CN104475138A - Vanadium-phosphorus-zirconium-titanium composite oxide catalyst for synthesising acrylic acid (ester) as well as preparation method and application of vanadium-phosphorus-zirconium-titanium composite oxide catalyst - Google Patents
Vanadium-phosphorus-zirconium-titanium composite oxide catalyst for synthesising acrylic acid (ester) as well as preparation method and application of vanadium-phosphorus-zirconium-titanium composite oxide catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesising acrylic acid (ester), especially relates to a vanadium-phosphorus-zirconium-titanium composite oxide catalyst for synthesising acrylic acid and ester as well as a preparation method and application of the vanadium-phosphorus-zirconium-titanium composite oxide catalyst, and belongs to the field of catalytic material preparation technologies and application. The catalyst disclosed by the invention takes one or the mixture of more of TiO2, SiO2 and a molecular sieve as a support for supporting active components and active auxiliaries; the active components are composite oxides of V, P, Zr and Ti, and the active auxiliaries are one or more oxides of B, Al, Ce and La and can be used for modifying the support. The catalyst disclosed by the invention is used in the reaction of synthesising acrylic acid (ester) from formaldehyde and acetic acid, and has high activity and selectivity; the per-pass conversion rate of the acetic acid achieves 50%, and the selectivity of the acrylic acid and ester of products is up to 90%; moreover, the catalyst is good in thermostability, and good in water resistance and carbon deposition resistance.
Description
Technical field
The present invention relates to the catalyst for the synthesis of acrylic acid (ester), especially relate to vanadium phosphorus zirconium titanium composite oxides Catalysts and its preparation method and the application of acrylic acid synthesizing (ester), belong to catalysis material technology of preparing and application.
Background technology
Acrylic acid (ester) is important Organic Chemicals.Acrylic acid (ester) is widely used in homopolymerization and copolyreaction, can react with multiple compounds, synthesizes a series of propylene copolymer.Be widely used in the industries such as building, health, plastics, packaging for foodstuff, automobile, electrical equipment and weaving.2014, China's acrylic acid (ester) demand reached 1,500,000 tons, accounts for more than 20% of world's aggregate consumption; It is expected that total demand in 2015 will reach 1,600,000 tons, genuine World Propylene acid (ester) will be become and consume big country.The large-scale acrylic acid of industrialization (ester) production technology nearly all both at home and abroad mainly adopts propylene two-step oxidizing process at present, and China's propylene resource shortage, current acrylic acid (ester) production capacity can not meet domestic demand completely.Therefore with cheap formalin and acetic acid for the technology of raw material one-step synthesis acrylic acid (ester) has broad application prospects.
At present, the catalyst research both at home and abroad for this technical process has many sections of bibliographical informations, and catalyst activity component mainly contains V
2o
5, P
2o
5, Cs, Nb, B etc., the auxiliary agent of interpolation is mainly alkalies and alkaline earth oxide, comprising: the elements such as K, Na, Mg, Ca, Ba, Sr, and the carrier selected comprises: SiO
2, Al
2o
3, TiO
2, molecular sieve, active carbon etc.In acetic acid/formaldehyde aldol reaction acrylic acid synthesizing process, many side reactions also can simultaneously or phase supervention raw, cause the reduction of reaction selectivity.Research shows, selects suitable catalyst can effectively reduce or avoid the generation of part side reaction, improves the selective of this reaction and yield.Thus, the exploitation of to take acetic acid as the core technology of Material synthesis acrylic acid process be catalyst.In fact, the research of the catalyst of such reaction has the history of decades.As far back as the sixties in last century, the people such as Vitcha find at 375 ~ 385 DEG C, under normal pressure, catalyst Dichlorodiphenyl Acetate/formaldehyde acrylic acid synthesizing prepared by the metal ions such as artificial zeolite (decalso) load sodium, potassium, rubidium, calcium, strontium, magnesium or nickel has activity, the wherein catalyst of artificial zeolite (decalso) load sodium, acrylic acid yield can reach 92%, but the space-time yield of this catalyst is too low, there is no that commercialization is worth.Its research also shows that temperature is higher, and raw material or decomposition product reaction increase, but temperature is too low, and formaldehyde conversion declines.MamoruAi finds V
2o
5-P
2o
5double oxide (P/V atomic ratio=1.06 ~ 1.2) catalyst Dichlorodiphenyl Acetate/formaldehyde condensation reaction is produced acrylic acid and is shown fabulous activity.When taking metaformaldehyde as formaldehyde source, when acetic acid/formaldehyde ratio is 2.5, in formaldehyde, acrylic acid yield reaches 98%; And when being formaldehyde source with formalin, acrylic acid yield reaches 75%.Produce acetone and carbon dioxide during the main side reaction of this reaction, and side reaction raises along with temperature and aggravates.This reaction and side reaction affect comparatively large by water, water significantly limit catalyst activity.
