CN103861640B - A kind of heteropolyacid catalyst and preparation method thereof - Google Patents
A kind of heteropolyacid catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of heteropolyacid catalyst and preparation method thereof.Described heteropolyacid catalyst contains phosphorus, molybdenum, vanadium, copper, arsenic as necessary active component, and uses the composition of cuprous oxide and cupric phosphate as all or part of copper-contained material of described heteropolyacid catalyst.Compound containing respective element is mixed with water and carries out drying through heating the settled solution obtained, the average grain diameter controlling dried catalyst powder is 0.2 ~ 10 μm, this catalyst powder of last baking inphases, the unimolecule crystallization water number of gained catalyst prod is 1 ~ 5.This catalyst is used for MAL when preparing metering system acid reaction, there is higher MAL conversion ratio and higher Methacrylic acid selectivity.
Description
Technical field
The invention belongs to catalyst field, be specifically related to a kind of heteropolyacid catalyst and preparation method thereof.
Background technology:
Methacrylic acid is a kind of important organic chemistry raw material and polymer monomer, mainly for the manufacture of organic hyaline monomer methyl methacrylate (MMA), is widely used in the fields such as coating, insulating materials, adhesive and ion exchange resin in addition.
Need through two-step reaction with the tert-butyl alcohol/isobutene for source produces methacrylic acid, first on Mo-Bi system poly-metal deoxide, generate MAL, and then generate methacrylic acid through catalytic gas phase oxidation.It is the heteropoly compound of representative that catalyst for second step reaction there will be a known with phosphomolybdic acid, comprises heteropoly acid, heteropolyacid salt.Wherein heteropolyacid catalyst has higher tolerance to the impurity (as acetone) in first step reaction gained MAL raw material, not easily carbon distribution, but due to its at high temperature easier recurring structure cave in, therefore need to react at lower temperatures to keep macrocyclic Stability Analysis of Structures.And easily there is over oxidation Formed oxide in MAL on heteropolyacid catalyst, so keep catalyst to have the difficult point that higher MAL conversion ratio and Methacrylic acid selectivity are its research simultaneously, be also that it has the precondition of industrial application value.
For the problems referred to above that heteropolyacid catalyst exists, some solutions are proposed.As Chinese patent CN102802790A mention by controlling temperature in shaping, calcination process, humidity stably manufactures high activity, dynamical heteropolyacid catalyst, the average grain diameter mentioning catalyst fines in its description is 30 ~ 150 μm, the conversion ratio about 81.5% of MAL, Methacrylic acid selectivity about 82.1%, but improve the preparation cost of catalyst by the method for control temperature/humidity, particularly in the winter that temperature and humidity is all lower.Chinese patent CN1270824C mentions and adopts Schweinfurt green as copper source to improve the conversion ratio of MAL, at air speed 1000h
-1, at reaction temperature 310 DEG C, the conversion ratio about 85.9% of MAL, Methacrylic acid selectivity about 84.8%, the shortcoming of the method is that the catabolite of Schweinfurt green in roasting process exists uncertain and catalyst preparing stability may be made to occur fluctuation.The stability data of all not mentioned catalyst of above patent.
Although existing patented technology all has certain effect in the performance improving heteropolyacid catalyst, in its preparation process or there is many uppity factors, or by controlling the both expensive that preparation condition adopts, the reappearance of catalyst preparing is not good.Therefore, need to develop a kind of heteropolyacid catalyst, this catalyst can improve the conversion ratio of MAL and the selective of methacrylic acid, and has the long reaction life-span, also needs the preparation method developing a kind of described catalyst.
Summary of the invention
An object of the present invention is: provide a kind of heteropolyacid catalyst, and this catalyst activity is high, long service life.
Another object of the present invention is to: the preparation method providing above-mentioned heteropolyacid catalyst, it is simple that this preparation method has technique, the feature of catalyst preparing favorable reproducibility.
Another object of the present invention is the purposes providing above-mentioned heteropolyacid catalyst, and this catalyst is used for MAL catalytic gas phase oxidation and has excellent conversion ratio and selective when preparing methacrylic acid.
