component supports thing, but the initiation material fractional precipitation that will contain each element of the above-mentioned statement formula of active component is in the ammonia spirit of ammonium molybdate, preparation has the active component predecessor that nucleocapsid distributes, and makes by dry, roasting again:
The concrete preparation process of this catalyst may further comprise the steps:
(a) mixed solution that at first will contain Co, Ni element joins in the ammonia spirit of ammonium molybdate, and under stirring condition, pH is 1～6 in control, 40～80 ℃ of temperature, and reaction generates precipitation, as the nucleus of next step reaction;
(b) mixed solution that will contain Fe, Bi, K element joins in the system of step a gained, and under stirring condition, pH is 1～6 in control, and 40～80 ℃ of temperature make on the nucleus of the precipitation deposition step a gained that reaction generates, and generate the mixed solution that contains precipitation;
(c) step b gained system is carried out drying, obtain having the active component presoma that nucleocapsid distributes; Dry method employing is selected from any in evaporation, flash distillation, vacuum drying, rotary evaporation, the spray-drying conventional drying method;
(d) with the active component presoma of step c gained, under air atmosphere, be warming up to 300 ℃ and be incubated 1～4hr with 1～20 ℃/min speed, be warming up to 460 ℃ and be incubated 2～5hr with 1～10 ℃/min again, obtain the biscuit firing product;
(e) add adhesive in the biscuit firing product with the steps d gained, and in rotary drum granulator, apply with the inertia alumina balls of 1.5 times of weights; The adhesive kind is to be selected from starch, methylcellulose, glycerine, the acrylate typical binders one or more; Apply on the gained catalyst of back, active component content is 15～50wt%, preferred 25～40%.
(f) with step e gained catalyst dry 10～20hr under 20～80 ℃, preferred 20～40 ℃ of drying 10～15hr;
(g) catalyst of step f gained is warming up to 500～550 ℃ with the speed of 5～30 ℃/min, roasting 3～8hr, preferred 4～5hr obtains the catalyst finished product.
2. method for making according to claim 1 is characterized in that; The catalyst that uses is the catalytic active component of forming shown in the following formula statement formula that has that is supported on the inert carrier:
Mo
aBi
bCo
cNi
dFe
eX
fY
gZ
hO
i
In the formula, X represents at least a of K, Na, Rb and Cs, and Y represents to be selected from least a among B, P and the W, and Z represents to be selected from least a among Mg, Ca, the Zn, and a～i represents each atoms of elements ratio, and i is the value that satisfies other element states of oxidation; And satisfy a=12, b=0.5～3, c+d=2～10, e=0.5～3, f=0.005～1, g=0～1, h=0.05～0.5.
3. method for making according to claim 1 is characterized in that; Active component is uneven distribution, CoMoO
4, NiMoO
4Be positioned at the kernel of catalyst activity component Deng the aluminate of divalent metal; Fe
2(MoO
4)
3And the MoO of free state
3Invest the skin of kernel; And the outermost layer of active component is a bismuth molybdate, forms nuclear---the state of shell layer distributed.
4. method for making according to claim 3 is characterized in that; The divalence molybdate is mainly beta phase structure in the active component, and α phase structure content in active component is very low or do not exist.
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2009
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| CN114471592A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for acrolein synthesis and preparation method and application thereof |
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