Chinese patent CN102151583A discloses a kind of phosphorus vanadium catalyst, and this catalyst is with phosphorus vanadium for active component, and its making step is: vanadic anhydride, isobutanol and phenmethylol are mixed, add hot reflux certain hour, stir simultaneously.Solid orthophosphoric acid and isobutanol Hybrid Heating are stirred, after orthophosphoric acid dissolves, by two parts of solution mixing, adds thermal agitation 4-10h, cooling, vacuum filtration, simultaneously dry, then calcining and activating.This catalyst manufacturing process is very long, complicated, and catalyst activity is not high, makes in the filtrate of catalyst and contains a large amount of isobutanol and phenmethylol, have toxicity, easily to environment.
For the acrylic acid catalyst of above research, all there is product acrylic acid (ester) at present selective low, catalyst poor heat stability, the problem that the life-span is short.And formaldehyde-acetic synthesis acrylic acid (ester) is the aldol reaction between low carbon atom number order, for such reaction, the adjustment of the soda acid power of catalyst on reaction conversion ratio and selective impact very large.And the existence of water is also very large on the impact of this synthetic reaction in reaction, research shows, when taking metaformaldehyde as formaldehyde source, acrylic acid (ester) is selective reaches 90%, and when being formaldehyde source with formalin, acrylic acid selectivity drops to 70%.And the existence of water can suppress main reaction speed, and comparatively large to catalysts influence, under high-temperature water heat condition, the catalyst activity components such as V, P, B, Cs easily run off and cause active reduction.
Summary of the invention
The technical problem to be solved in the present invention is avoid above-mentioned the deficiencies in the prior art part and provide a kind of catalyst being active component with the composite oxides of V, P, Zr, Ti, add B, Al acidic oxide and rare earth element ce, La carries out modification to catalyst carrier, by the carrier of modified catalyst for catalyst provides suitable specific area, increases acid site density, sour type, increases carbon accumulation resisting ability, improves mechanical strength etc.
Another object of the present invention is to provide the preparation method of above-mentioned catalyst.
Another object of the present invention is to provide the application of above-mentioned catalyst.
The object of the invention is realized by following technical proposals:
A vanadium phosphorus zirconium titanium composite oxides catalyst for acrylic acid synthesizing and ester thereof, with TiO
2, SiO
2, one or more mixtures in molecular sieve are carrier, load active component and coagent; Described active component is the composite oxides of V, P, Zr, Ti, and described coagent is one or more oxides of B, Al, Ce, La, carries out modification to carrier.
Preferably, described catalyst composition is counted with catalyst gross mass: 5 ~ 20%V, 10% ~ 25%P, 1 ~ 5%Zr, 5 ~ 30Ti%, described coagent is 0.5% ~ 5%.
Preferred further, described active component V is selected from ammonium metavanadate, and P is selected from phosphoric acid, and Zr is selected from zirconium nitrate, and Ti is selected from titanium dioxide or butyl titanate; Described coagent is selected from the nitrate of Al, Ce, La, and B is selected from boric acid; Described molecular screening is from HZSM-5.
