CN103721756A - Catalyst carrier, preparation method thereof, and composite oxide catalyst - Google Patents
Catalyst carrier, preparation method thereof, and composite oxide catalyst Download PDFInfo
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- CN103721756A CN103721756A CN201210388877.3A CN201210388877A CN103721756A CN 103721756 A CN103721756 A CN 103721756A CN 201210388877 A CN201210388877 A CN 201210388877A CN 103721756 A CN103721756 A CN 103721756A
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Abstract
The invention relates to a catalyst carrier. The catalyst carrier comprises 5-100wt% of aluminum dihydrogen phosphate and 0-95wt% of a compound selected from silicon carbide, graphite, silicon powder and alumina, and a mixture formed by using two or more of silicon carbide, graphite, silicon powder and alumina. A preparation method of the catalyst carrier comprises the following steps: 1, providing a catalyst carrier composition; and 2, roasting the catalyst carrier composition in an oxygen-containing gas at 120-1000DEG C for 1-24h. The invention also provides the preparation method of the catalyst carrier, and a composite oxide catalyst.
Description
Technical field
The present invention relates to a kind of catalyst carrier, it has the effect that improves catalyst mechanical strength and anti-wear performance.The invention still further relates to the composite oxide catalysts that comprises this catalyst carrier, this catalyst is especially applicable to propylene (or isobutene) oxidation and prepares methacrylaldehyde (or MAL) or be further oxidized to acrylic acid (or methacrylic acid).The invention still further relates to the preparation method of described catalyst carrier.
Background technology
Since the eighties in 20th century, acrylic acid production device in the world mainly adopts propylene two-step oxidizing process, and this method technology is ripe, and economy is good, is still so far the main flow technique of acrylic acid industry.
The acrylic acid catalyst of propylene two-step oxidation system has experienced the process improving constantly with performance of updating.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, also has higher requirement to catalyst strength and life-span.Therefore, need to provide a kind of catalyst when thering is the good capacity of heat transmission with superior strength, for the catalyst performance of catalytic performance and prolong of stability under high propylene air speed, must be even more important.
To methacrylaldehyde, gaseous oxidation generates acrylic acid catalyst and conducts extensive research prior art.But these researchs mainly concentrate on the aspects such as raising of catalyst activity, selective and stability.
For example, EP 427508, EP 235760, JP 200055, WO27437, JP 210991, WO 99/08788, CN1050779C, CN1697692A, CN1112968C etc. have reported the method that improves catalyst activity and stability by changing the composition of catalyst.CN1853786 has reported that methacrylaldehyde gas-phase oxidation catalyst is with-5.6≤H
0≤ 1.5 solid acid has original performance during as carrier.JP 847641 and JP 847643 have described in composite oxide catalysts acid strength H
0≤-11.93 solid super-strong acid during as carrier, can improve activity and the stability of catalyst.CN100345631C has introduced and a kind ofly by changing catalyst, has consisted of to distribute mutually obtain the acrylic acid catalyst that high, the selective height of activity and life-span grow body to surperficial catalyst.CN 1321110A has introduced the catalyst by producing as antimony source with antimony acetate, has larger mechanical strength, high activity and good repeatability.
Yet catalyst mechanical strength and anti-wear performance that said method is produced are not fine, can not make the higher acrylic acid yield of maintenance of propylene long-term stability under high-speed.
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 improved mechanical strength and anti-wear performance.
Summary of the invention
A goal of the invention of the present invention is to provide a kind of catalyst that forms acrylic acid (or isobutylene oxidation formation methacrylic acid) for propylene oxidation, and this catalyst has improved mechanical strength and anti-wear performance.
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 that form with arbitrary proportion in them; Described catalyst support compositions makes with the following method:
(i) provide 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 that form 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 ℃.
Another aspect of the present invention relates to the manufacture method of catalyst carrier of the present invention, and it comprises the steps:
(i) provide 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 that form 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 ℃.
Of the present inventionly relate in one aspect to again 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 the determined numerical value of oxidation state by component;
Z is said catalyst carrier of the present invention.
