CN103721756B - Catalyst carrier and preparation method thereof, composite oxide catalysts - Google Patents
Catalyst carrier and preparation method thereof, composite oxide catalysts Download PDFInfo
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- CN103721756B CN103721756B CN201210388877.3A CN201210388877A CN103721756B CN 103721756 B CN103721756 B CN 103721756B CN 201210388877 A CN201210388877 A CN 201210388877A CN 103721756 B CN103721756 B CN 103721756B
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Abstract
The present invention relates to a kind of catalyst carrier, comprising: the aluminium dihydrogen phosphate of 5-100 % by weight; 0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them; It obtains with the following method: (i) provides catalyst support compositions; (ii) by described catalyst support compositions in oxygen-containing gas at the roasting temperature 1-24 hour of 120-1000 DEG C.Preparation method and the composite oxide catalysts of this catalyst carrier are also provided.
Description
Technical field
The present invention relates to a kind of catalyst carrier, it has the effect improving catalytic mechanical intensity and anti-wear performance.The invention still further relates to the composite oxide catalysts comprising this catalyst carrier, this catalyst is especially applicable to propylene (or isobutene) oxidation and prepares methacrylaldehyde (or MAL) or be oxidized to acrylic acid (or methacrylic acid) further.The invention still further relates to the preparation method of described catalyst carrier.
Background technology
From the eighties in 20th century, acrylic acid production device in the world mainly adopts propylene two-step oxidizing process, this method mature technology, and economy is good, is still the prevailing technology of acrylic acid industry so far.
The acrylic acid catalyst of propylene two-step oxidation system experienced by the process updated and improve constantly with performance.At present, the propylene air speed of most industry process units is from the 60h at industrialization initial stage
-1be increased to 90h
-1above, some even reaches 120h
-1above.The raising of propylene air speed, it is also proposed higher requirement to catalyst strength and life-span.Therefore, need to provide a kind of there is the good capacity of heat transmission while there is the catalyst of superior strength, must be even more important for the catalyst performance of catalytic performance and prolong of stability under high propylene air speed.
Prior art generates acrylic acid catalyst to methacrylaldehyde gaseous oxidation and conducts extensive research.But these researchs mainly concentrate on the aspect such as raising of catalyst activity, selective and stability.
Such as, EP 427508, EP 235760, JP 200055, WO27437, JP 210991, WO 99/08788, CN1050779C, CN1697692A, CN1112968C etc. report the method being improved catalyst activity and stability by the composition of change catalyst.CN1853786 reports methacrylaldehyde gas-phase oxidation catalyst with-5.6≤H
0the solid acid of≤1.5 is as having original performance during carrier.JP 847641 and JP 847643 describes acid strength H in composite oxide catalysts
0when the solid super-strong acid of≤-11.93 is as carrier, activity and the stability of catalyst can be improved.CN100345631C describe a kind of by change catalyst by body mutually to surface catalyst form distribution obtain activity high, selective height and the life-span length acrylic acid catalyst.CN 1321110A describes the catalyst by using antimony acetate to produce as antimony source, has larger mechanical strength, high activity and good repeatability.
But the catalytic mechanical intensity that said method is produced and anti-wear performance are not very well, the acrylic acid yield that the maintenance that propylene can not be made steady in a long-term under high-speed is higher.
Therefore, prior art still needs to find the catalyst that a kind of propylene oxidation forms acrylic acid (or isobutylene oxidation formation methacrylic acid), and this catalyst has mechanical strength and the anti-wear performance of improvement.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of catalyst forming acrylic acid (or isobutylene oxidation formation methacrylic acid) for propylene oxidation, and this catalyst has mechanical strength and the anti-wear performance of improvement.
Therefore, one aspect of the present invention is to provide a kind of catalyst carrier, and it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them; Described catalyst support compositions obtains with the following method:
I () provides catalyst support compositions, it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them;
(ii) by described catalyst support compositions in oxygen-containing gas at the roasting temperature 1-24 hour of 120-1000 DEG C.
Another aspect of the present invention relates to the manufacture method of catalyst carrier of the present invention, and it comprises the steps:
I () provides catalyst support compositions, it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them;
(ii) by described catalyst support compositions in oxygen-containing gas at the roasting temperature 1-24 hour of 120-1000 DEG C.