Prepare a method for the vanadium phosphorus zirconium titanium composite oxides catalyst of aforesaid propylene acid and ester thereof, comprise the following steps:
(1) support modification: get one or more of B, Al, Ce, La compound, add deionized water dissolving and prepare certain density solution, then get support powder and add in solution, normal temperature dipping 4 ~ 8h, dry 6h at 80 ~ 120 DEG C, then at 300 ~ 600 DEG C roasting 3 ~ 8h;
(2) vanadium phosphorus zirconium titanium complex sol preparation
A, get absolute ethyl alcohol, deionized water, titanium colloidal sol prepared by a certain percentage by glacial acetic acid, then adds a certain amount of zirconates, obtained titanium zirconium mixed sols, getting a certain amount of phosphoric acid more slowly adds in titanium zirconium colloidal sol, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol;
B, get a certain amount of deionized water, add a small amount of oxalic acid, this mixed solution is heated to 50 ~ 80 DEG C, add solid ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus zirconium titanium complex sol;
(3) get modified support and put into vanadium phosphorus zirconium titanium complex sol, be heated to 50 ~ 90 DEG C, slowly add a small amount of phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 2 ~ 6h at 80 ~ 120 DEG C, catalyst solid after dried puts into Muffle furnace, and pass into air and carry out roasting, temperature programming is roasting 2 ~ 4h at 150 ~ 300 DEG C, be warming up to 550 DEG C of roasting 4 ~ 6h again, obtain catalyst.
A kind of application of catalyst described above, described catalyst application is in formaldehyde and acetic synthesis acrylicacidandesters, this reaction adopts fixed bed reactors, reaction is gas solid catalytic reaction, and reaction temperature is 320 ~ 380 DEG C, passes into inert nitrogen gas as carrier gas in reaction system, and pass into a certain proportion of oxygen, raw material formaldehyde and acetic acid mol ratio are 1:3 ~ 1:6, and raw material formaldehyde source can be selected from formalin solution or metaformaldehyde, add a certain amount of methyl alcohol as solvent in raw material.Methyl alcohol can suppress oxymethylene polymerization as while solvent, and is conducive to methyl acrylate generation.
This catalyst is used for formaldehyde-acetic synthesis acrylic acid (ester) reaction, its key reaction mechanism is: formaldehyde and acetic acid aldol reaction occur under acid catalyst effect and generates principal product acrylic acid, acetic acid and methyl alcohol generation side reaction generate methyl acetate, and methyl acetate generates a small amount of methyl acrylate with formaldehyde again.Key reaction formula is:
HCHO+CH
3COOH→CH
2CHCOOH+H
2O
CH
3COOH+CH
3OH→CH
3COOCH
3+H
2O
CH
3COOCH
3+HCHO→CH
3COOCHCH
2
Compared with prior art, the invention has the beneficial effects as follows:
(1) add B, Al acidic oxide and rare earth element ce, La carries out modification to catalyst carrier, make catalyst have higher specific area, more acid site and suitable sour kind, and catalyst has stronger carbon accumulation resisting ability.
(2) catalyst adopts sol-gel process preparation, makes active component V, P, Zr, Ti define ZrP
2o
7, TiP
2o
7, ZrV
2o
7deng composite oxides, and this type oxide has very high heat endurance, and maintain higher acid activity position, conversion ratio and the acrylic acid (ester) with excellence are selective, acetic acid conversion per pass reaches 50%, and product acrylicacidandesters is selective up to 90%, and water-resistance is good, there is higher heat endurance, catalyst long service life.
Detailed description of the invention
Below in conjunction with detailed description of the invention, foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should comprise within the scope of the invention.Embodiment 1:
(1) support modification: take titanium dioxide as carrier, B, Ce oxide is modified additive.
Take boric acid 2.3g (in boron oxide, accounting for 3% of vehicle weight), six nitric hydrate cerium 4.3g (in cerium oxide, accounting for 4% of vehicle weight) add deionized water 35g obtain solution, then take 40gTiO
2powder, joins in the solution prepared, floods 4h under normal temperature, then dry 5h at 100 DEG C, then puts into Muffle furnace roasting 4h at 500 DEG C, obtained modified support.
(2) vanadium phosphorus zirconium titanium complex sol is prepared
Get butyl titanate 42.5g, be dissolved in 80ml absolute ethyl alcohol, and add a small amount of deionized water and glacial acetic acid, take zirconium nitrate 7.1g again to add, stir obtained titanium zirconium colloidal sol, then the phosphoric acid solution getting 100ml 8mol/L slowly adds in above-mentioned mixed sols, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol; Get a certain amount of deionized water, add a small amount of oxalic acid, and be heated to 50 DEG C, add 34.7g ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus titanium zirconium complex sol.