For reaching above object, the present invention adopts following technical scheme:
Heteropolyacid catalyst of the present invention has following general formula:
Mo
12P
aV
bCu
cAs
dX
eO
f·nH
2O，
Wherein, Mo is molybdenum, and P is phosphorus, and V is vanadium, and Cu is copper, and As is arsenic, and O is oxygen; X for being selected from least one element in tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium and nickel, at least one element in preferred tellurium, boron, antimony, tungsten, uranium, bismuth and iron; The atomic ratio of various element is:
A=0.5 ~ 3, preferably a=1 ~ 2;
B=0.1 ~ 2, preferably b=0.2 ~ 1;
C=0.01 ~ 1, preferably c=0.05 ~ 1;
D=0.01 ~ 1, preferably d=0.05 ~ 1;
E=0.0 ~ 1, preferably e=0.01 ~ 1;
F is for meeting the atom ratio of oxygen required for each element valence; Described heteropolyacid catalyst uses cuprous oxide and cupric phosphate as all or part of copper-contained material; The powder of described heteropolyacid catalyst has the average grain diameter of 0.2 ~ 10 μm, preferably the average grain diameter of 0.5 ~ 6 μm; The unimolecule crystallization water number of described heteropolyacid catalyst is n=1 ~ 5, is preferably n=2 ~ 4.
The preparation method of heteropolyacid catalyst of the present invention comprises the following steps:
(1) copper-contained material containing cupric phosphate, cuprous oxide and the compound containing Mo, P, V, As and other optional element are placed in water, heating for dissolving obtains settled solution;
(2) solution in drying steps (1), obtains heteropolyacid catalyst powder;
(3) calcination steps (2) gained heteropolyacid catalyst powder, obtains heteropolyacid catalyst.
In the inventive method, step (1) described cupric phosphate and cuprous oxide add in the form of compositions, and cupric phosphate and the copper atom number ratio contained by cuprous oxide are 20/1 ~ 1/2, and preferably 10/1 ~ 1/1.Except other copper-containing compound except cuprous oxide of cupric phosphate also can together with use, as long as the ratio that cupric phosphate and the copper atom number sum contained by cuprous oxide account for copper atom sum in copper-contained material is 1/3 ~ 1, other described copper-containing compound can be selected from cupric oxide, copper nitrate, Schweinfurt green etc.In step (1), the temperature of heating is 80 ~ 100 DEG C, is preferably 90 ~ 100 DEG C, because higher temperature can accelerate the rate of dissolution of added compound, in this temperature range, adopts atmospheric pressure reflux or hydro-thermal method, is not particularly limited.Other described element is selected from least one in tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium and nickel; " optionally " expression is with or without.
In the present invention, in step (1) except cupric phosphate, cuprous oxide and other copper-containing compound aforesaid, the compound of Mo, P, V, As and other element can be selected from the corresponding oxide of these elements, nitrate, acetate, chloride and oxyacid etc., the oxides such as preferred molybdenum trioxide, vanadic anhydride, uranium dioxide, tellurium dioxide, antimony oxide, iron oxide, the Nitrateses such as ferric nitrate, the oxyacid classes etc. such as phosphoric acid, arsenic acid, boric acid, telluric acid, phosphotungstic acid.The compound of respective element can be used alone, also can two or more is used in combination, as long as guarantee to form clear transparent solutions when using.
In the present invention, in step (1), the consumption of water is without particular limitation, as long as the compound added can be made to reach consoluet degree, can select according to the needs of follow-up drying means (as rate of drying, energy consumption and powder granule size etc.).Preferably, be 100 parts in the weight of added molybdenum trioxide, the consumption of water is 300 ~ 1500 weight portions.
About the use of copper-containing compound in the present invention, the present inventor finds, cupric phosphate and cuprous oxide be used in combination in experimentation the phenomenon that there will be solution turned blue, and gained catalyst application is prepared in the reaction of methacrylic acid in metering system is oxidation of aldehydes, the selective of methacrylic acid is improved significantly, and the life-span of catalyst is also extended.Experimentally the use of the known cuprous oxide of phenomenon makes part metals element reduce, and exists with the form compared with low-oxidation-state, and this existence compared with low-oxidation-state is favourable to raising the selective of catalyst; Also find simultaneously, if be used alone cuprous oxide can not both improve the selective of methacrylic acid, the extending catalyst life-span while of again, infer that the amount added mainly through the stable firmly crystallization water of cupric phosphate is maintained to the secondary or tertiary structure that make heteropoly acid, and then make the structure of catalyst more firm, reach the effect improving catalyst stability.For reaching good result of use, the use amount of cuprous oxide and cupric phosphate needs to control in certain proportion, if because the amount ratio of cuprous oxide and cupric phosphate is excessive, can over reduction be there is in other metallic elements then on heteropoly acid outside copper removal, even cause heteropoly acid primary structure to become unstable, reaction conversion ratio is in first increasing the trend reduced afterwards, and namely the activity of catalyst is higher at first, but As time goes on can decline, poor stability; If the ratio of cuprous oxide and cupric phosphate is too small, then other metallic element reducing degrees on heteropoly acid outside copper removal are too weak, and the structure of catalyst is substantially unaffected, but the selective meeting of catalyst is poor.Specifically, copper atom mole ratio contained in cupric phosphate and cuprous oxide is 20/1 ~ 1/2, preferably 10/1 ~ 1/1.
Next, in step of the present invention (2), solution obtains catalyst powder through super-dry.Described drying means is not particularly limited, and can use any drying means known in the art, such as evaporation drying, drum dried, spraying dry etc., but should be noted that baking temperature does not exceed the decomposition temperature of heteropoly acid.
The present inventor is through deep research, find that the size of dried catalyst powder particle directly affects the activity of heteropolyacid catalyst, prepare in the oxidation reaction of methacrylic acid being applied to MAL, the conversion ratio of MAL is down to after below 10 μm in the size of catalyst granules and is significantly improved.N is carried out to catalyst of the present invention
2physical absorption characterizes, find that the specific area of catalyst, pore volume and aperture almost do not change before and after change of size, but consider the false liquid phase behavior of heteropoly acid, still can think that the reduction of particle diameter facilitates the contact of reactant and catalyst, and then improve the conversion ratio of MAL metering system acid reaction.For the size of dried catalyst powder particle, larger difficulty is there is when preparing and being less than the particle of 0.2 μm owing to adopting conventional method, cost is higher, and reduction catalyst powder granular size observes catalyst activity appearance decline on the contrary further, infer that this causes heteropoly acid to dewater completely in roasting process because powder granule is too small and causes caused by false liquid phase behavior disappearance, therefore the size of step of the present invention (2) gained catalyst powder particle is preferably at 0.2 ~ 10 μm, more preferably at 0.5 ~ 6 μm.
For controlling the particle diameter of dry gained catalyst powder at 0.2 ~ 10 μm, the present invention has carried out accurate control to dry run and/or post-processing step.Such as, when adopting pneumatic spray drying method, by controlling the pressure of air-flow and the speed etc. of charging, the powder of above-mentioned particle diameter can be obtained; When adopting centrifugal spray drying method, by the rotating speed of control centrifugal atomizing dish and the speed etc. of charging, also can obtain the powder of above-mentioned particle diameter; When adopting evaporation drying method, the powder obtained drying may be needed through pulverising step to obtain having the powder of above-mentioned particle size range again.As the drying means of step (2), the present invention preferably can obtain the pneumatic spray drying method of above-mentioned particle size range by precise hard_drawn tuhes condition, during spraying dry, spray dryer inlet temperature is 100 ~ 250 DEG C, preferably 120 ~ 200 DEG C; Outlet temperature is 60 ~ 150 DEG C, preferably 70 ~ 110 DEG C; Compressed air is 300 ~ 3000m/s, preferably 500 ~ 2000m/s from the speed that nozzle sprays.
In the present invention, the method of roasting of catalyst powder is not particularly limited, any conventional bake method known in the art can be used, preferred employing baking inphases method: in roasting temperature-rise period, catalyst powder stops 0.5 ~ 5h respectively in 80 ~ 120 DEG C, 130 ~ 170 DEG C, 180 ~ 220 DEG C three temperature ranges, then within the scope of 250 ~ 400 DEG C, preferably 270 ~ 350 DEG C, stop 1 ~ 10h, roasting process can pass into the oxygen-containing gas such as the air of flowing.In conjunction with aforementioned drying methods, this method of roasting gained catalyst is adopted to have good catalytic effect.
By carrying out thermogravimetric analysis to the catalyst after roasting of the present invention, the present inventor finds that crystallization water number suitable on unimolecule heteropolyacid catalyst is 1 ~ 5, all there is the situation of conversion ratio and selective deficiency in the catalyst exceeding this crystallization water number scope, therefore, catalyst powder particle diameter needs within the specific limits, and catalyst has the crystallization water of certain content simultaneously.Unimolecule heteropolyacid catalyst general formula of the present invention is described as: Mo
12p
av
bcu
cas
dx
eo
fnH
2during O, n is crystallization water number, n=1 ~ 5, preferably 2 ~ 4.
Heteropolyacid catalyst of the present invention can be applicable to the gaseous oxidation of catalysis MAL and prepares methacrylic acid.Raw material MAL, oxygen-containing gas and steam are after preheating, pass in the fixed-bed tube reactor that catalyst is housed and carry out reaction and prepare methacrylic acid, described oxygen-containing gas can be air or air and dilute gas mixture or molecular oxygen and dilute gas mixture, molecular oxygen can come from pure oxygen, oxygen enrichment or air, and diluent gas can be N2, CO
2with a kind of in steam or their mixtures in any proportion.
This heteropolyacid catalyst is used for the oxidation of aldehydes reaction condition preparing methacrylic acid of metering system: reaction temperature 250 ~ 400 DEG C, preferably 280 ~ 360 DEG C; Pressure (absolute pressure) 0.01 ~ 0.15MPa, preferred normal pressure; The total air speed 400 ~ 4000h of reaction raw materials gaseous mixture
-1, preferably 800 ~ 2000h
-1; In gaseous mixture, the molar concentration of MAL is 1 ~ 15%, preferably 3 ~ 8%; O
2be 0.5 ~ 6:1, preferably 1 ~ 4:1 with the mol ratio of MAL; Mol ratio 1 ~ the 15:1 of steam and MAL, preferably 2 ~ 10:1.
Adopt gained catalyst of the present invention when preparing metering system acid reaction for MAL, MAL conversion ratio and Methacrylic acid selectivity all can be stabilized in more than 80%, are in the high value in existing patent level.After catalyst stabilization runs 2000h, MAL conversion ratio and Methacrylic acid selectivity kept stable.
Accompanying drawing illustrates:
Fig. 1 is ESEM (SEM) picture of embodiment 1 gained catalyst powder
Fig. 2 is ESEM (SEM) picture of comparative example 1 gained catalyst powder
Fig. 3 is X-ray diffraction (XRD) spectrogram of embodiment 1 and comparative example 1 gained catalyst
Detailed description of the invention
Further describe Catalysts and its preparation method provided by the present invention by the following examples, but the present invention is not therefore subject to any restriction.
The form of catalyst powder and particle size are carried out observation by SEM (Hitachi, model S-4800) and are calculated; X-ray powder diffraction test (XRD) adopts Panalytical X ' the Pert Pro type of Philips company to turn target X-ray powder diffractometer; The crystallization water number of catalyst measures and adopts thermogravimetric analyzer (METTLER TOLEDO, model TGA/DSC1) to carry out analytical calculation.
Metering system is oxidation of aldehydes to be prepared the conversion ratio of methacrylic acid and to be selectively defined as follows:
MAL conversion ratio=(amount of substance of the MAL of the amount of substance/raw material supplying of the MAL of consumption) × 100%
Methacrylic acid selectivity=(amount of substance of the MAL of the amount of substance/consumption of the methacrylic acid of generation) × 100%
Embodiment 1
1) preparation of catalyst
490.50g molybdenum trioxide (MoO is added in 4000g deionized water
3), 23.44g vanadic anhydride (V
2o
5), the phosphoric acid (H of 41.08g85wt% mass concentration
3pO
4), the arsenic acid (H of 24.71g80wt%
3asO
4), 0.88g boric acid (H
3bO
3), at 98 DEG C, add 2.40g cupric phosphate (Cu after stirring and refluxing 1h
3(PO
4)
23H
2o), 0.69g cuprous oxide (Cu
2o), glaucous solution is obtained after continuing return stirring 10h, this solution is carried out spraying dry on air flow type spray drying machine, increasing atomizing gas pressure (absolute pressure, lower same) be 0.35MPa, compressed air is 1500m/s from the speed that nozzle sprays, and the inlet temperature of spray dryer is 140 ~ 150 DEG C, outlet temperature is 70 ~ 80 DEG C, and the average grain diameter obtaining powder is 2.5 μm (as Fig. 1).Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.The secondary of catalyst prod or tertiary structure obtain its spectrogram as shown in Figure 3 through XRD test.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x3H
2o(oxygen content cannot be determined because of the valence state change of each element).
2) oxidation reaction of MAL
Fill in fixed bed device after being mixed with 10 gram of 10 ~ 20 object quartz sand by 20 grams of catalyst granules, raw material constitutive molar ratio is: MAL: oxygen: water: nitrogen=1:1.8:5:17.0, and the total air speed of material mixed gas is 1100h
-1, salt temperature is 300 DEG C, and for carrying out the oxidation reaction of MAL under the reaction condition of 0.13MPa, obtain MAL conversion ratio after successive reaction 50h is 85.6% to pressure (absolute pressure, lower same), and Methacrylic acid selectivity is 85.2%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 85.4%, and Methacrylic acid selectivity is 85.5%.
Comparative example 1
According to embodiment 1 Kaolinite Preparation of Catalyst, difference is to change pneumatic spray drying into centrifugal spray drying, the atomizer rotating speed of spray dryer is 10600 revs/min, inlet temperature is 140 ~ 150 DEG C, outlet temperature is 70 ~ 80 DEG C, the median particle size obtaining catalyst powder is 50.1 μm (see Fig. 2, they have obviously larger particle diameter compared with catalyst shown in Fig. 1).During roasting obstructed enter moving air, catalyst powder is directly warming up to 320 DEG C, stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.The secondary of catalyst prod or tertiary structure obtain its spectrogram as shown in Figure 3 through XRD test.Can find out, the heteropolyacid catalyst of comparative example 1 has and the different secondary of the heteropolyacid catalyst of embodiment 1 or tertiary structure, and this shows that both crystal water content are different.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x11H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 22.5%, and Methacrylic acid selectivity is 78.5%.
Embodiment 2
Except the pneumatic spray drying in embodiment 1 is changed into except centrifugal spray drying, other is all prepared by the method for embodiment 1, the atomizer rotating speed of spray dryer is 38000 revs/min, inlet temperature is 140 ~ 150 DEG C, outlet temperature is 70 ~ 80 DEG C, and the median particle size obtaining catalyst powder is 9.4 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x5H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 80.4%, and Methacrylic acid selectivity is 84.2%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 80.1%, and Methacrylic acid selectivity is 84.4%.
Comparative example 2
Except by the 2.40g cupric phosphate in embodiment 1,0.69g cuprous oxide is replaced with 6.85g copper nitrate (Cu (NO
3)
23H
2o), the phosphoric acid of 41.08g85% mass concentration is replaced with outside the phosphoric acid of 42.47g85% mass concentration, other are all prepared by the method for embodiment 1, and different phenomenon is the solution obtained after stirring and refluxing is bronzing, and the median particle size of catalyst powder is 2.3 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x3H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 81.5%, and Methacrylic acid selectivity is 76.8%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 70.2%, and Methacrylic acid selectivity is 77.1%.
Embodiment 3
Except by the catalyst powder after centrifugal spray drying in comparative example 1 in micronizer (Guangzhou Xu Lang plant equipment Co., Ltd, model XL-20B) under pulverize outside, other is all prepared by the method for embodiment 1, and the median particle size obtaining catalyst powder is 5.8 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x4H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 82.1%, and Methacrylic acid selectivity is 84.5%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 82.8%, and Methacrylic acid selectivity is 84.4%.
Comparative example 3
Except the 2.40g cupric phosphate in embodiment 1 is replaced with 4.52g copper nitrate, the phosphoric acid of 41.08g85% mass concentration is replaced with outside the phosphoric acid of 42.47g85% mass concentration, other is all prepared by the method for embodiment 1, obtain solution colour after stirring and refluxing also in blue-green, the median particle size of catalyst powder is 2.7 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.3v
0.9cu
0.1as
0.50b
0.05o
x4H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 80.7%, and Methacrylic acid selectivity is 86.1%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 71.4%, and Methacrylic acid selectivity is 85.8%.
Embodiment 4
1) preparation of catalyst
490.50g molybdenum trioxide is added in 4000g deionized water, 20.84g vanadic anhydride, 0.66g tungstic acid, the phosphoric acid of 43.57g85% mass concentration, the arsenic acid of 29.65g80wt%, 3.60g cupric phosphate is added after stirring and refluxing 1h at 98 DEG C, 1.04g cuprous oxide and 3.35g cupric oxide, glaucous solution is obtained after continuing return stirring 10h, gained solution is carried out spraying dry on air flow type spray drying machine, increasing atomizing gas pressure is 0.25MPa, compressed air is 1000m/s from the speed that nozzle sprays, the inlet temperature of spray dryer is 140 ~ 150 DEG C, outlet temperature is 70 ~ 80 DEG C, the median particle size obtaining powder is 3.2 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.4v
0.8cu
0.3as
0.60w
0.01o
x2H
2o(oxygen content cannot be determined because of the valence state change of each element).