Another aspect of the invention relates to a kind of catalyst with following general formula:
Mo
12V
aCu
bW
cX
dY
eO
f/Z
Wherein, X is Nb, Sb, Te, Ce, at least one in La, Nd, Sm, Cs, Ge;
Y is at least one in Mg, Ca, Sr, Ba;
A is 1 ~ 10;
The scope of b is 0 ~ 6;
The scope of c is 0 ~ 7;
The scope of d is 0 ~ 4;
The scope of e is 0 ~ 5;
F is by the determined numerical value of the oxidation state of component;
Z is said catalyst carrier of the present invention.
Detailed description of the invention
For finding a kind of catalyst forming acrylic acid (or isobutylene oxidation formation methacrylic acid) for propylene oxidation with improvement mechanical strength and anti-wear performance, the present inventor has conducted intensive studies, final discovery has high temperature resistant through the aluminium dihydrogen phosphate of specially treated, easily shaping, intensity is high, the characteristics such as anti-strip, by aluminium dihydrogen phosphate in oxygen-containing gas under the condition of 120 ~ 1000 DEG C roasting be used as a part for catalyst carrier or carrier after 1 ~ 24 hour, mechanical strength and the anti-wear performance of catalyst can be significantly improved, enhance the stability of catalyst, extend the service life of catalyst.The present invention completes on the basis of this discovery.Catalyst of the present invention is not only applicable to exhaust gas circulation process, but also is applicable to non-exhaust gas circulation process.
A.
catalyst carrier and preparation method thereof
The present invention relates to a kind of catalyst carrier.Catalyst carrier of the present invention comprises the aluminium dihydrogen phosphate through specially treated.
Aluminium dihydrogen phosphate is a kind of colorless and odorless and sticky liquid or white powder, and it has following structure:
When described aluminium dihydrogen phosphate is used as catalyst carrier, need its at high temperature heat treatment a period of time.Suitable heat treatment temperature is by any two the arbitrary temp scopes formed as end points in 120 DEG C, 1000 DEG C, 300 DEG C, 950 DEG C, 400 DEG C, 900 DEG C, 500 DEG C and 850 DEG C, at a better example fat of the present invention, suitable heat treatment temperature is 120-1000 DEG C, preferably 300-950 DEG C, more preferably 400-900 DEG C, preferred 500-850 DEG C.
Suitable heat treatment time is at least 1 hour, such as, by any two the random time sections formed as end points in 1 hour, 24 hours, 2 hours, 22 hours, 3 hours, 20 hours, 5 hours, 15 hours.Such as suitable heat treatment time is 1 hour-24 hours, better 2 hours-22 hours, more preferably 3 hours-20 hours, preferably 5 hours-15 hours.
Described heat treatment is carried out under an oxygen-containing atmosphere, and suitable oxygen-containing atmosphere comprises the gas mixture etc. of oxygen, air, oxygen-inert gas.In the mist of described oxygen-inert gas, the amount of oxygen accounts for 1-99 volume %, better accounts for 5-80 volume %, better accounts for 10-65 volume %, preferred 15-50 volume %.
The inert gas be suitable for can be any conventional inert gas known in the art, and its not limiting example has, such as nitrogen, argon gas, helium etc., or the mixture of two or more in above-mentioned inert gas.
Catalyst carrier of the present invention can be substantially pure aluminium dihydrogen phosphate, and namely except inevitable impurity, the amount of aluminium dihydrogen phosphate accounts for 100 % by weight; But also can be the mixture that aluminium dihydrogen phosphate is formed with the material being commonly used for catalyst carrier, as long as the content of aluminium dihydrogen phosphate accounts for 5-99.99 % by weight (aluminium dihydrogen phosphate and the described summation being commonly used for the material of catalyst carrier are 100 % by weight).In a better example of the present invention, described catalyst carrier is aluminium dihydrogen phosphate and is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with the mixture that arbitrary proportion is formed in them, wherein, the amount of aluminium dihydrogen phosphate is by 5 % by weight, 99.99 % by weight, 10 % by weight, 95 % by weight, 20 % by weight, 90 % by weight, 30 % by weight, 85 % by weight, 40 % by weight, any two content ranges formed as end points in 80 % by weight, surplus is carborundum, graphite, silica flour, aluminium oxide or two or more mixtures formed with arbitrary proportion in them.
