CN103801398A - Preparation method of catalyst for preparing methacrylic acid - Google Patents
Preparation method of catalyst for preparing methacrylic acid Download PDFInfo
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- CN103801398A CN103801398A CN201410000384.7A CN201410000384A CN103801398A CN 103801398 A CN103801398 A CN 103801398A CN 201410000384 A CN201410000384 A CN 201410000384A CN 103801398 A CN103801398 A CN 103801398A
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Abstract
The invention provides a preparation method of a catalyst for preparing methacrylic acid. The preparation method comprises the following steps: coating catalyst powder containing heteropolyacid and/or salt of molybdenum, molybdenum and phosphor as active ingredient on a carrier, and then roasting the carrier, wherein inorganic binder is used in the coating process, the sol of oxide of Al, Si, Ti or mixture thereof is adopted as the inorganic binder, which is sodium ion type, non-sodium ion type stable sol or mixture thereof; the particle size of the oxide in the sol is 5-30nm, the content of the oxide is at least 5wt%, the particle size of the sol latex particle is at least 500nm, the density is 1.0-1.3g/cm <3>, the pH (potential of hydrogen) is 8.0-11.0; the adding amount of the sol is 2-30wt% of the amount of the active ingredient; the catalyst prepared according to the preparation method for preparing methacrylic acid has the advantages of high mechanical strength, low pulverization degree, high activity and high performance, and can be used for carrying out selective catalytic oxidation reaction on methylacrolein gas with molecular oxygen in a gas phase, so as to produce methacrylic acid.
Description
Technical field
The present invention relates to catalyst preparation technical field, be specifically related to molecular oxygen, MAL gas be carried out in gas phase the preparation method of selective catalytic oxidation reaction with the catalyst of generation methacrylic acid.
Background technology
Producing metering system carboxylic acid by MAL gas phase selective catalytic oxidation is one of general production method of chemical industry.Producing metering system carboxylic acid by MAL gas phase selective catalytic oxidation is also: after MAL, molecular oxygen precursor are mixed with steam, enter the fixed bed reactors that suitable catalyst reaction is housed, make MAL generate methacrylic acid.Be generally heteropoly acid and/or salt catalyst for the catalyst of this chemical reaction, take the heteropoly acid of molybdenum, vanadium, phosphorus, copper and other preparation of metals and/or salt as basic comprising, there is good MAL activity of conversion.But heteropoly acid and/or salt catalyst have poor heat stability, mechanical strength is low, use life is short, produce the deficiencies such as MAA poor selectivity.For fear of these deficiencies, people are in the relative composition of research, physical property, manufacture method and improvement project.United States Patent (USP) (US462115) discloses " ammonium salt or nitrogenous heterocyclic compound are joined in carbon monoxide-olefin polymeric to improve the selective of MAA ", still, does like this mechanical strength that but greatly reduces catalyst.Japan Patent (JP55-79340) discloses " in the composition of catalyst, improving the mechanical strength of catalyst with metal sulfate ", still, does like this activity and selectivity that but greatly reduces catalyst.
At present, in the time of industrial use heteropoly acid and/or salt catalyst production methacrylic acid, the general heat exchange calandria type fixed bed reactor that uses, need to be at the reaction tube top catalyst filling of several meters long in the filling process of catalyst, therefore, described catalyst not only needs to have high activity and target product selectivity, and need to have enough mechanical strengths.In industrial production, the mechanical strength of catalyst relates generally to following two aspects: the friction between catalyst and tote wall, catalyst and catalyst that () occurs manufacturing, in filling and transportation, and the situation (hereinafter to be referred as efflorescence degree) of the catalyst surface efflorescence causing due to airflow scouring and temperature contrast.(2) peeling off of the breakage of the catalyst causing in filling process self or catalytic component.Consider the application conditions of catalyst, the deficiency of mechanical strength can cause coming off of a large amount of active components, this may cause the problem of two aspects: on the one hand, catalyst is after the operations such as transportation, filling, the amount and the theoretical value that are filled in the catalyst activity component in reactor differ larger, cause industrial production cannot reach the requirement of production technology.On the other hand, particle and powder that catalyst produces through operations such as transportation, fillings are present in reactor, cause reactor pressure decrease increase, production efficiency to reduce.These are all unfavorable for the use of catalyst and the acquisition of economic benefit.In addition, make because related catalyst has numerous slaines or its oxide, the dust of catalyst can produce harm to environment and to human body.Therefore,, no matter from which angle, the mechanical strength and the reduction efflorescence degree that improve catalyst are all necessary.