(3) get roasting modified support and put into vanadium phosphorus titanium zirconium complex sol, be heated to 60 DEG C, slowly add 16.4g phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 6h at 100 DEG C, catalyst solid after dried puts into Muffle furnace, pass into air and carry out roasting, with the heating rate temperature programming of 2 DEG C/min to 200 DEG C of roasting 2h, be warming up to 300 DEG C of roasting 2h again, be warming up to 550 DEG C of roasting 4h again, obtained 150g is with B, the V-P-Zr-Ti composite oxide catalysts of Ce modification, wherein each element accounts for catalyst sum-rate and is: 10%V, 20%P, 1%Zr, 30Ti%, change titanium dioxide, butyl titanate, zirconium nitrate, ammonium metavanadate and phosphoric acid addition can obtain the catalyst of different loads amount.
Embodiment 2:
(1) support modification: take HZSM-5 as carrier, B, Ce, La oxide is modified additive.
Take boric acid 1.9g (in boron oxide, account for 3% of vehicle weight), six nitric hydrate cerium 3.5g (in cerium oxide, accounting for 4% of vehicle weight), lanthanum nitrate 1.9g is (in lanthana, account for 2% of carrier gross weight) add deionized water 30g obtain solution, then take 32gHZSM-5 molecular sieve powder, join in the solution prepared, 4h is flooded under normal temperature, then dry 5h at 100 DEG C, then put into Muffle furnace roasting 4h at 500 DEG C, obtained modified support.
(2) vanadium phosphorus zirconium titanium complex sol is prepared
Get butyl titanate 70.8g, be dissolved in 120ml absolute ethyl alcohol, and add a small amount of deionized water and glacial acetic acid, take zirconium nitrate 28.3g again to add, stir obtained titanium zirconium colloidal sol, then the phosphoric acid solution getting 100ml 8mol/L slowly adds in above-mentioned mixed sols, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol; Get a certain amount of deionized water, add a small amount of oxalic acid, and be heated to 80 DEG C, add 91.7g ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus zirconium titanium complex sol.
(3) get roasting modified support and put into above-mentioned complex sol, be heated to 60 DEG C, slowly add 16.4g phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 6h at 100 DEG C, catalyst solid after dried puts into Muffle furnace, pass into air and carry out roasting, with the heating rate temperature programming of 2 DEG C/min to 200 DEG C of roasting 2h, be warming up to 300 DEG C of roasting 2h again, be warming up to 550 DEG C of roasting 4h again, obtained 200g is with B, Ce, the V-P-Zr-Ti composite oxide catalysts of La modification, wherein each element accounts for catalyst sum-rate and is: 20%V, 15%P, 3%Zr, 5Ti%, change butyl titanate, zirconium nitrate, ammonium metavanadate and phosphoric acid addition can obtain the catalyst of different loads amount.
Embodiment 3:
(1) support modification: with TiO
2, SiO
2for carrier, Al, Ce, La oxide is modified additive.
Take aluminum nitrate 15.4g (in aluminium oxide, account for 6% of vehicle weight), six nitric hydrate cerium 4.4g are (in cerium oxide, account for 5% of vehicle weight), lanthanum nitrate 1.9g is (in lanthana, account for 2% of carrier gross weight) add deionized water 40g obtain solution, then take 20gTiO
2and 10gSiO
2powder, joins in the solution prepared, floods 4h under normal temperature, then dry 5h at 100 DEG C, then puts into Muffle furnace roasting 4h at 500 DEG C, obtained modified support.
(2) vanadium phosphorus zirconium titanium complex sol is prepared
Get butyl titanate 81.6g, be dissolved in 120ml absolute ethyl alcohol, and add a small amount of deionized water and glacial acetic acid, take zirconium nitrate 47.1g again to add, stir obtained titanium zirconium colloidal sol, then the phosphoric acid solution getting 180ml 8mol/L slowly adds in above-mentioned mixed sols, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol; Get a certain amount of deionized water, add a small amount of oxalic acid, and be heated to 50 DEG C, add 22.9g ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus zirconium titanium complex sol.
(3) get roasting modified support and put into above-mentioned complex sol, be heated to 60 DEG C, slowly add 16.9g phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 6h at 100 DEG C, catalyst solid after dried puts into Muffle furnace, pass into air and carry out roasting, with the heating rate temperature programming of 2 DEG C/min to 200 DEG C of roasting 2h, be warming up to 300 DEG C of roasting 2h again, be warming up to 550 DEG C of roasting 4h again, obtained 200g is with Al, Ce, the V-P-Zr-Ti composite oxide catalysts of La modification, wherein each element accounts for catalyst sum-rate and is: 5%V, 25%P, 5%Zr, 15Ti%, change titanium dioxide, butyl titanate, zirconium nitrate, ammonium metavanadate and phosphoric acid addition can obtain the catalyst of different loads amount.
Embodiment 4:
(1) support modification: with TiO
2, HZSM-5 is carrier, B, Ce, La oxide is modified additive.
Take boric acid 2.8g (in boron oxide, account for 3% of vehicle weight), six nitric hydrate cerium 5.2g are (in cerium oxide, account for 3% of vehicle weight), lanthanum nitrate 2.1g is (in lanthana, account for 2% of carrier gross weight) add deionized water 30g obtain solution, take 17gTiO2 again, 25gHZSM-5 molecular sieve powder, join in the solution prepared, under normal temperature, flood 4h, then dry 5h at 100 DEG C, put into Muffle furnace roasting 4h at 500 DEG C again, obtained modified support.
(2) vanadium phosphorus zirconium titanium complex sol is prepared
Get butyl titanate 70.8g, be dissolved in 120ml absolute ethyl alcohol, and add a small amount of deionized water and glacial acetic acid, take zirconium nitrate 28.3g again to add, stir obtained titanium zirconium colloidal sol, then the phosphoric acid solution getting 100ml 8mol/L slowly adds in above-mentioned mixed sols, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol; Get a certain amount of deionized water, add a small amount of oxalic acid, and be heated to 80 DEG C, add 73.4g ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus zirconium titanium complex sol.
(3) get roasting modified support and put into above-mentioned complex sol, be heated to 60 DEG C, slowly add 16.4g phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 6h at 100 DEG C, catalyst solid after dried puts into Muffle furnace, pass into air and carry out roasting, with the heating rate temperature programming of 2 DEG C/min to 200 DEG C of roasting 2h, be warming up to 300 DEG C of roasting 2h again, be warming up to 550 DEG C of roasting 4h again, obtained 200g is with B, Ce, the V-P-Zr-Ti composite oxide catalysts of La modification, wherein each element accounts for catalyst sum-rate and is: 16%V, 15%P, 3%Zr, 10Ti%, change titanium dioxide, butyl titanate, zirconium nitrate, ammonium metavanadate and phosphoric acid addition can obtain the catalyst of different loads amount.
Embodiment 5:
Catalyst prepared by Example 1, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is formalin and the acetic acid of 36%, prepares, react under normal pressure by formaldehyde/acetic acid mol ratio=1:3, at temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Embodiment 6:
Catalyst prepared by Example 1, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is metaformaldehyde and acetic acid, prepares, add quantitative methyl alcohol as solvent in raw material by formaldehyde/acetic acid mol ratio=1:3, at reaction temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Embodiment 7:
Catalyst prepared by Example 2, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is metaformaldehyde and acetic acid, prepares, add a certain amount of methyl alcohol as solvent in raw material by formaldehyde/acetic acid mol ratio=1:3, at reaction temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Embodiment 8:
Catalyst prepared by Example 3, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is metaformaldehyde and acetic acid, prepares, add a certain amount of methyl alcohol as solvent in raw material by formaldehyde/acetic acid mol ratio=1:4, at reaction temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Embodiment 9:
Catalyst prepared by Example 4, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is metaformaldehyde and acetic acid, prepares, add a certain amount of methyl alcohol as solvent in raw material by formaldehyde/acetic acid mol ratio=1:4, at reaction temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Embodiment 10:
Catalyst prepared by Example 4, grinding screening 20-40 object catalyst 20ml, fill on fixed bed reactors, catalyst upper-lower section all loads a certain amount of quartz sand and is fixed, reaction raw materials is metaformaldehyde and acetic acid, prepares, add a certain amount of methyl alcohol as solvent in raw material by formaldehyde/acetic acid mol ratio=1:6, at reaction temperature is respectively 340 DEG C, 360 DEG C, 380 DEG C, acetic acid conversion ratio, acrylic acid (ester) is selective and space-time yield result is as shown in the table:
Claims (5)
1. a vanadium phosphorus zirconium titanium composite oxides catalyst for acrylic acid synthesizing and ester thereof, is characterized in that: with TiO
2, SiO
2, one or more mixtures in molecular sieve are carrier, load active component and coagent; Described active component is the composite oxides of V, P, Zr, Ti, and described coagent is one or more oxides of B, Al, Ce, La, carries out modification to carrier.
2. the vanadium phosphorus zirconium titanium composite oxides catalyst of acrylic acid synthesizing and ester thereof according to claim 1, it is characterized in that: described catalyst composition is counted with catalyst gross mass: 5% ~ 20%V, 10% ~ 25%P, 1% ~ 5%Zr, 5% ~ 30Ti%, described coagent is 0.5% ~ 5%.
3. the vanadium phosphorus zirconium titanium composite oxides catalyst of acrylic acid synthesizing according to claim 1 and ester thereof, it is characterized in that: described active component V is selected from ammonium metavanadate, and P is selected from phosphoric acid, and Zr is selected from zirconium nitrate, Ti is selected from titanium dioxide or butyl titanate; Described coagent is selected from the nitrate of Al, Ce, La, and B is selected from boric acid; Described molecular screening is from HZSM-5.
4. prepare a method for the vanadium phosphorus zirconium titanium composite oxides catalyst of acrylicacidandesters as described in any one of claims 1 to 3, it is characterized in that, comprise the following steps:
(1) support modification: get one or more of B, Al, Ce, La compound, add deionized water dissolving and prepare certain density solution, then get support powder and add in solution, normal temperature dipping 4 h ~ 8h, dry 6h at 80 DEG C ~ 120 DEG C, then at 300 DEG C ~ 600 DEG C roasting 3 h ~ 8h;
(2) vanadium phosphorus zirconium titanium complex sol preparation
A, get absolute ethyl alcohol, deionized water, titanium colloidal sol prepared by a certain percentage by glacial acetic acid, then adds a certain amount of zirconates, obtained titanium zirconium mixed sols, getting a certain amount of phosphoric acid more slowly adds in titanium zirconium colloidal sol, stirred at ambient temperature 1-3h, obtained titanium phosphate, basic zirconium phosphate complex sol;
B, get a certain amount of deionized water, add a small amount of oxalic acid, this mixed solution is heated to 50 ~ 80 DEG C, add solid ammonium metavanadate, be stirred to and dissolve completely, the vanadium solution prepared is added in above-mentioned complex sol, stir 1 ~ 3h, obtained vanadium phosphorus zirconium titanium complex sol;
(3) get modified support and put into vanadium phosphorus zirconium titanium complex sol, be heated to 50 DEG C ~ 90 DEG C, slowly add a small amount of phosphoric acid while stirring, then the gel of formation is put into vacuum drying chamber dry 2 ~ 6h at 80 DEG C ~ 120 DEG C, catalyst solid after dried puts into Muffle furnace, passes into air and carries out roasting, and temperature programming is roasting 2 h ~ 4h at 150 DEG C ~ 300 DEG C, be warming up to 550 DEG C of roasting 4 h ~ 6h again, obtain catalyst.
5. the application of a catalyst as claimed any one in claims 1 to 3, it is characterized in that: described catalyst application is in formaldehyde and acetic synthesis acrylicacidandesters, this reaction adopts fixed bed reactors, reaction is gas solid catalytic reaction, reaction temperature is 320 DEG C ~ 380 DEG C, inert nitrogen gas is passed into as carrier gas in reaction system, and pass into a certain proportion of oxygen, raw material formaldehyde and acetic acid mol ratio are 1:3 ~ 1:6, raw material formaldehyde source can be selected from formalin solution or metaformaldehyde, adds a certain amount of methyl alcohol as solvent in raw material.
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