In a better example of the present invention, use the aluminium dihydrogen phosphate of 100 % by weight.In another better example of the present invention, the amount of aluminium dihydrogen phosphate accounts for 5-99.99 % by weight, better accounts for 10-95 % by weight, better accounts for 20-90 % by weight, preferably accounts for 30-85 % by weight, preferably accounts for 40-80 % by weight.
The form of suitable biphosphate aluminum feedstock is without particular limitation, can be liquid or pulverous.When adopting Powdered biphosphate aluminum feedstock, its particle diameter is without particular limitation, can be any conventional particle size known in the art, as long as it does not affect the performance as catalyst carrier.
In addition, the carborundum, graphite, silica flour and/or the aluminium oxide that use as catalyst carrier are without particular limitation, can be any carborundum known in the art, graphite, silica flour and/or aluminium oxide.
Pressure for calcined catalyst carrier is without particular limitation, can be normal pressures known in the art.It can be such as normal pressure etc.
In an example of the present invention, aluminium dihydrogen phosphate and optional carborundum, graphite, silica flour and/or aluminium oxide are processed 12-24 hour, the catalyst support powder needed for formation at the temperature of 800-1000 DEG C.
In another example of the present invention, aluminium dihydrogen phosphate and optional carborundum, graphite, silica flour and/or aluminium oxide are processed 12-24 hour at the temperature of 800-1000 DEG C, obtain catalyst support powder, be molded into required shape (be such as molded into spherical, compressing tablet is hollow cylindrical particles, compressing tablet be solid cylindrical particle, be molded into trilobal cross etc.) subsequently, obtained required catalyst carrier.
In another example of the present invention, aluminium dihydrogen phosphate and optional carborundum, graphite, silica flour and/or aluminium oxide are processed 12-24 hour at the temperature of 800-1000 DEG C, catalyst carrier needed for formation, shaping assistant and strength improving agent is added in the catalyst carrier obtained, be shaped to the catalyst shape needed for catalytic reaction by conventional method subsequently, such as, be molded into that spherical, compressing tablet is hollow cylindrical particles, compressing tablet is solid cylindrical particle, is molded into trilobal cross etc.
In an example of the present invention, will the catalyst carrier of required form be shaped in oxygen-containing gas, roasting 1 ~ 24 hour under the condition of 350 ~ 410 DEG C, form preformed catalyst carrier for subsequent use.Suitable oxygen-containing atmosphere comprises the gas mixture etc. of oxygen, air, oxygen-inert gas.In the mist of described oxygen-inert gas, the amount of oxygen accounts for 1-99 volume %, better accounts for 5-80 volume %, better accounts for 10-65 volume %, preferred 15-50 volume %; Described inert gas can be any inert gas known in the art, comprises such as nitrogen, argon gas, helium or its two or more mixtures formed.
The addition of described shaping assistant is the 0.01%-25% of catalyst carrier weight, preferably 0.05-20%, more preferably 0.1-15 % by weight, is preferably 0.5-10 % by weight.
The addition of described strength improving agent is the 0.01%-15% of catalyst carrier weight, and preferably 0.05-12%, more preferably 0.1-10%, be preferably 0.5-8%.
The shaping assistant be suitable for is without particular limitation, can be any conventional shaping assistant known in the art.Its not limiting example has, such as, among water, Ludox, glycerine, cellulose one or more.
The strength improving agent be suitable for is without particular limitation, can be any conventional intensity improver known in the art.Its not limiting example has, such as, among ceramic fibre, inorganic crystal whisker one or more.
B.
composite oxide catalysts
The present invention also provides the composite oxide catalysts of a kind of carrier band in catalyst carrier of the present invention.Composite oxide catalysts of the present invention has following general formula:
Mo
12V
aCu
bW
cX
dY
eO
f/Z
Wherein:
X is Nb, Sb, Te, Ce, at least one in La, Nd, Sm, Cs, Ge (such as two or more); One preferably in Nb, La, Cs, two or more;
Y is at least one in Mg, Ca, Sr, Ba;
A is that such as, a is 1 ~ 10 by any two any number scopes formed for end points in 1,10,1.5,9.5,2,9,2.5,8.5,3,8,3.5,7.5, be preferably 1.5-9.5, preferably 2-9, more preferably 2.5-8.5, be preferably 3-8, preferred 3.5-7.5;
B is by any two any number scopes formed as end points in 0,6,0.5,5.5,1,5,1.5,4.5,2,4,2.5,3.5.Be preferably, b is 0 ~ 6, is preferably 0.5-5.5, preferably 1-5, more preferably 1.5-4.5, is preferably 2-4, preferred 2.5-3.5.