The specific embodiment
For finding a kind of catalyst for propylene oxidation formation acrylic acid (or isobutylene oxidation formation methacrylic acid) that improves mechanical strength and anti-wear performance that has, the present inventor has conducted intensive studies, final discovery has high temperature resistant through the aluminium dihydrogen phosphate of specially treated, easily moulding, intensity is high, the characteristics such as anti-strip, by aluminium dihydrogen phosphate in oxygen-containing gas under the condition of 120 ~ 1000 ℃ roasting after 1 ~ 24 hour as the part of catalyst carrier or carrier, can significantly improve mechanical strength and the anti-wear performance of catalyst, strengthened the stability of catalyst, extended 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 to catalyst carrier, need to be by its at high temperature heat treatment a period of time.Suitable heat treatment temperature is any two the arbitrary temp scopes that form as end points in 120 ℃, 1000 ℃, 300 ℃, 950 ℃, 400 ℃, 900 ℃, 500 ℃ and 850 ℃, at a better example fat of the present invention, suitable heat treatment temperature is 120-1000 ℃, 300-950 ℃ preferably, 400-900 ℃ more preferably, preferably 500-850 ℃.
Suitable heat treatment time is at least 1 hour, for example any two the random time sections that form as end points in 1 hour, 24 hours, 2 hours, 22 hours, 3 hours, 20 hours, 5 hours, 15 hours.For example suitable heat treatment time is 1 hour-24 hours, better 2 hours-22 hours, and more preferably 3 hours-20 hours, preferably 5 hours-15 hours.
Described heat treatment is carried out under oxygen-containing atmosphere, and suitable oxygen-containing atmosphere comprises the gas mixture of oxygen, air, oxygen-inert gas etc.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 %, preferably 15-50 volume %.
Applicable inert gas can be any conventional inert gas known in the art, and its non-limiting example has, such as nitrogen, argon gas, helium etc., or two or more the mixture in above-mentioned inert gas.
Catalyst carrier of the present invention can be substantially pure aluminium dihydrogen phosphate, and, except inevitable impurity, the amount of aluminium dihydrogen phosphate accounts for 100 % by weight; But the mixture that can be also aluminium dihydrogen phosphate form with the material that is commonly used for catalyst carrier, if the content of aluminium dihydrogen phosphate account for 5-99.99 % by weight (aluminium dihydrogen phosphate and described in be commonly used for the material of catalyst carrier summation be 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, the mixture that aluminium oxide and two or more mixtures that form with arbitrary proportion in them form, 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 that form as end points in 80 % by weight, surplus is carborundum, graphite, silica flour, aluminium oxide or two or more mixtures that form 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 diameter 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 as catalyst carrier, use 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 conventional pressure known in the art.Such as being 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 to 12-24 hour at the temperature of 800-1000 ℃, form required catalyst support powder.
In another example of the present invention, aluminium dihydrogen phosphate and optional carborundum, graphite, silica flour and/or aluminium oxide are processed to 12-24 hour at the temperature of 800-1000 ℃, obtain catalyst support powder, be molded into subsequently required shape (, compressing tablet spherical such as being molded into is that hollow cylindrical particle, compressing tablet are solid cylindrical particle, are molded into trilobal cross etc.), 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 to 12-24 hour at the temperature of 800-1000 ℃, form required catalyst carrier, in the catalyst carrier obtaining, add shaping assistant and strength improving agent, by conventional method, be shaped to the required catalyst shape of catalytic reaction subsequently,, compressing tablet spherical such as being molded into is that hollow cylindrical particle, compressing tablet are solid cylindrical particle, are molded into trilobal cross etc.
In an example of the present invention, by the catalyst carrier that is shaped to required form, in oxygen-containing gas, under the condition of 350～410 ℃, roasting is 1～24 hour, forms preformed catalyst carrier standby.Suitable oxygen-containing atmosphere comprises the gas mixture of oxygen, air, oxygen-inert gas etc.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 %, preferably 15-50 volume %; Described inert gas can be any inert gas known in the art, comprises for example mixture of nitrogen, argon gas, helium or its two or more formation.
The addition of described shaping assistant is the 0.01%-25% of catalyst carrier weight, 0.05-20% preferably, and 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, 0.05-12% preferably, and more preferably 0.1-10%, is preferably 0.5-8%.
Applicable shaping assistant is without particular limitation, can be any conventional shaping assistant known in the art.Its non-limiting example has, for example one or more among water, Ludox, glycerine, cellulose.