2) oxidation reaction of MAL
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 85.7%, and Methacrylic acid selectivity is 84.5%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 84.6%, and Methacrylic acid selectivity is 84.9%.
Comparative example 4
According to embodiment 4 Kaolinite Preparation of Catalyst, the median particle size obtaining powder is 3.2 μm, not 100 DEG C, 150 DEG C and 200 DEG C of stops when difference is catalyst roasting, and directly stop 5h at 320 DEG C, roasting process obstructed enter moving air, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.4v
0.8cu
0.3as
0.60w
0.01o
x7H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 64.3%, and Methacrylic acid selectivity is 83.2%.
Embodiment 5
1) preparation of catalyst
490.50g molybdenum trioxide is added, 18.24g vanadic anhydride, 9.05g tellurium dioxide (TeO in 4000g deionized water
2), 5.36g uranium dioxide (UO
2), the phosphoric acid of 43.57g85% mass concentration, the arsenic acid (H of 24.71g80wt%
3asO
4), 3.60g cupric phosphate is added after stirring and refluxing 1h at 98 DEG C, 2.03g cuprous oxide and 13.57g copper nitrate, obtain dark blue solution after continuing return stirring 10h, gained solution is carried out spraying dry on air flow type spray drying machine, and increasing atomizing gas pressure is 0.24MPa, compressed air is 1200m/s from the speed that nozzle sprays, the inlet temperature of spray dryer is 140 ~ 150 DEG C, and outlet temperature is 70 ~ 80 DEG C, and the median particle size obtaining powder is 2.9 μm.Catalyst powder is placed in roasting under moving air atmosphere, specifically stops 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, and 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.4v
0.7cu
0.4as
0.50u
0.07te
0.2o
x3H
2o(oxygen content cannot be determined because of the valence state change of each element).
2) oxidation reaction of MAL
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 83.7%, and Methacrylic acid selectivity is 85.4%.Under this condition after successive reaction 2000h, obtaining MAL conversion ratio is 84.0%, and Methacrylic acid selectivity is 85.6%.
Comparative example 5
According to embodiment 5 Kaolinite Preparation of Catalyst, difference is gained solution to be placed in 90 DEG C of dry 12h of baking oven, obtain greenish yellow solid, grind to form the following fine powder of 200 order, the median particle size obtaining powder is 33.6 μm, be placed on roasting under moving air atmosphere, specifically stop 2h in 100 DEG C, 150 DEG C stop 1h, and 200 DEG C stop 1h, 320 DEG C stop 5h, obtain the catalyst granules of 10 ~ 20 order sizes after compressing tablet sieves.
By analysis, the composition of catalyst is described as: Mo
12p
1.4v
0.7cu
0.4as
0.50u
0.07te
0.2o
x5H
2o(oxygen content cannot be determined because of the valence state change of each element).
Carry out MAL oxidation reaction according to the method identical with embodiment 1, obtaining MAL conversion ratio after successive reaction 50h is 44.3%, and Methacrylic acid selectivity is 83.2%.
By the explanation of above-described embodiment and comparative example, can find out that the activity/stability of heteropolyacid catalyst catalysis MAL synthesize methyl acrylic acid reaction is remarkable by the impact in catalyst powder granular size, crystallization water number and copper source.Under suitable preparation condition, catalyst has high MAL conversion ratio/Methacrylic acid selectivity and good life-span.
Claims (11)
1. a heteropolyacid catalyst, it has following general formula:
Mo
12P
aV
bCu
cAs
dX
eO
f·nH
2O
Wherein,
Mo is molybdenum, and P is phosphorus, and V is vanadium, and Cu is copper, and As is arsenic, and O is oxygen;
X is for being selected from least one element in tellurium, boron, antimony, germanium, tungsten, uranium, bismuth, iron, cobalt, ruthenium, nickel; The atomic ratio of various element is:
a＝0.5～3；
b＝0.1～2；
c＝0.01～1；
d＝0.01～1；
e＝0～1；
F is for meeting the atom ratio of oxygen required for each element valence;
Prepare in the copper-contained material of described heteropolyacid catalyst and comprise cuprous oxide and cupric phosphate; The powder of described heteropolyacid catalyst has the average grain diameter of 0.2 ~ 10 μm; The unimolecule crystallization water number of described heteropolyacid catalyst is n=1 ~ 5; Preparing cupric phosphate and the copper atom number ratio contained by cuprous oxide in the copper-contained material of this catalyst is 20/1 ~ 1/2.
2. heteropolyacid catalyst according to claim 1, is characterized in that, in described catalyst, the atomic ratio of various element is:
a＝1～2；
b＝0.2～1；
c＝0.05～1；
d＝0.05～1；
e＝0.01～1。
3. heteropolyacid catalyst according to claim 1, is characterized in that, the powder of described heteropolyacid catalyst has the average grain diameter of 0.5 ~ 6 μm.
4. heteropolyacid catalyst according to claim 1, is characterized in that, preparing cupric phosphate and the copper atom number ratio contained by cuprous oxide in the copper-contained material of this catalyst is 10/1 ~ 1/1.
5. heteropolyacid catalyst according to claim 1, is characterized in that, the unimolecule crystallization water number of heteropolyacid catalyst is n=2 ~ 4.
6. heteropolyacid catalyst according to claim 1, is characterized in that, in copper-contained material, the ratio that cupric phosphate and the copper atom number sum contained by cuprous oxide account for copper atom sum in copper-contained material is 1/3 ~ 1.
7. prepare a method for the heteropolyacid catalyst as described in any one of claim 1 ~ 6, it is characterized in that, comprise the following steps:
(1) comprise cupric phosphate, the copper-contained material of cuprous oxide and the compound containing Mo, P, V, As and other optional element of metering are placed in water, heating for dissolving obtains solution;
(2) solution obtained in drying steps (1), obtains heteropolyacid catalyst powder;
(3) calcination steps (2) gained heteropolyacid catalyst powder, obtains heteropolyacid catalyst.
8. the preparation method of heteropolyacid catalyst according to claim 7, is characterized in that, drying means used in step (2) is spray drying process.
9. the preparation method of heteropolyacid catalyst according to claim 8, is characterized in that, drying means used in step (2) is pneumatic spray drying method.
10. the preparation method of heteropolyacid catalyst according to claim 7, it is characterized in that, method of roasting described in step (3) is baking inphases method, catalyst powder stops 1 ~ 10h at 250 ~ 400 DEG C after stopping 0.5 ~ 5h at 80 ~ 120 DEG C, 130 ~ 170 DEG C, 180 ~ 220 DEG C respectively.
Catalyst prepared by 11. methods according to any one of the heteropolyacid catalyst in claim 1 ~ 6 described in any one or 7 ~ 10, is characterized in that, this catalyst is used for the gaseous oxidation of catalysis MAL and prepares methacrylic acid.
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| CN105363491B (en) * | 2015-10-21 | 2018-09-04 | 中国科学院过程工程研究所 | A kind of carried heteropoly acid catalyst for methacrolein oxidation preparing isobutene acid |
| CN105749944A (en) * | 2016-03-23 | 2016-07-13 | 重庆紫光海力催化剂有限公司 | Catalyst for preparing alpha-methacrylic acid from 2-methylacrolein with gas-phase catalytic oxidation method |
| CN106582278B (en) * | 2016-12-29 | 2022-10-11 | 山东大学 | Preparation method of heteropoly acid modified nano-ring composite material for removing NOx |
| CN109331850B (en) * | 2018-10-08 | 2021-07-23 | 万华化学集团股份有限公司 | Core-shell type catalyst carrier and coating catalyst |
| EP4063039A4 (en) * | 2019-11-22 | 2024-02-21 | Kinsei Matec Co Ltd | Casting sand and kit for sand mold |
| CN114471644A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Porous heteropolyacid catalyst and preparation method and application thereof |
| CN115487868B (en) * | 2021-06-18 | 2023-07-04 | 中国石油化工股份有限公司 | Vanadium-containing heteropolyacid modified catalyst, preparation method and application thereof, and butene oxidative dehydrogenation method |
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| US6812188B2 (en) * | 2000-09-21 | 2004-11-02 | Nippon Kayaku Kabushiki Kaisha | Catalyst for methacrylic acid production, coated catalyst, and process for producing the same |
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