C is by any two any number scopes formed for end points in 0,7,0.5,6.5,1,6,1.5,5.5,2,5,2.5,4.5.Be preferably, c is 0 ~ 7, is preferably 0.5-6.5, preferably 1-6, more preferably 1.5-5.5, is preferably 2-5, preferred 2.5-4.5.
D is by any two any number scopes formed for end points in 0,4,0.5,3.5,1,3,1.5,2.5.Be preferably, d is 0 ~ 4, preferably 0.5-3.5, more preferably 1-3, preferred 1.5-2.5.
E is by any two number ranges formed for end points in 0,5,0.5,4.5,1,4,1.5,3.5,2,3,2.2,2.8.Be preferably, e is 0 ~ 5, is preferably 0.5-4.5, preferably 1-4, more preferably 1.5-3.5, is preferably 2-3, preferred 2.2-2.8.
F is by the determined numerical value of the oxidation state of component.
Z is catalyst carrier of the present invention.In an example of the present invention, z is a kind of catalyst carrier, and it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them; Described catalyst support compositions obtains with the following method:
I () provides catalyst support compositions, it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them;
(ii) by described catalyst support compositions in oxygen-containing gas at the roasting temperature 1-24 hour of 120-1000 DEG C.
Catalyst of the present invention can adopt common method known in the art to obtain.In a better example of the present invention, the preparation method of catalyst of the present invention comprises Mo source, V source and W source solution A soluble in water under 70 ~ 100 DEG C of conditions, B solution is obtained by soluble in water under 60 ~ 80 DEG C of conditions to Cu source, X source and Y source, under 40 ~ 80 DEG C of conditions, B solution is poured in solution A and obtain C solution, directly add Z component in solution to be uniformly mixed and to obtain solution D, solution D drying is obtained catalyst powder.
In another better example of the present invention, the preparation method of catalyst of the present invention comprises Mo source, V source and W source solution A soluble in water under 70 ~ 100 DEG C of conditions, B solution is obtained by soluble in water under 60 ~ 80 DEG C of conditions to Cu source, X source and Y source, under 40 ~ 80 DEG C of conditions, B solution is poured in solution A and obtain C solution, C solution drying is obtained powder, then this powder is mixed to obtain catalyst powder with Z component.
In a better example of the present invention, described drying under 90 ~ 200 DEG C of conditions, carries out static state drying or carry out spraying dry under inlet temperature 280 ~ 350 DEG C, outlet temperature 130 ~ 160 DEG C of conditions.
In an example of the present invention, Mo source adopts molybdic acid, ammonium paramolybdate or molybdenum oxide; V source adopts ammonium metavanadate, vanadium oxide or vanadyl oxalate; W source adopts wolframic acid, ammonium paratungstate or ammonium metatungstate; Cu source adopts copper nitrate, Schweinfurt green or cupric oxalate; X and Y source adopts corresponding oxide maybe can be decomposed into salt or the hydroxide of oxide.
In an example of the present invention, described z component is catalyst carrier of the present invention.In another example of the present invention, described z component comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them; Described z component obtains with the following method:
I () provides catalyst support compositions, it comprises:
The aluminium dihydrogen phosphate of 5-100 % by weight;
0-95 % by weight is selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures formed with arbitrary proportion in them;
(ii) by described catalyst support compositions in oxygen-containing gas at the roasting temperature 1-24 hour of 120-1000 DEG C.
Obtained catalyst powder can be shaped to required shape above.In an example of the present invention, in catalyst powder obtained upward, add shaping assistant and strength improving agent, be shaped to the catalyst shape needed for catalytic reaction by conventional method subsequently.