Applicable strength improving agent is without particular limitation, can be any conventional strength improving agent known in the art.Its non-limiting example has, for example one or more among ceramic fibre, inorganic crystal whisker.
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 (for example two or more); Nb preferably, La, in Cs a kind of, two or more;
Y is at least one in Mg, Ca, Sr, Ba;
A is any two any number scopes that form for end points in 1,10,1.5,9.5,2,9,2.5,8.5,3,8,3.5,7.5, and for example, a is 1 ~ 10, be preferably 1.5-9.5, preferably 2-9, more preferably 2.5-8.5, be preferably 3-8, preferably 3.5-7.5;
B is any two any number scopes that form 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 0.5-5.5,1-5 preferably, and more preferably 1.5-4.5, is preferably 2-4, preferably 2.5-3.5.
C is any two any number scopes that form 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 0.5-6.5,1-6 preferably, and more preferably 1.5-5.5, is preferably 2-5, preferably 2.5-4.5.
D is any two any number scopes that form 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, preferably 1.5-2.5.
E is any two number ranges that form 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 0.5-4.5,1-4 preferably, and more preferably 1.5-3.5, is preferably 2-3, preferably 2.2-2.8.
F is the determined numerical value of oxidation state by 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 that form with arbitrary proportion in them; Described catalyst support compositions makes with the following method:
(i) provide 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 that form 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 ℃.
Catalyst of the present invention can adopt common method known in the art to make.In a better example of the present invention, the preparation method of catalyst of the present invention comprises Mo source, V source and the W source A solution that obtains soluble in water under 70～100 ℃ of conditions, by Cu source, X source and the Y source B solution that obtains soluble in water under 60～80 ℃ of conditions, pour B solution into A solution under 40～80 ℃ of conditions in, obtain C solution, in solution, directly add Z component to be uniformly mixed and obtain D solution, by the dry catalyst powder that obtains of D solution.
In another better example of the present invention, the preparation method of catalyst of the present invention comprises Mo source, V source and the W source A solution that obtains soluble in water under 70～100 ℃ of conditions, by Cu source, X source and the Y source B solution that obtains soluble in water under 60～80 ℃ of conditions, pour B solution into A solution under 40～80 ℃ of conditions in, obtain C solution, C solution is dried and obtains powder, then this powder is mixed to obtain to catalyst powder with Z component.
In a better example of the present invention, described being dried is under 90～200 ℃ of conditions, to carry out static state be dried or under 280～350 ℃ of inlet temperatures, 130～160 ℃ of conditions of outlet temperature, spray dry.
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 oxalic acid vanadyl; W source adopts wolframic acid, ammonium paratungstate or ammonium metatungstate; Cu source adopts copper nitrate, Schweinfurt green or cupric oxalate; X and Y source adopt 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 that form with arbitrary proportion in them; Described z component makes with the following method:
(i) provide 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 that form 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 ℃.
The catalyst powder making can be shaped to required shape above.In an example of the present invention, in the catalyst powder making upward, add shaping assistant and strength improving agent, by conventional method, be shaped to the required catalyst shape of catalytic reaction subsequently.
In an example of the present invention, by the catalyst that is shaped to required form, in oxygen-containing gas, under the condition of 350～410 ℃, roasting is 1～24 hour.Suitable oxygen-containing atmosphere comprises the gas mixture of oxygen, air, oxygen-inert gas etc.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 %, preferably 2.0-21 volume %.Described inert gas can be any conventional inert gas known in the art, for example, be nitrogen, argon gas, helium or its two or more mixture of forming with arbitrary proportion.
The addition of described shaping assistant is the 0.01%-25% of catalyst powder weight, 0.05-20% preferably, and 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, 0.05-12% preferably, and more preferably 0.1-10%, is preferably 0.5-8%.
Applicable shaping assistant is without particular limitation, can be any conventional shaping assistant known in the art.Its non-limiting example has, for example one or more among water, Ludox, glycerine, cellulose.
Applicable strength improving agent is without particular limitation, can be any conventional strength improving agent known in the art.Its non-limiting example has, for example one or more among ceramic fibre, inorganic crystal whisker.