Research is found, normally by preparing, the operations such as mixed liquor, dry, moulding, calcining complete above-mentioned catalyst (heteropoly acid and/or salt catalyst), and forming process is wherein to improve catalyst mechanical strength, keep one of important step of its catalytic activity and stability.As the method for shaping of catalyst, there is at present the several different methods such as compression molding, extrusion molding.To this, Chinese patent (CN1126718A) discloses " water is obtained to cylindrical catalyst as moulding auxiliary material ".Chinese patent (CN102105223A) discloses " adopting extrusion forming method to obtain preformed catalyst ".Chinese patent (CN101641156A) discloses: in order to improve the mechanical strength of catalyst, a certain amount of glass fibre and a small amount of ethanol are added in catalyst fines, then adopt extrusion moulding to obtain the catalyst of moulding.Chinese patent (CN1461236) discloses " in catalyst-coated process, used ethanol as binding agent, and selected ball type carrier, such as carborundum, aluminium oxide etc. ".Chinese patent (CN10280790A) discloses " consider the catalyst moisture content of active component and environmental condition of coating in forming process, used equally ethanol as binding agent, and selected ball type carrier ".Chinese patent (CN101193704A) discloses " after active component and binding agent are mixed into suspension, spraying on carrier ".What the disclosed catalyst of Chinese patent (CN1117039A) was selected is that titanium dioxide is as carrier.The disclosed catalyst of Chinese patent (CN1165055A) is in catalyst precalcining powder, preferably to use adhesive.The disclosed method of above-mentioned patent documentation can be improved the mechanical strength of catalyst to a certain extent, but, to by the rare report of mechanical strength, high activity and high selectivity that is coated to the catalyst forming on carrier and can improves catalyst with heteropoly acid and/or salt as the catalyst fines of active component or shaping assistant.Now, methacrylic acid millions of tons is produced in the whole world per year.Methacrylic acid is as the important source material of producing methyl methacrylate, and its demand improves the raising along with methyl methacrylate output.Therefore,, producing with MAL in the production process of methacrylic acid, all will have an immense impact on to world's chemical industry to any improvement of catalyst.
Summary of the invention
The object of the invention is to address the above problem, be provided for molecular oxygen and MAL gas carried out in gas phase to selective catalytic oxidation reaction to produce the preparation method of catalyst of methacrylic acid, the catalyst of preparation has advantages of good mechanical strength, lower efflorescence degree, high activity and high selectivity.
For achieving the above object, the present invention has taked following technical scheme.
Be used for the preparation method of the catalyst of producing methacrylic acid, the heteropoly acid that contains molybdenum, vanadium and phosphorus and/or salt are coated on carrier as the catalyst fines of active component, again it is calcined, it is characterized in that, in described catalyst fines is coated to the process on carrier, use inorganic binder.
Further, described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture.
Further, described colloidal sol is stable type colloidal sol, comprises sodium-ion type, non-sodium-ion type stable type colloidal sol or its mixture.
Further, in described colloidal sol, the particle diameter of oxide is 5～30nm, at least 5wt.% of the content of oxide.
Further, at least 500nm of the particle diameter of described colloidal sol emulsion particle, density is 1.05～1.3g/cm
3, pH value is 8.0～11.0.
Further, 2～30wt.% that the addition of described colloidal sol is amount of active ingredients.
Further, the general structure of described active component is: Mo
av
bp
ccu
dx
ey
fz
go
h;
In formula:
Mo, V, P, Cu and O represent respectively molybdenum, vanadium, phosphorus, copper and oxygen;
X is at least one of V A family element (except P element);
Y is at least one of III A family element;
Z is at least one of K, Rb, Cs, Sb, Fe, Ce, Zn, Sn and/or Zr;
A, b, c, d, e, f, g, h represent the atomic ratio of each element, wherein: 8≤a≤12,0.1≤b≤4,0.4≤c≤6,0.01≤d≤3,0.1≤e≤3,0.01≤f≤3,0.01≤g≤3;
G is wherein by the chemical valence of other each elements beyond deoxygenation and the ratio that ratio determines.
Further, the preparation method of described active component comprises the following steps:
(1) mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that preparation contains Mo, V and P, be called for short A liquid;
(2) mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z, is called for short B liquid;
(3) B liquid step (2) Suo Shu is slowly added dropwise in the described A liquid of step (1), preparation contains (1) and the aqueous solution of the described each element of step (2) or their aqueous based dispersions in steps, is called for short C liquid;
(4) aqueous solution of one or more compounds that contain ammonia is joined in the described C liquid of step (3), prepare final aqueous based dispersions, be called for short slurry;
(5) slurry step (4) being obtained is dried processing, obtains dry slurry, i.e. described active component.
The present invention is used for the preparation method of the catalyst of producing methacrylic acid, it is characterized in that, comprises the following steps:
(1) prepare active component
1. mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that under mechanical agitation, preparation contains Mo, V and P, be called for short A liquid;
2. mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z, is called for short B liquid;
3. by step 2. described B liquid be slowly added dropwise to step 1. in described A liquid, under mechanical agitation preparation containing in steps 1. with the 2. aqueous solution of described each element or their aqueous based dispersions of step, be called for short C liquid;
4. the aqueous solution of one or more compounds that contain ammonia is joined to step 3. in described C liquid, then at 90～95 ℃, refluxes 1～9 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hrepresent active component;
(2) dry broken
The active component of the paste-like that step (1) is obtained is dried by forced air drying, freeze drying or vacuum drying mode, obtains dry thing; Then, will be dried thing broken, cross 60 order sub-sieves, obtain particle diameter≤300
catalyst activity component powders;
(3) coating molding
Getting the catalyst activity component powders that step (2) obtains adopts inorganic binder to be coated on inert carrier by rotating comminution granulation or centrifugal flow coating method, the amount of described catalyst activity component powders on described inert carrier is 15～65wt.% of inert carrier consumption, the addition of described inorganic binder is 2～30wt.% of amount of active ingredients, forms spheric catalyst particle presoma;
Described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture, is sodium-ion type or non-sodium-ion type stable type colloidal sol or its mixture, and in inorganic binder, the particle diameter of oxide is 5～30nm, and density is 1.05～1.3g/cm
3, pH value is 8.0～11.0, at least 5wt.% of the content of described oxide;
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 300～540 ℃ of temperature lower calcinations 2～16 hours, obtains finished product type coated catalysts.
Further, the present invention is used for the preparation method of the catalyst of producing methacrylic acid, it is characterized in that, comprises the following steps:
(1) prepare active component
1. mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that under mechanical agitation, preparation contains Mo, V and P, be called for short A liquid;
2. mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z under mechanical agitation, is called for short B liquid;
3. by step 2. described B liquid be slowly added dropwise to step 1. in described A liquid, preparation containing in steps 1. with the 2. aqueous solution of described each element or their aqueous based dispersions of step, be called for short C liquid;
4. the aqueous solution of one or more compounds that contain ammonia is joined to step 3. in described C liquid, then at 90～95 ℃, refluxes 1～5 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hrepresent active component;
(2) dry broken
The active component of the paste-like that step (1) is obtained is dried by forced air drying, freeze drying or vacuum drying mode, obtains dry thing; Then, will be dried thing broken, cross 80 order sub-sieves, obtain particle diameter≤200
catalyst activity component powders;
(3) coating molding
Getting the catalyst activity component powders that step (2) obtains adopts inorganic binder to be coated on inert carrier by rotating comminution granulation or centrifugal flow coating method, the amount of described catalyst activity component powders on described inert carrier is 20～55wt.% of inert carrier consumption, the addition of described inorganic binder is 5～25wt.% of amount of active ingredients, forms spheric catalyst particle presoma;
Described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture, is sodium-ion type or non-sodium-ion type stable type colloidal sol or its mixture, and in inorganic binder, the particle diameter of oxide is 8～20nm, and density is 1.05～1.3g/cm
3, pH value is 8.0～11.0, the content at least 15～45wt.% of described oxide;
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 350～500 ℃ of temperature lower calcinations 3～8 hours, obtains finished product type coated catalysts.
Good effect of the present invention is:
(1) adopt that prepared by the method for the present invention catalyst of producing methacrylic acid has that mechanical strength is high, efflorescence degree is low, high activity and high performance advantage.
(2) the described catalyst of producing methacrylic acid can be used for, with molecular oxygen, MAL gas is being carried out to selective catalytic oxidation reaction production methacrylic acid in gas phase.
The specific embodiment
Below continue to explain the specific embodiment of the present invention, it is pointed out that enforcement of the present invention is not limited to following enforcement and application mode.
The present invention is used for the preparation method of the catalyst of producing methacrylic acid, comprises following preparation process and Attention Points:
(1) prepare active component
1. mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that preparation contains Mo, V and P, be called for short A liquid.
2. mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z, is called for short B liquid.
3. the B liquid 2. step being obtained is slowly added dropwise in the A liquid that 1. step obtain, preparation containing in steps 1. with the 2. aqueous solution of described each element or their aqueous based dispersions of step, be called for short C.
In the preparation of described active component, the usage ratio of each component cpd is not particularly limited, as long as can make the atomic ratio of each composition reach ratio and form kiggen type heteropoly acid and/or salt, as long as the consumption of water can make all compounds of amount dissolve completely or dispersed mixing.
4. the aqueous solution of one or more compounds that contain ammonia is joined to step 3. in described C liquid, then at 90～95 ℃, refluxes 1～9 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hrepresent active component; In formula: Mo, V, P, Cu and O represent respectively molybdenum, vanadium, phosphorus, copper and oxygen; X is at least one of V A family element (except P element); Y is at least one of III A family element; Z is at least one of K, Rb, Cs, Sb, Fe, Ce, Zn, Sn and/or Zr; A, b, c, d, e, f, g, h represent the atomic ratio of each element, wherein: 8≤a≤12,0.1≤b≤4,0.4≤c≤6,0.01≤d≤3,0.1≤e≤3,0.01≤f≤3,0.01≤g≤3; G is wherein by the chemical valence of other each elements beyond deoxygenation and the ratio that ratio determines.