In an example of the present invention, will the catalyst of required form be shaped in oxygen-containing gas, roasting 1 ~ 24 hour under the condition of 350 ~ 410 DEG C.Suitable oxygen-containing atmosphere comprises the gas mixture etc. of oxygen, air, oxygen-inert gas.In the mist of described oxygen-inert gas, the amount of oxygen accounts for 0.5-50 volume %, better accounts for 1.0-40 volume %, better accounts for 1.5-30 volume %, preferred 2.0-21 volume %.Described inert gas can be any conventional inert gas known in the art, be such as nitrogen, argon gas, helium or its two or more with arbitrary proportion formed mixture.
The addition of described shaping assistant is the 0.01%-25% of catalyst powder weight, preferably 0.05-20%, more preferably 0.1-15 % by weight, is preferably 0.5-10 % by weight.
The addition of described strength improving agent is the 0.01%-15% of catalyst powder weight, and preferably 0.05-12%, more preferably 0.1-10%, be preferably 0.5-8%.
The shaping assistant be suitable for is without particular limitation, can be any conventional shaping assistant known in the art.Its not limiting example has, such as, among water, Ludox, glycerine, cellulose one or more.
The strength improving agent be suitable for is without particular limitation, can be any conventional intensity improver known in the art.Its not limiting example has, such as, among ceramic fibre, inorganic crystal whisker one or more.
The shape of the preformed catalyst be suitable for is without particular limitation, can be any conventional shape known in the art.In an example of the present invention, described catalyst fines is formed as spherical, solid and/or hollow cylindrical particle.
C.
acrolein oxidation reacts
It is popular response known in the art that acrolein oxidation prepares acrylic acid, and it is the oxidation reaction of carrying out under the existence of catalyst of the present invention in molecular oxygen.In an example of the present invention, feed gas volume consists of methacrylaldehyde 2 ~ 14%, oxygen 0.5 ~ 25%, steam 1 ~ 30%, inert gas 15 ~ 80%, and reaction temperature is 200 ~ 300 DEG C, and reaction pressure is normal pressure ~ 0.02Mpa, and air speed is 900 ~ 8000h
-1.
D.
the advantage of catalyst carrier of the present invention
The present invention adds the carrier of aluminium dihydrogen phosphate as catalyst or a part for carrier in catalyst preparation process, (it reaches 60-95N/cm by the compression strength that the method described in embodiment records to significantly improve the mechanical strength of catalyst and anti-wear performance, scuff resistance reaches 99-99.9%), thus enhance the stability of catalyst, extend the service life of catalyst.
The present invention is further described by the following embodiment, but protection domain is not by the restriction of embodiment.
embodiment
method of testing
1. the mensuration of catalyst radial crushing strength:
Determining instrument: Intelligent testing machine for particle (ZQJ-II type, large connection intelligent testing machine factory), slide measure.
Assay method: be recorded as a (cm) with the height of vernier caliper measurement candidate particles; Adjust the height of resistance to compression head, in the middle of particle is laterally put into, press and release the button, after pending data is stable, record data b (N); Catalyst radial crushing strength A (N/cm) is calculated to obtain subsequently with following formula:
A=b/a
When candidate particles is close to spherical particle.By diameter slightly general goal be considered as longitudinal direction, its vertical direction is considered as transverse direction.When candidate particles is spherical particle, vertical and horizontal are its diametric(al).
2. the mensuration of catalyst scuff resistance:
Determining instrument: tablet friability analyzer (CJY-300D type, Shanghai Huanghai Sea medicine inspection Instrument Ltd.)
Assay method: taking and being sized to particle diameter is 3 object candidate particles 200g, is loaded friability instrument (CJY-300D type, Shanghai Huanghai Sea medicine inspection Instrument Ltd.) cylinder; Arranging the friability instrument drum rotating number of turns is 45 circles; Start friability instrument, drum rotating 45 encloses rear autostop, closes friability instrument; Take out particle in cylinder, remove powder and fragment with 2.80mm screen cloth sieve, residue sheet grain takes weight; Gained weight, divided by 200, gets percentage, is the scuff resistance of catalyst.