The shape of applicable preformed catalyst 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 reaction
It is popular response known in the art that acrolein oxidation is prepared 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%, and steam 1～30%, inert gas 15～80%, reaction temperature is 200～300 ℃, 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 aluminium dihydrogen phosphate as a part for carrier or the carrier of catalyst in catalyst preparation process, (it reaches 60-95N/cm by the compression strength that the method described in embodiment records to have significantly improved the mechanical strength of catalyst and anti-wear performance, scuff resistance reaches 99-99.9%), thereby strengthened the stability of catalyst, extended the service life of catalyst.
The present invention is further described by the following embodiment, but protection domain is not subject to 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, greatly connection intelligent testing machine factory), slide measure.
Assay method: with the height of vernier caliper measurement particle to be measured and be recorded as a (cm); 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); With following formula, calculate to obtain catalyst radial crushing strength A (N/cm) subsequently:
A=b/a
When particle to be measured is when approaching spherical particle.By diameter slightly general goal be considered as longitudinally, its vertical direction being considered as laterally.When particle to be measured is spherical particle, vertical and horizontal are its diametric(al).
2. the mensuration of catalyst scuff resistance:
Determining instrument: tablet friabilator (CJY-300D type, Shanghai Huanghai Sea medicine inspection Instrument Ltd.)
Assay method: taking and being sized to particle diameter is 3 object particle 200g to be measured, is packed into friability instrument (CJY-300D type, Shanghai Huanghai Sea medicine inspection Instrument Ltd.) cylinder; It is 45 circles that the friability instrument drum rotating number of turns is set; Start friability instrument, autostop after drum rotating 45 circles, cuts out friability instrument; Take out particle in cylinder, with 2.80mm screen cloth sieve, remove powder and fragment, residue sheet grain takes weight; Gained weight, divided by 200, is got 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 catalyst of 40% inertia bead dilution for the filling of reactor inlet place, and loading height is 1000mm; The catalyst of 10% inertia bead dilution for the filling of lower end, loading height is 2000mm; Oxidation reaction condition is: methacrylaldehyde 7%, and oxygen 9%, steam 15%, unreacted propylene and other organic compound 1.3%, all the other are nitrogen, air speed 1500h
-1; Before reaction, be used in the mixture that 300 ℃ is 1:1 by air and steam volume ratio catalyst system processed 48 hours, then cool the temperature to reaction temperature and react, with following formula, calculate to obtain acrolein conversion rate and acrylic acid yield:
The methacrylaldehyde molal quantity of acrolein conversion rate (mol%)=100 * (supply with methacrylaldehyde molal quantity-reaction after remaining methacrylaldehyde molal quantity)/supply with
The methacrylaldehyde molal quantity of acrylic acid yield (mol%)=100 * (reaction generate acrylic acid molal quantity)/supply with
embodiment 1
catalyst preparation:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
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 for 5 hours by its roasting in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 ℃.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 60N/cm, catalyst scuff resistance are 99.0%; Under 256 ℃ of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.5%.
embodiment 2
catalyst preparation:
By aluminium dihydrogen phosphate under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 287g ammonium metatungstate and 395g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 474g copper nitrate and 28g strontium nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, in C solution, directly add the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 1000g, be uniformly mixed and obtain D solution.D solution is obtained to dry powder for dry 10 hours at 150 ℃.
In the dry powder making on 1880g, add 120g glycerine and 195g Ludox (20%) to 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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 62N/cm, catalyst scuff resistance are 99.2%; Under 256 ℃ of reaction temperatures, acrolein conversion rate is 99.6%, and acrylic acid yield is 97.5%.
embodiment 3
the preparation of catalyst:
Aluminium dihydrogen phosphate is under the atmosphere of 21% oxygen (surplus is nitrogen), standby after 24 hours in 600 ℃ of processing.
In the 6000g water of 90 ℃, add 1302g ammonium molybdate, 284g ammonium metatungstate and 381g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 800g water of 60 ℃, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 20 hours at 120 ℃.At dry powder described in 1000g and above-mentioned 38g graphite and the 190g Ludox (30%) of adding in the aluminium dihydrogen phosphate of high-temperature process of 900g, mix, 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 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 65N/cm, catalyst scuff resistance are 99.4%; Under 260 ℃ 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), standby after 8 hours in 1000 ℃ of processing.
In the 6000g water of 90 ℃, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 800g water of 60 ℃, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 20 hours at 120 ℃.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 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 65N/cm, catalyst scuff resistance are 99.4%; Under 259 ℃ 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), standby after 8 hours in 1000 ℃ of processing.
In the 6000g water of 90 ℃, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 800g water of 60 ℃, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 20 hours at 120 ℃.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 that diameter is 5mm spherical particle, this particle in the atmosphere of 5% oxygen (surplus is nitrogen) at 380 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 88N/cm, catalyst scuff resistance are 99.8%; Under 259 ℃ of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.4%.
embodiment 6
the preparation of catalyst:
Aluminium dihydrogen phosphate, under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 ℃ of processing 12 hours, is shaped to the spherical of particle diameter 5mm subsequently, standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution is coated on above-mentioned spherical aluminium dihydrogen phosphate, at 150 ℃, is dried 10 hours, and in the atmosphere of 5% oxygen (surplus is nitrogen), at 380 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 92N/cm, catalyst scuff resistance are 99.7%; Under 260 ℃ of reaction temperatures, acrolein conversion rate is 99.5%, and acrylic acid yield is 97.3%.
embodiment 7
the preparation of catalyst:
The mixture that the weight ratio of preparing silica flour and aluminium dihydrogen phosphate is 1:1.By aluminium dihydrogen phosphate/silica flour mixture under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 60N/cm, catalyst scuff resistance are 99.6%; Under 260 ℃ of reaction temperatures, acrolein conversion rate is 99.3%, and acrylic acid yield is 98.1%.
embodiment 8
the preparation of catalyst:
The mixture that the weight ratio of preparing graphite and aluminium dihydrogen phosphate is 1:2.By aluminium dihydrogen phosphate/graphite powder mixture under the atmosphere of 21% oxygen (surplus is nitrogen), in 800 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate, 18g magnesium nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 60.5N/cm, catalyst scuff resistance are 99.4%; Under 260 ℃ 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 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
At dry powder described in 1000g and the above-mentioned 195g Ludox (20%) that adds in the carborundum of high-temperature process of 880g, mix, 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 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 18N/cm, catalyst scuff resistance are 95.5%; Under 256 ℃ 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 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 287g ammonium metatungstate and 395g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 474g copper nitrate and 28g strontium nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, in C solution, directly add the above-mentioned aluminium dihydrogen phosphate through high-temperature process of 1000g, be uniformly mixed and obtain D solution.D solution is obtained to dry powder for dry 10 hours at 150 ℃.In 1880g dry powder, add 120g glycerine and 195g Ludox (20%) to 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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 10N/cm, catalyst scuff resistance are 93.2%; Under 256 ℃ 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 that is 0.106mm by particle diameter is under the atmosphere of 21% oxygen (surplus is nitrogen), standby after 24 hours in 600 ℃ of processing.
In the 6000g water of 90 ℃, add 1302g ammonium molybdate, 284g ammonium metatungstate and 381g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 800g water of 60 ℃, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 20 hours at 120 ℃.At 1000g dry powder and above-mentioned 38g graphite and the 190g Ludox (30%) of adding in the aluminium dihydrogen phosphate of high-temperature process of 900g, mix, 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 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 40N/cm, catalyst scuff resistance are 97.4%; Under 260 ℃ 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), standby after 8 hours in 1000 ℃ of processing.
In the 6000g water of 90 ℃, add 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 800g water of 60 ℃, add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 20 hours at 120 ℃.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 ℃ roasting within 5 hours, obtain catalyst.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 30N/cm, catalyst scuff resistance are 97.4%; Under 259 ℃ 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 ℃ process 12 hours standby.
In the 7500g water of 80 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
At dry powder described in 1000g and the above-mentioned 195g Ludox (20%) that adds in the aluminium dihydrogen phosphate of heat treated of 880g, 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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 45N/cm, catalyst scuff resistance are 97.3%; Under 280 ℃ 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 ℃, add 1630g ammonium molybdate, 313g ammonium metatungstate and 475g ammonium metavanadate, stirring and dissolving obtains A solution.
In the 1000g water of 60 ℃, add 21g lanthanum nitrate and 474g copper nitrate, stirring and dissolving obtains B solution.
At 60 ℃, B solution is poured in A solution and obtained C solution, C solution obtains dry powder for dry 10 hours at 150 ℃.