(2) dry broken
The active component of the paste-like that step (1) is obtained is by forced air drying, freeze drying or vacuum drying mode, and preferably forced air drying is dried, and obtains dry thing; Then, will be dried thing fragmentation sieves and makes catalyst activity component powders.
To the method for described fragmentation, there is no particular limitation in the present invention, as long as it is broken will to be dried thing, can be to pulverize or grind.The particle diameter of described catalyst activity component powders answers≤300
, be preferably 200
.
(3) coating molding
The catalyst activity component powders that step (2) is obtained adopts inorganic binder to be coated on inert carrier by rotating comminution granulation or centrifugal flow coating method, described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture, is preferably the colloidal sol of Si and Ti oxide; Described colloidal sol is stable type colloidal sol, comprises sodium-ion type, non-sodium-ion type stable type colloidal sol or its mixture, preferred non-sodium-ion type stable type colloidal sol; The particle diameter of the oxide in inorganic binder is 5～30nm, preferably 8～20nm, and its density is 1.05～1.3g/cm
3, pH value is 8.0～11.0; At least 5wt.% of the content of described oxide, is preferably 15～45wt.%; In colloidal sol, answer≤200nm of the particle diameter of emulsion particle, is preferably 500nm.
Described catalyst activity component powders is coated in the process on inert carrier, the addition of inorganic binder is 2～30wt.% of amount of active ingredients, be preferably 5～25wt.%(inorganic binder consumption very few, catalyst activity component powders is difficult to load on carrier, and on carrier, the minimizing of catalyst activity component powders load capacity can affect the activity of catalyst; Inorganic binder consumption is too much, and catalyst activity component powders is easily attached to the wall of coating unit, causes the waste of catalyst activity component powders, can improve production cost).
The present invention is not particularly limited the kind of described inert carrier, can adopt aluminium oxide, silica, silica and aluminium oxide, titanium oxide, magnesia, steatite, silicon nitride any one or multiple, preferably silica, silica and aluminium oxide.The present invention is not particularly limited the shape of described inert carrier, can be the effigurate any inert carrier of tool, is preferably spherical and inert carrier ring-type.
The painting method of described catalyst activity component powders on described inert carrier can use existing rotation comminution granulation or centrifugal flow coating method.The amount of described catalyst activity component powders on described inert carrier is 15～65wt.% of inert carrier consumption, preferably 20～55wt.%.
In order to reduce the loss of reaction gas pressure, reduce the pressure drop of reaction unit, the average diameter for the catalyst of producing methacrylic acid of preparation method's manufacture of the present invention is 2～15mm, is preferably 4～9mm.
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 300～540 ℃, preferably calcines 2～16 hours for 350～500 ℃, preferably 3～8 hours, obtains finished product type coated catalysts.
The assay method of the mechanical strength to the catalyst of producing methacrylic acid of preparing by method of the present invention:
The stainless steel reaction pipe vertical direction of long 5000mm, internal diameter 25mm is arranged, clog the lower end of described reaction tube with the stainless steel receiver sheet of thick 1mm.The catalyst of 50g is filled in reaction tube from the upper end of described reaction tube, taken away the stainless steel receiver sheet that is arranged on described reaction tube lower end, from reaction tube, slowly take out catalyst.By the catalyst taking out, by the sieve screening of 4mm, by the intensity of following computing formula evaluate catalysts, numerical value is higher means that catalyst strength is higher.
Catalyst efflorescence degree (wt.%)=[(remaining in the quality of the catalyst on screen cloth)/(quality of the catalyst falling from the upper end of reaction tube)] × 100.
Assay method to the catalyst efflorescence degree of producing methacrylic acid of preparing by method of the present invention:
Take 100g catalyst, add in the cylinder drum type stainless steel closed container of diameter 254mm, height 152mm, on the wall of described container one side, have the baffle plate that 51mm is high.Make described container centered by the central shaft of its horizontal direction, under 60 ± 5rpm/min, rotate 30 minutes, from described container, take out afterwards described catalyst, the catalyst taking out is sieved by the sieve of 4mm, by the intensity of following computing formula evaluate catalysts.Numerical value is higher means that catalyst strength is higher.
Catalyst efflorescence degree (wt.%)=[(catalyst quality adding in container)-(remaining in the quality of the catalyst on screen cloth)/(catalyst quality adding in container)] × 100.
Below provide 5 embodiment and 4 comparative examples so that the present invention will be described in more detail.
In following examples and comparative example:
Part represents mass parts;
The mechanical strength of catalyst, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate, MAL yield are respectively as shown in the formula the percentage definition to calculate based on molar basis shown in (2), (3), (4), (5), (6);
In addition, reactant carries out qualitative, quantitative by gas chromatography.
Catalyst mechanical strength (wt.%)=[(remaining in the quality of the catalyst on screen cloth)/(quality of the catalyst falling from the upper end of reaction tube)] × 100 (2)
Catalyst efflorescence degree (wt.%)=[(catalyst quality adding in container)-(remaining in the quality of the catalyst on screen cloth)/(catalyst quality adding in container)] × 100 (3).
MAL conversion ratio (%)=[(molal quantity of the MAL having reacted)/(molal quantity of the MAL of supply)] × 100 (4).
Methacrylic acid selection rate (%)=[(molal quantity of the methacrylic acid of production)/(molal quantity of the MAL having reacted)] × 100 (5).
Methacrylic acid yield (%)=[(molal quantity of the methacrylic acid of production)/(molal quantity of the MAL of supply)] × 100 (6).
embodiment 1
The preparation method who is used for the catalyst of producing methacrylic acid, comprises following preparation process:
(1) prepare active component
1. 3000g molybdenum trioxide, 113.7g vanadium pentoxide, 283.2g phosphorous acid (85wt.%) are dispersed or dissolved in the deionized water of 20L, then under mechanical agitation 90～95 ℃ add hot reflux 9 hours, obtain the A liquid of rufous.
2. 66.2g cupric oxide, 246.4g arsenic acid, 15.2g antimony trioxide, 73.2g cesium nitrate, 50.1g boric acid are dispersed or dissolved in the deionized water of 500mL, obtain mixed solution, be called for short B liquid.
3. the B liquid 2. step being obtained joins in the A liquid that 1. step obtain, and then at 90～95 ℃, refluxes 5 hours, obtains yellowish green C liquid.
4. in the B liquid 2. obtaining in step, drip gradually the ammoniacal liquor 1000g of 25wt.%, then at 90～95 ℃, reflux 1 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hthe active component representing.
(2) dry broken
The active component of the paste-like that step (1) is obtained at 105 ℃ while stirring evaporation drying to leather hard, transfer to constant temperature convection oven at 110 ℃ dry 16 hours, obtain dry thing; Then, described dry thing is placed in to high speed disintegrator and pulverizes 1 minute, cross 60 order sub-sieves, obtain particle diameter≤300
catalyst activity component powders.
(3) coating molding
Get the catalyst activity component powders 200g that step (2) obtains, adopt rolling comminution granulation in the coating pan of rotation, to splash into that the non-sodium-ion type stable type of 10g Si oxide sol---Ludox (wherein, in Ludox, the particle diameter of silica is 8nm, and content is 45wt.%; In Ludox, the particle diameter of emulsion particle is 500nm; Density is 1.28g/cm
3, pH value is 8.0), progressive spraying, to the spherical porous alumina support of 1000g, forms spheric catalyst particle presoma; In coating procedure, observe the loss of a small amount of powder.
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 300 ℃ of temperature lower calcinations 16 hours, obtains finished product type coated catalysts, and described catalyst contains formula M o
12v
0.55p
1.2cu
0.4as
0.5b
0.4cs
0.2sb
0.06the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by embodiment 1 is referring to table 1.
comparative example 1(being the comparison with embodiment 1)
The preparation method who is used for the catalyst of producing methacrylic acid, preparation process is with embodiment 1.
Comparative example 1 is with the difference of embodiment 1, and in step (3) coating molding process, get the Ludox of 20g, wherein, in Ludox, the particle diameter of silica is 15nm, and content is 30wt.%; The particle diameter of emulsion particle is 800nm; Density is 1.19g/cm
3, pH value is 9.0; Obtain finished product type coated catalysts and contain formula M o
12v
0.55p
1.2cu
0.4as
0.5b
0.4cs
0.2sb
0.06the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by comparative example 1 is referring to table 1.
comparative example 2(being the comparison with embodiment 1)
The preparation method who is used for the catalyst of producing methacrylic acid, preparation process is with embodiment 1.
Comparative example 2 is with the difference of embodiment 1, in step (3) coating molding process, and the deionized water that the binding agent of employing is 10g.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by comparative example 2 is referring to table 1.
embodiment 2
The preparation method who is used for the catalyst of producing methacrylic acid, comprises following preparation process:
(1) prepare active component
1. by 2450g ammonium paramolybdate, 304.9g ammonium metavanadate, 151.2g(85wt.%) phosphorous acid be dispersed or dissolved in the deionized water of 20L, under mechanical agitation, 90～95 ℃ add hot reflux 6 hours, obtain the A liquid of rufous.
2. the ferric nitrate of the thallium nitrate of the cesium nitrate of 338.5g copper nitrate, 200.1g arsenic acid, 13.2g cerium oxide, 353.9g, 19.4g, 159.3g is dispersed or dissolved in the deionized water of 2000mL and obtains mixed solution, be called for short B liquid.
3. the mixed solution 2. step being obtained, joins in the red tan solution that 1. step obtain, and then at 90～95 ℃, refluxes 9 hours, obtains active component russet, i.e. C liquid.
(2) dry broken
The active component russet that step (1) is obtained at 105 ℃ while stirring evaporation drying to leather hard, transfer to constant temperature convection oven at 110 ℃ dry 12 hours, obtain dry thing; Then, described dry thing is placed in to high speed disintegrator and pulverizes 1 minute, cross 80 order sub-sieves, obtain particle diameter≤200
catalyst activity component powders.
(3) coating molding
Get the catalyst activity component powders 500g that step (2) obtains, (wherein, in titanium colloidal sol, the particle diameter of titanium oxide is 5nm, and content is 5wt.% to adopt rolling comminution granulation in the coating pan of rotation, to splash into ammonia stable type Ti oxide sol-titanium colloidal sol of 100g; In titanium colloidal sol, the particle diameter of emulsion particle is 800nm; Density is 1.05g/cm
3, pH value is 11.0), progressive spraying, to the spherical porous sial ball of 1000g carrier, forms spheric catalyst particle presoma.In coating procedure, almost do not observe the loss of powder.
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 540 ℃ of temperature lower calcinations 2 hours, obtains finished product type coated catalysts, and described catalyst contains formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by embodiment 2 is referring to table 1.
comparative example 3(being the comparison with embodiment 2)
The preparation method who is used for the catalyst of producing methacrylic acid, preparation process is with embodiment 2.
Comparative example 3 is with the difference of embodiment 2, and in step (3) coating molding process, (wherein, in titanium colloidal sol, the particle diameter of titanium oxide is 30nm, and content is 35wt.% to adopt ammonia stable type Ti oxide sol-titanium colloidal sol of 100g; The particle diameter of emulsion particle is 500nm; Density is 1.35g/cm
3, pH value is 11.0), progressive spraying, to the spherical porous sial ball of 1000g carrier, forms spheric catalyst particle presoma; In coating procedure, almost do not observe the loss of powder.Obtain finished product type coated catalysts and contain formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by comparative example 3 is referring to table 1.
embodiment 3
The preparation method who is used for the catalyst of producing methacrylic acid, comprises following preparation process:
(1) prepare active component (with embodiment 1).
(2) dry broken (with embodiment 1).
(3) coating molding
Get the catalyst activity component powders 800g that step (2) obtains, (wherein, in Ludox, the particle diameter of silica is 20nm, and content is 15wt.% to adopt rolling comminution granulation in the coating pan of rotation, to splash into ammonia stable type Si oxide sol-Ludox of 160g; In Ludox, the particle diameter of emulsion particle is 1000nm; Density is 1.10g/cm
3, pH value is 9.0), progressive spraying, to the spherical porous alumina support of 2000g, forms spheric catalyst particle presoma.In coating procedure, almost do not observe the loss of powder.
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 400 ℃ of temperature lower calcinations 8 hours, obtains finished product type coated catalysts, described catalyst
containthere is formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by embodiment 3 is referring to table 1.
embodiment 4
The preparation method who is used for the catalyst of producing methacrylic acid, comprises following preparation process:
(1) prepare active component (with embodiment 1).
(2) dry broken (with embodiment 1).
(3) coating molding
Get the catalyst activity component powders 300g that step (2) obtains, (wherein, in titanium colloidal sol, the particle diameter of titanium oxide is 20nm, and content is 40wt.% to adopt rolling comminution granulation in the coating pan of rotation, to splash into ammonia stable type Ti oxide sol-titanium colloidal sol of 60g; In titanium colloidal sol, the particle diameter of emulsion particle is 750nm; Density is 1.30g/cm
3, pH value is 8.0), progressive spraying, to the spherical porous sial ball of 1000g carrier, forms spheric catalyst particle presoma.In coating procedure, almost do not observe the loss of powder.
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 440 ℃ of temperature lower calcinations 6 hours, obtains finished product type coated catalysts, and described catalyst contains formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by embodiment 4 is referring to table 1.
embodiment 5
The preparation method who is used for the catalyst of producing methacrylic acid, comprises following preparation process:
(1) prepare active component (with embodiment 1).
(2) dry broken (with embodiment 1).
(3) coating molding
Get the catalyst activity component powders 300g that step (2) obtains, (wherein, in titanium colloidal sol, the particle diameter of titanium oxide is 20nm, and content is 40wt.% to adopt rolling comminution granulation in the coating pan of rotation, to splash into ammonia stable type Ti oxide sol-titanium colloidal sol of 30g; In titanium colloidal sol, the particle diameter of emulsion particle is 750nm; Density is 1.30g/cm
3, pH value is 8.0) and molten (wherein, in Ludox, the particle diameter of silica is 10nm, and content is 35wt.% with 30g ammonia stable type Si oxide sol-silicon; The particle diameter of emulsion particle is 800nm; Density is 1.19g/cm
3, pH value is 9.0) mix, progressive spraying, to the spherical porous silica support of 1200g, forms spheric catalyst particle presoma.In coating procedure, almost do not observe the loss of powder.
(4) calcining and activating (with embodiment 4)
Obtain finished product type coated catalysts, described catalyst contains formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by embodiment 5 is referring to table 1.
comparative example 4(being the comparison with embodiment 2)
The preparation method who is used for the catalyst of producing methacrylic acid, preparation process is with embodiment 2.
Comparative example 4 is with the difference of embodiment 2:
In step (3) coating molding process, the ethanol that the binding agent of employing is 100g.
In step (4) calcining and activating process, the spheric catalyst particle presoma that step (3) obtains roasting 8 hours in 370 ℃ of air streams, obtains finished product type coated catalysts, and described catalyst contains formula M o
8v
1.5p
0.9cu
0.8as
0.8tl
0.044cs
1.0fe
0.2ce
0.04the active component composition representing.
The test result of mechanical strength, efflorescence degree, MAL conversion ratio, methacrylic acid selection rate and the methacrylic acid yield of catalyst prepared by comparative example 4 is referring to table 1.
Table 1. embodiment 1～5 and relatively every test result of the catalyst of 1～4 preparation
Above test result shows:
Adopt the heteropoly acid of producing methacrylic acid prepared by method of the present invention and/or salt coated catalysts mechanical strength is high, efflorescence degree is lower, can be used for utilizing MAL to manufacture the production process of methacrylic acid by calandria type fixed bed reactor, and selection rate and the yield of the conversion ratio of MAL, methacrylic acid be all higher.
Claims (10)
1. for producing the preparation method of catalyst of methacrylic acid, the heteropoly acid that contains molybdenum, vanadium and phosphorus and/or salt are coated on carrier as the catalyst fines of active component, again it is calcined, it is characterized in that, in described catalyst fines is coated to the process on carrier, use inorganic binder.
2. according to claim 1ly it is characterized in that for producing the preparation method of catalyst of methacrylic acid, described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture.
3. according to claim 2ly it is characterized in that for producing the preparation method of catalyst of methacrylic acid, described colloidal sol is stable type colloidal sol, comprises sodium-ion type, non-sodium-ion type stable type colloidal sol or its mixture.
According to described in claim 2 or 3 for producing the preparation method of catalyst of methacrylic acid, it is characterized in that, in described colloidal sol, the particle diameter of oxide is 5～30nm, at least 5wt.% of the content of oxide.
According to described in claim 2 or 3 for producing the preparation method of catalyst of methacrylic acid, it is characterized in that, at least 500nm of the particle diameter of described colloidal sol emulsion particle, density is 1.05～1.3g/cm
3, pH value is 8.0～11.0.
According to described in claim 2 or 3 for producing the preparation method of catalyst of methacrylic acid, it is characterized in that 2～30wt.% that the addition of described colloidal sol is amount of active ingredients.
7. according to claim 1ly it is characterized in that for producing the preparation method of catalyst of methacrylic acid, the general structure of described active component is: Mo
av
bp
ccu
dx
ey
fz
go
h;
In formula:
Mo, V, P, Cu and O represent respectively molybdenum, vanadium, phosphorus, copper and oxygen;
X is at least one of V A family element (except P element);
Y is at least one of III A family element;
Z is at least one of K, Rb, Cs, Sb, Fe, Ce, Zn, Sn and/or Zr;
A, b, c, d, e, f, g, h represent the atomic ratio of each element, wherein: 8≤a≤12,0.1≤b≤4,0.4≤c≤6,0.01≤d≤3,0.1≤e≤3,0.01≤f≤3,0.01≤g≤3;
G is wherein by the chemical valence of other each elements beyond deoxygenation and the ratio that ratio determines.
8. according to claim 7ly it is characterized in that for producing the preparation method of catalyst of methacrylic acid, the preparation method of described active component comprises the following steps:
(1) mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that preparation contains Mo, V and P, be called for short A liquid;
(2) mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z, is called for short B liquid;
(3) B liquid step (2) Suo Shu is slowly added dropwise in the described A liquid of step (1), preparation contains (1) and the aqueous solution of the described each element of step (2) or their aqueous based dispersions in steps, is called for short C liquid;
(4) aqueous solution of one or more compounds that contain ammonia is joined in the described C liquid of step (3), prepare final aqueous based dispersions, be called for short slurry;
(5) slurry step (4) being obtained is dried processing, obtains dry slurry, i.e. described active component.
9. for producing the preparation method of catalyst of methacrylic acid, it is characterized in that, comprise the following steps:
(1) prepare active component
1. mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that under mechanical agitation, preparation contains Mo, V and P, be called for short A liquid;
2. mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z, is called for short B liquid;
3. by step 2. described B liquid be slowly added dropwise to step 1. in described A liquid, under mechanical agitation preparation containing in steps 1. with the 2. aqueous solution of described each element or their aqueous based dispersions of step, be called for short C liquid;
4. the aqueous solution of one or more compounds that contain ammonia is joined to step 3. in described C liquid, then at 90～95 ℃, refluxes 1～9 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hrepresent active component;
(2) dry broken
The active component of the paste-like that step (1) is obtained is dried by forced air drying, freeze drying or vacuum drying mode, obtains dry thing; Then, will be dried thing broken, cross 60 order sub-sieves, obtain particle diameter≤300
catalyst activity component powders;
(3) coating molding
Getting the catalyst activity component powders that step (2) obtains adopts inorganic binder to be coated on inert carrier by rotating comminution granulation or centrifugal flow coating method, the amount of described catalyst activity component powders on described inert carrier is 15～65wt.% of inert carrier consumption, the addition of described inorganic binder is 2～30wt.% of amount of active ingredients, forms spheric catalyst particle presoma;
Described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture, is sodium-ion type or non-sodium-ion type stable type colloidal sol or its mixture, and in inorganic binder, the particle diameter of oxide is 5～30nm, and density is 1.05～1.3g/cm
3, pH value is 8.0～11.0, at least 5wt.% of the content of described oxide;
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 300～540 ℃ of temperature lower calcinations 2～16 hours, obtains finished product type coated catalysts.
10. for producing the preparation method of catalyst of methacrylic acid, it is characterized in that, comprise the following steps:
(1) prepare active component
1. mix with water containing at least one compound of Mo, V, P, the heteropoly acid of kiggen structure and/or the aqueous solution of salt that under mechanical agitation, preparation contains Mo, V and P, be called for short A liquid;
2. mix with water containing at least one compound of Cu, X, Y, Z, the aqueous solution that preparation contains Cu, X, Y and Z under mechanical agitation, is called for short B liquid;
3. by step 2. described B liquid be slowly added dropwise to step 1. in described A liquid, preparation containing in steps 1. with the 2. aqueous solution of described each element or their aqueous based dispersions of step, be called for short C liquid;
4. the aqueous solution of one or more compounds that contain ammonia is joined to step 3. in described C liquid, then at 90～95 ℃, refluxes 1～5 hour, obtain paste-like, by formula M o
av
bp
ccu
dx
ey
fz
go
hrepresent active component;
(2) dry broken
The active component of the paste-like that step (1) is obtained is dried by forced air drying, freeze drying or vacuum drying mode, obtains dry thing; Then, will be dried thing broken, cross 80 order sub-sieves, obtain particle diameter≤200
catalyst activity component powders;
(3) coating molding
Getting the catalyst activity component powders that step (2) obtains adopts inorganic binder to be coated on inert carrier by rotating comminution granulation or centrifugal flow coating method, the amount of described catalyst activity component powders on described inert carrier is 20～55wt.% of inert carrier consumption, the addition of described inorganic binder is 5～25wt.% of amount of active ingredients, forms spheric catalyst particle presoma;
Described inorganic binder is the colloidal sol of the oxide of Al, Si, Ti or its mixture, is sodium-ion type or non-sodium-ion type stable type colloidal sol or its mixture, and in inorganic binder, the particle diameter of oxide is 8～20nm, and density is 1.05～1.3g/cm
3, pH value is 8.0～11.0, the content at least 15～45wt.% of described oxide;
(4) calcining and activating
The spheric catalyst particle presoma that step (3) is obtained is placed in 350～500 ℃ of temperature lower calcinations 3～8 hours, obtains finished product type coated catalysts.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104801351A (en) * | 2015-04-01 | 2015-07-29 | 万华化学集团股份有限公司 | Preparation method of coating catalyst and coating catalyst prepared by using method |
| CN108325533A (en) * | 2018-02-01 | 2018-07-27 | 上海东化环境工程有限公司 | Modified support, O composite metallic oxide catalyst and method for producing acrylic acid |
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| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
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| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104801351A (en) * | 2015-04-01 | 2015-07-29 | 万华化学集团股份有限公司 | Preparation method of coating catalyst and coating catalyst prepared by using method |
| CN108325533A (en) * | 2018-02-01 | 2018-07-27 | 上海东化环境工程有限公司 | Modified support, O composite metallic oxide catalyst and method for producing acrylic acid |
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