3. catalyst activity evaluation:
Oxidation reaction is carried out on the single hose system of internal diameter 27mm, long 3000mm, the reactor inlet place filling catalyst of 40% inertia bead dilution, and loading height is 1000mm; The lower end filling catalyst of 10% inertia bead dilution, loading height is 2000mm; Oxidation reaction condition is: methacrylaldehyde 7%, oxygen 9%, steam 15%, and unreacted propylene and other organic compound 1.3%, all the other are nitrogen, air speed 1500h
-1; Be used in before reaction 300 DEG C by air and steam volume ratio be the mixture of 1:1 by catalyst system process 48 hours, then cool the temperature to reaction temperature and react, calculate to obtain acrolein conversion rate and acrylic acid yield with following formula:
The methacrylaldehyde molal quantity of acrolein conversion rate (mol%)=100 × (the methacrylaldehyde molal quantity-reaction supplied after remaining methacrylaldehyde molal quantity)/supply
The methacrylaldehyde molal quantity of acrylic acid yield (mol%)=100 × (reaction generate acrylic acid molal quantity)/supply
embodiment 1
catalyst preparing:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
1000g dry powder and the above-mentioned 195g Ludox (20%) that adds in the aluminium dihydrogen phosphate of high-temperature process of 880g are mixed, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, obtains catalyst in 5 hours by its roasting in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 60N/cm, catalyst scuff resistance is 99.0%; Under 256 DEG C of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.5%.
embodiment 2
catalyst preparing:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 287g ammonium metatungstate and 395g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 474g copper nitrate and 28g strontium nitrate, stirring and dissolving obtains B solution.
At 60 DEG C, B solution is poured in solution A and obtain C solution, directly add the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 1000g in C solution, be uniformly mixed and obtain solution D.Solution D is obtained dry powder in dry 10 hours at 150 DEG C.
120g glycerine is added and 195g Ludox (20%) mixes in dry powder obtained on 1880g, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 62N/cm, catalyst scuff resistance is 99.2%; Under 256 DEG C of reaction temperatures, acrolein conversion rate is 99.6%, and acrylic acid yield is 97.5%.
embodiment 3
the preparation of catalyst:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), for subsequent use after 24 hours in 600 DEG C of process.
In the 6000g water of 90 DEG C, add 1302g ammonium molybdate, 284g ammonium metatungstate and 381g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 800g water of 60 DEG C, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 20 hours at 120 DEG C.At dry powder described in 1000g with 900g is above-mentioned adds 38g graphite and 190g Ludox (30%) mixes in the aluminium dihydrogen phosphate of high-temperature process, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 65N/cm, catalyst scuff resistance is 99.4%; Under 260 DEG C of reaction temperatures, acrolein conversion rate is 99.7%, and acrylic acid yield is 97.5%.
embodiment 4
the preparation of catalyst:
Make aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), for subsequent use after 8 hours in 1000 DEG C of process.
In the 6000g water of 90 DEG C, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 800g water of 60 DEG C, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 20 hours at 120 DEG C.Dry powder described in 1000g is mixed with the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 900g, 38g graphite and 190g Ludox (30%), compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 65N/cm, catalyst scuff resistance is 99.4%; Under 259 DEG C of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.4%.
embodiment 5
the preparation of catalyst:
Make aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), for subsequent use after 8 hours in 1000 DEG C of process.
In the 6000g water of 90 DEG C, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 800g water of 60 DEG C, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 20 hours at 120 DEG C.Dry powder described in 1000g is mixed with the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 900g, 38g graphite and 190g Ludox (30%), compression molding is diameter is 5mm spherical particle, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 88N/cm, catalyst scuff resistance is 99.8%; Under 259 DEG C of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.4%.
embodiment 6
the preparation of catalyst:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C of process 12 hours, be shaped to the spherical of particle diameter 5mm subsequently, for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution is coated on above-mentioned spherical aluminium dihydrogen phosphate, and drying 10 hours at 150 DEG C, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 92N/cm, catalyst scuff resistance is 99.7%; Under 260 DEG C of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.3%.
embodiment 7
the preparation of catalyst:
The weight ratio preparing silica flour and aluminium dihydrogen phosphate is the mixture of 1:1.By aluminium dihydrogen phosphate/silica flour mixture under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
1000g dry powder and the above-mentioned 195g Ludox (20%) that adds in the aluminium dihydrogen phosphate/silica flour of high-temperature process of 880g are mixed, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 60N/cm, catalyst scuff resistance is 99.6%; Under 260 DEG C of reaction temperatures, acrolein conversion rate is 99.3%, and acrylic acid yield is 98.1%.