In 1000g dry powder and the commercially available aluminium dihydrogen phosphate of 880g, add 195g Ludox (20%) to 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 ℃, roasting obtains catalyst for 5 hours.
the evaluation of catalyst
With said method, measure catalyst radial crushing strength and catalyst scuff resistance, and evaluation of catalyst activity, the radial crushing strength that result records catalyst is that 43N/cm, catalyst scuff resistance are 97.0%; Under 280 ℃ 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 can greatly improve mechanical strength and the anti-wear performance of catalyst.
Claims (10)
1. a catalyst carrier, 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 that form with arbitrary proportion in them; Described catalyst carrier makes with the following method:
(i) provide 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 that form 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 ℃.
2. catalyst carrier as claimed in claim 1, is characterized in that by described catalyst support compositions the sintering temperature under oxygen-containing gas is 300-950 ℃, more preferably 400-900 ℃, preferably 500-850 ℃; Roasting time is 2 hours-22 hours, more preferably 3 hours-20 hours, and preferably 5 hours-15 hours.
3. catalyst carrier as claimed in claim 1 or 2, the amount that it is characterized in that described aluminium dihydrogen phosphate accounts for 10-95 % by weight, better account for 20-90 % by weight, preferably account for 30-85 % by weight, preferably account for 40-80 % by weight, surplus is to be selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures that form with arbitrary proportion in them.
4. a manufacture method for catalyst carrier, described catalyst carrier 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 that form with arbitrary proportion in them;
Described method comprises the steps:
(i) provide 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 that form 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 ℃.
5. method as claimed in claim 4, is characterized in that by described catalyst support compositions the sintering temperature under oxygen-containing gas is 300-950 ℃, more preferably 400-900 ℃, preferably 500-850 ℃; Roasting time is 2 hours-22 hours, more preferably 3 hours-20 hours, and preferably 5 hours-15 hours.
6. the method as described in claim 4 or 5, the amount that it is characterized in that described aluminium dihydrogen phosphate accounts for 10-95 % by weight, better account for 20-90 % by weight, preferably account for 30-85 % by weight, preferably account for 40-80 % by weight, surplus is to be selected from carborundum, graphite, silica flour, aluminium oxide and two or more mixtures that form with arbitrary proportion in them.
7. a 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 the determined numerical value of oxidation state by component;
Z is the catalyst carrier described in any one in claim 1-3.
8. catalyst as claimed in claim 7, is characterized in that X is Nb, La, in Cs a kind of, two or more;
A is 1.5-9.5,2-9 preferably, and more preferably 2.5-8.5, is preferably 3-8, preferably 3.5-7.5;
B is for being preferably 0.5-5.5,1-5 preferably, and more preferably 1.5-4.5, is preferably 2-4, preferably 2.5-3.5;
C is 0.5-6.5,1-6 preferably, and more preferably 1.5-5.5, is preferably 2-5, preferably 2.5-4.5;
D is 0.5-3.5, more preferably 1-3, preferably 1.5-2.5;
E is 0.5-4.5,1-4 preferably, and more preferably 1.5-3.5, is preferably 2-3, preferably 2.2-2.8.
9. catalyst as claimed in claim 7 or 8, is characterized in that, by the catalyst that is shaped to required form, in oxygen-containing gas, under the condition of 350～410 ℃, roasting is 1～24 hour.
10. catalyst is produced the purposes in (methyl) acrylic acid at (methyl) acrolein oxidation as claimed in any one of claims 7-9.
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| CN107848935A (en) * | 2015-08-24 | 2018-03-27 | 罗门哈斯公司 | The inert determination method of the material used in monomer production |
| CN107848934A (en) * | 2015-08-24 | 2018-03-27 | 罗门哈斯公司 | Determine the inert method of material used in monomer production |
| CN108283925A (en) * | 2018-01-10 | 2018-07-17 | 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107848935A (en) * | 2015-08-24 | 2018-03-27 | 罗门哈斯公司 | The inert determination method of the material used in monomer production |
| CN107848934A (en) * | 2015-08-24 | 2018-03-27 | 罗门哈斯公司 | Determine the inert method of material used in monomer production |
| CN108283925A (en) * | 2018-01-10 | 2018-07-17 | 辽宁石油化工大学 | Catalyst for preparing trichlorosilane through silicon tetrachloride hydrogenation and preparation method thereof |
| 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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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. |