embodiment 8
the preparation of catalyst:
The weight ratio preparing graphite and aluminium dihydrogen phosphate is the mixture of 1:2.By aluminium dihydrogen phosphate/graphite powder mixture under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate, 18g magnesium nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
1000g dry powder and the above-mentioned 195g Ludox (20%) that adds in the aluminium dihydrogen phosphate/silica flour of high-temperature process of 880g are mixed, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 60.5N/cm, catalyst scuff resistance is 99.4%; Under 260 DEG C of reaction temperatures, acrolein conversion rate is 99.2%, and acrylic acid yield is 98.3%.
comparative example 1
the preparation of catalyst:
By carborundum under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
Mix at dry powder described in 1000g and the above-mentioned 195g Ludox (20%) that adds in the carborundum of high-temperature process of 880g, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, by its in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 18N/cm, catalyst scuff resistance is 95.5%; Under 256 DEG C of reaction temperatures, acrolein conversion rate is 99.2%, and acrylic acid yield is 97.4%.
comparative example 2
the preparation of catalyst:
By graphite under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 287g ammonium metatungstate and 395g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 474g copper nitrate and 28g strontium nitrate, stirring and dissolving obtains B solution.
At 60 DEG C, B solution is poured in solution A and obtain C solution, directly add the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 1000g in C solution, be uniformly mixed and obtain solution D.Solution D is obtained dry powder in dry 10 hours at 150 DEG C.120g glycerine is added and 195g Ludox (20%) mixes in 1880g dry powder, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 10N/cm, catalyst scuff resistance is 93.2%; Under 256 DEG C of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 96.5%.
comparative example 3
the preparation of catalyst:
The silicon powder by particle diameter being 0.106mm is under the atmosphere of 21% oxygen (surplus is nitrogen), for subsequent use after 24 hours in 600 DEG C of process.
In the 6000g water of 90 DEG C, add 1302g ammonium molybdate, 284g ammonium metatungstate and 381g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 800g water of 60 DEG C, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 20 hours at 120 DEG C.At 1000g dry powder with 900g is above-mentioned adds 38g graphite and 190g Ludox (30%) mixes in the aluminium dihydrogen phosphate of high-temperature process, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 40N/cm, catalyst scuff resistance is 97.4%; Under 260 DEG C of reaction temperatures, acrolein conversion rate is 98.6%, and acrylic acid yield is 97.5%.
comparative example 4
the preparation of catalyst:
Make aluminium oxide under the atmosphere of 21% oxygen (surplus is nitrogen), for subsequent use after 8 hours in 1000 DEG C of process.
In the 6000g water of 90 DEG C, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 800g water of 60 DEG C, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 20 hours at 120 DEG C.1000g dry powder is mixed with the above-mentioned aluminium oxide through high-temperature process of 900g, 38g graphite and 190g Ludox (30%), compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 DEG C roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 30N/cm, catalyst scuff resistance is 97.4%; Under 259 DEG C of reaction temperatures, acrolein conversion rate is 98.3%, and acrylic acid yield is 95.2%.
comparative example 5
the preparation of catalyst:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 50 DEG C process 12 hours for subsequent use.
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
In dry powder described in 1000g and the above-mentioned aluminium dihydrogen phosphate through heating of 880g, add 195g Ludox (20%) mix, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 45N/cm, catalyst scuff resistance is 97.3%; Under 280 DEG C of reaction temperatures, acrolein conversion rate is 99.0%, and acrylic acid yield is 95.0%.
comparative example 6
the preparation of catalyst
In the 7500g water of 80 DEG C, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains solution A.
In the 1000g water of 60 DEG C, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
B solution poured at 60 DEG C in solution A and obtain C solution, C solution obtains dry powder in dry 10 hours at 150 DEG C.
In 1000g dry powder and the commercially available aluminium dihydrogen phosphate of 880g, add 195g Ludox (20%) mix, compression molding is external diameter 5mm, internal diameter 2mm, the hollow cylindrical particle of high 3mm, in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 DEG C, roasting obtains catalyst in 5 hours.
the evaluation of catalyst
Measure catalyst radial crushing strength and catalyst scuff resistance with said method, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is 43N/cm, catalyst scuff resistance is 97.0%; Under 280 DEG C of reaction temperatures, acrolein conversion rate is 99.1%, and acrylic acid yield is 95.1%.
From experimental result above, adopt catalyst carrier of the present invention greatly can improve mechanical strength and the anti-wear performance of catalyst.
Claims (12)
1. a catalyst carrier, is made up of aluminium dihydrogen phosphate; Described catalyst carrier obtains with the following method:
I () provides aluminium dihydrogen phosphate;
(ii) by described aluminium dihydrogen phosphate in oxygen-containing gas at the roasting temperature 1-24 hour of 500-1000 DEG C.
2. catalyst carrier as claimed in claim 1, is characterized in that by the sintering temperature of described aluminium dihydrogen phosphate under oxygen-containing gas be 500-950 DEG C; Roasting time is 2 hours-22 hours.
3. catalyst carrier as claimed in claim 1 or 2, is characterized in that the roasting time of described aluminium dihydrogen phosphate under oxygen-containing gas is 5 hours-15 hours.
4. a manufacture method for catalyst carrier, described catalyst carrier is made up of aluminium dihydrogen phosphate,
Described method comprises the steps:
I () provides aluminium dihydrogen phosphate;
(ii) by described aluminium dihydrogen phosphate in oxygen-containing gas at the roasting temperature 1-24 hour of 500-1000 DEG C.
5. method as claimed in claim 4, to it is characterized in that the sintering temperature of described aluminium dihydrogen phosphate under oxygen-containing gas be 500-950 DEG C of roasting time is 2 hours-22 hours.
6. the method as described in claim 4 or 5, is characterized in that the roasting time of described aluminium dihydrogen phosphate under oxygen-containing gas is 5 hours-15 hours.
7. one kind has the catalyst of following general formula:
Mo
12V
aCu
bW
cX
dY
eO
f/Z
Wherein, X is Nb, Sb, Te, Ce, at least one in La, Nd, Sm, Cs, Ge;
Y is at least one in Mg, Ca, Sr, Ba;
A is 1 ~ 10;
The scope of b is 0 ~ 6;
The scope of c is 0 ~ 7;
The scope of d is 0 ~ 4;
The scope of e is 0 ~ 5;
F is by the determined numerical value of the oxidation state of component;
The catalyst carrier of Z according to any one of claim 1-3.
8. catalyst as claimed in claim 7, it is characterized in that X be one in Nb, La, Cs, two or more;
A is 1.5-9.5, b be 0.5-5.5, c be 0.5-6.5, d be 0.5-3.5, e is 0.5-4.5.
9. catalyst as claimed in claim 7 or 8, is characterized in that, will be shaped to the catalyst of required form in oxygen-containing gas, roasting 1 ~ 24 hour under the condition of 350 ~ 410 DEG C.
10. catalyst as claimed in claim 7, is characterized in that a be 2-9, b be 1-5, c be 1-6, d be 1-3, e is 1-4.
11. catalyst as claimed in claim 7, is characterized in that a be 3.5-7.5, b be 2.5-3.5, c be 2.5-4.5, d be 1.5-2.5, e is 2.2-2.8.
12. catalyst according to any one of claim 7-11 produce the purposes in (methyl) acrylic acid at (methyl) acrolein oxidation.
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| JP6799581B2 (en) * | 2015-08-24 | 2020-12-16 | ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ | How to determine the inertness of a material for use in monomer production |
| CN108283925B (en) * | 2018-01-10 | 2020-07-21 | 辽宁石油化工大学 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
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| CN101376830A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier and preparation thereof |
| CN102039143A (en) * | 2010-11-18 | 2011-05-04 | 中国海洋石油总公司 | Preparation method of catalyst for acrylic acid by oxidizing acraldehyde |
| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
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| CN101376830A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier and preparation thereof |
| CN102039143A (en) * | 2010-11-18 | 2011-05-04 | 中国海洋石油总公司 | Preparation method of catalyst for acrylic acid by oxidizing acraldehyde |
| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
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Effective date of registration: 20170120 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |