CN114471529B - Catalyst for synthesizing acrylic acid and preparation method thereof - Google Patents
Catalyst for synthesizing acrylic acid and preparation method thereof Download PDFInfo
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- CN114471529B CN114471529B CN202011164243.0A CN202011164243A CN114471529B CN 114471529 B CN114471529 B CN 114471529B CN 202011164243 A CN202011164243 A CN 202011164243A CN 114471529 B CN114471529 B CN 114471529B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000012798 spherical particle Substances 0.000 claims abstract description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 41
- 239000002243 precursor Substances 0.000 claims description 35
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 150000002751 molybdenum Chemical class 0.000 claims description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000007858 starting material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 4
- 238000002791 soaking Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 8
- 241000276425 Xiphophorus maculatus Species 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-O azanium;hydron;hydroxide Chemical compound [NH4+].O VHUUQVKOLVNVRT-UHFFFAOYSA-O 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/40—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides a catalyst for synthesizing acrylic acid, which comprises a catalyst having the general formula Mo 12 V a W b O g Wherein a = 0.5-10.0; b=0.1-6.0; g is a value determined by the total valence of the elements other than oxygen in the general formula, wherein the active component is spherical particles, and the surface of the active component is provided with protruding rod-shaped grains. The invention also provides a preparation method of the catalyst. The catalyst with the active component with the stable rod-shaped crystal structure is used for synthesizing acrylic acid, and has the advantages of higher catalytic efficiency, longer service life, better selectivity, high product yield, simple preparation method process and convenient operation.
Description
Technical Field
The invention relates to a catalyst for synthesizing acrylic acid and a preparation method thereof.
Background
Acrylic acid and its ester are widely used in the fields of building, electronics, automobile industry, etc., synthetic paint, adhesive, water absorbent resin, etc., the global acrylic acid productivity exceeds 300 ten thousand tons/year, and the Chinese acrylic acid productivity reaches 180 ten thousand tons/year.
At present, the two-step oxidation method of propylene is used for industrially preparing acrylic acid, wherein in a first reactor, propylene is oxidized to generate acrolein under the action of a Mo-Bi composite oxide catalyst, and in a second reactor, the acrolein is oxidized to generate acrylic acid under the action of a Mo-V composite oxide catalyst, and CO are generated simultaneously 2 Byproducts such as acetaldehyde and acetic acid, and emits a large amount of heat.
The existing common methods for preparing the catalyst mostly adopt the processes of preparing a metal compound into a solution, adding an insoluble oxide for evaporation, and then calcining, crushing and forming, and the catalyst obtained by the preparation methods generally lacks stable crystal morphology, has shorter service life, lower conversion rate and selectivity of the catalyst and lower yield of products.
Recently, those skilled in the art have improved the performance of catalysts by changing the molding method of the catalysts in order to extend the service life thereof. For example, currently, cylindrical or hollow cylindrical catalysts have the advantages of higher strength and attrition of the catalyst, more active components of the catalyst, and longer service life. However, in the actual acrylic acid production process, hot spots frequently occur in the catalyst bed, so that the activity of the catalyst is reduced, the catalyst needs to be frequently regenerated, and the production period of an acrylic acid device is shortened. The spherical catalyst has the advantages of higher effective utilization factor of the active components of the catalyst and capability of effectively removing the reaction heat, but is greatly influenced by a forming process, and the specific surface loss of the catalyst is large, so that the activity and the selectivity of the catalyst are reduced.
Disclosure of Invention
Aiming at the problems of short service life and low product yield of a catalyst used in the reaction of synthesizing acrylic acid by oxidizing acrolein in the prior art, the invention provides a catalyst capable of obtaining a stable rod-shaped grain structure, long service life and high product yield and a preparation method thereof.
In a first aspect the present invention provides a catalyst for the synthesis of acrylic acid comprising a catalyst having the general formula Mo 12 V a W b O g Wherein the active ingredient of the composition comprises, in the active ingredient,
a=0.5-10.0，
b=0.1-6.0，
g is a number determined by the total valence of the elements other than oxygen in the formula,
wherein the active component is spherical particles, and the surface of the active component is provided with protruding rod-shaped grains.
According to some embodiments of the invention, the spherical particles have a diameter of 5-50 microns.
According to some embodiments of the invention, the rod-shaped grains have a diameter of 0.1-5 microns and a length of 1-15 microns.
According to some embodiments of the invention, the rod-shaped grains have an aspect ratio of 10 to 150.
According to some embodiments of the invention, the rod-shaped grains have a crystal phase of Mo 3 VO 11 。
According to some embodiments of the invention, the catalyst further comprises a support carrying the active component, preferably the support is selected from the group consisting of SiO 2 、Al 2 O 3 、ZrO 2 And TiO 2 One or more of the following.
According to some embodiments of the invention, the catalyst includes 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the support.
In a second aspect, the present invention provides a method for preparing a catalyst for synthesizing acrylic acid, comprising the steps of:
s1: pre-roasting powder of a raw material compound containing Mo, V and W elements to obtain a catalyst precursor (I);
s2: impregnating the catalyst precursor (I) in impregnating solution containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
s3: and mixing the catalyst precursor (II) with a carrier, and then forming and roasting to obtain the catalyst.
In the invention, the catalyst precursor (II) is the active component of the catalyst.
According to some embodiments of the invention, the feedstock compound comprises oxygen-containing salts of Mo, V and W elements.
According to some embodiments of the invention, the starting compounds further comprise an oxygen-containing salt of one or more elements selected from Cu, sb, ca, fe, te and Nb.
According to some embodiments of the invention, the feedstock compounds include ammonium heptamolybdate and/or a hydrate thereof, ammonium metavanadate and/or a hydrate thereof, and ammonium tungstate and/or a hydrate thereof.
According to some embodiments of the invention, the oxygen-containing salt of Mo element is added after the oxygen-containing salt of V element.
According to some embodiments of the invention, the soluble molybdenum salt is selected from ammonium heptamolybdate and/or a hydrate thereof.
According to some embodiments of the invention, the support is selected from the group consisting of SiO 2 、Al 2 O 3 、ZrO 2 、TiO 2 And one or more of their precursors.
According to some embodiments of the invention, the molar ratio of the oxygen-containing salt of the Mo, V and W elements in the raw material compound is 12 (0.5-10.0): 0.1-6.0, based on the Mo, V and W elements.
According to some embodiments of the invention, the catalyst comprises 20 to 90 parts of the catalyst precursor (II) and 10 to 80 parts of the support in parts by weight.
According to some embodiments of the invention, in S1, a powder is obtained by spraying a dispersion of a raw material compound comprising Mo, vi and W elements.
According to some embodiments of the invention, the dispersion is an aqueous dispersion.
According to some embodiments of the invention, the concentration of ammonium heptamolybdate and/or hydrate thereof in the dispersion is from 1 to 50wt%.
According to a preferred embodiment of the invention, the concentration of ammonium heptamolybdate and/or hydrate thereof in the dispersion is 2 to 15 wt.%.
According to some embodiments of the invention, in S2, the impregnation is an isovolumetric impregnation.
According to some embodiments of the invention, the concentration of the soluble molybdenum salt in the impregnation fluid is in the range of 1 to 50wt%.
According to a preferred embodiment of the invention, the concentration of the soluble molybdenum salt in the impregnation fluid is between 10 and 25wt%.
According to some embodiments of the invention, the impregnating solution is an aqueous solution.
According to some embodiments of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 2 to 50:1, for example, may be 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, and any value therebetween.
According to some embodiments of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 2 to 20:1.
according to a preferred embodiment of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is between 2 and 10:1.
according to a further preferred embodiment of the invention, the molar ratio of the dispersion to the soluble molybdenum salt in the impregnation fluid is from 3 to 5:1.
according to some embodiments of the invention, in S1, the pre-firing temperature is 200-1000 ℃.
According to some embodiments of the invention, in S1, the pre-firing time is 0.5 to 100 hours.
According to some embodiments of the invention, in S1, the pre-firing temperature is 300-600 ℃.
According to some embodiments of the invention, in S1, the pre-firing temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, in S1, the pre-firing time is 4-30 hours.
According to some embodiments of the invention, in S1, the pre-firing time is 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours, and any value therebetween.
According to some embodiments of the invention, in S3, the firing temperature is 200-1000 ℃.
According to some embodiments of the invention, in S3, the firing time is 0.5 to 100 hours.
According to some embodiments of the invention, in S3, the firing temperature is 400-700 ℃.
According to some embodiments of the invention, in S3, the firing temperature may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, in S3, the firing time is 1 to 30 hours.
According to some specific embodiments of the invention, in S3, the firing time is 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours, and any value therebetween.
According to some embodiments of the invention, in S1, the firing time is 3-10 hours.
According to some embodiments of the invention, the temperature of the pre-firing in S1 is lower than the temperature of the firing in S3.
A third aspect of the present invention provides the use of a catalyst according to the first aspect or a catalyst obtainable by a process according to the second aspect in the synthesis of acrylic acid.
According to some embodiments of the invention, the use comprises contacting the catalyst with acrolein.
According to some embodiments of the invention, the contacting temperature is 240-320 ℃.
According to some embodiments of the invention, the propylene has a volumetric space velocity of from 100 to 150 mL.h -1 •g -1 。
According to some embodiments of the invention, the contacting conditions include: the temperature was 270℃and the volume space velocity of propylene was 110 mL.h -1 •g -1 。
The beneficial effects of the invention are as follows: the catalyst obtained by the preparation method has the active components with stable rod-shaped grain structures, and has the advantages of higher catalytic efficiency, longer service life, better selectivity, high product yield, simple preparation method process and convenient operation.
Drawings
Fig. 1 shows the microstructure of the catalyst prepared according to example 1 of the present invention.
Fig. 2 shows the microstructure of the catalyst prepared according to example 1 of the present invention.
Fig. 3 is an XRD pattern of the catalyst precursor (II) prepared according to example 1 of the present invention.
Fig. 4 is an XRD pattern of the catalyst prepared according to example 1 of the present invention.
Fig. 5 shows the microstructure of the catalyst prepared according to example 2 of the present invention.
Fig. 6 is an XRD pattern of the catalyst prepared according to example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention in any way.
The catalyst evaluation methods used in the following examples were:
introducing the reactant acrolein into a fixed bed reactor filled with a catalyst to be detected, absorbing the reacted product by using dilute acid at 0 ℃, analyzing by using gas chromatography, calculating carbon balance in the analysis process, and selecting data when the carbon balance is 95-105% as effective data, wherein the reaction conditions are as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25.4 mm and a length of 750 mm;
catalyst loading: 150 g;
reaction temperature: 270 ℃;
reaction time: 500 hours;
the volume ratio of the raw materials is as follows: acrolein to air to water vapor = 1:3.2:2.1;
acrolein volume space velocity: 110 mL.h -1 •g -1 。
[ example 1 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 800g of an aqueous solution, stirring for 10 minutes, spray-drying, and roasting the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 And O) 200g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The microstructure of the obtained catalyst is observed by a scanning electron microscope SEM, and as shown in figures 1 and 2, the active component in the obtained catalyst is catalyst particles with special appearance, the surface of each spherical particle is provided with a convex rod-shaped crystal grain, the diameter of each spherical particle is about 20 microns, the length of each rod-shaped crystal grain is 1-5 microns, and the diameter of each rod-shaped crystal grain is 0.5-1 micron.
FIG. 3 shows the XRD pattern of the precursor (II), which is amorphous and FIG. 4 shows the XRD pattern of the catalyst, which has a crystal form of Mo 3 VO 11， Is shown as a crystalline rodThe crystal structure of the material.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 2 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 500g of an aqueous solution, stirring for 10min, spray drying, and baking the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 O) 500g of aqueous solution, and uniformly stirring, and then drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 3 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 900g of an aqueous solution, stirring for 10min, spray-drying, and baking the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 O) 100g of aqueous solution, and uniformly stirring, and then drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 4 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 950g of an aqueous solution, stirring for 10min, spray-drying, and baking the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 50g of aqueous solution, and uniformly stirring, and then drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 5 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 975g of an aqueous solution, stirring for 10min, spray-drying, and baking the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 And O) 25g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 6 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 987.5g of an aqueous solution, stirring for 10 minutes, spray-drying, and baking the obtained powder in a muffle furnace at 395℃for 8 hours to obtain a precursor (I).
Then, 20wt% of ammonium heptamolybdate ((NH) was added to the precursor (I) 4 ) 6 Mo 7 O 24 •4H 2 O) 12.5g of aqueous solution, and after stirring uniformly, drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Mixing graphite 1.6g and deionized water 3.2g, tabletting with tabletting machine at 3kN, and tablettingAnd finally roasting the catalyst at 405 ℃ for 4 hours to obtain the catalyst for synthesizing the acrylic acid.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 7 ]
22 g of ammonium metavanadate (NH) 4 VO 3 ) 38.2 g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O) 1000g of an aqueous solution, stirring for 10min, spray-drying, and baking the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then 21.9g of 20wt% ammonium metavanadate aqueous solution is added into the obtained precursor (I), and the mixture is uniformly stirred and dried at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The microstructure of the obtained catalyst was observed by SEM, and as shown in fig. 5, spherical particles of the active component in the obtained catalyst were seen. Fig. 6 is an XRD pattern of the catalyst.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
[ example 8 ]
43.9 g of ammonium metavanadate (NH) 4 VO 3 ) 19.1g ammonium tungstate ((NH) 4 ) 5 H 5 [H 2 (WO 4 ) 6 ]•H 2 O) was dissolved in 1000ml of deionized water, to which 20wt% ammonium heptamolybdate ((NH) was added 4 ) 6 Mo 7 O 24 •4H 2 O）1000g of aqueous solution, stirring for 10min, spray drying, and roasting the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then 19.1g of 20wt% ammonium tungstate aqueous solution is added into the obtained precursor (I), and the mixture is uniformly stirred and dried at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) and 40 g of SiO were taken 2 Uniformly mixing 1.6g of graphite and 3.2g of deionized water, setting a tabletting pressure of 3kN by a tablet press, tabletting and forming to obtain a round platy formed catalyst with a diameter of 5mm and a tablet thickness of 4mm, and finally roasting at 405 ℃ for 4 hours to obtain the catalyst for acrylic acid synthesis.
The obtained catalyst was evaluated by the catalyst evaluation method, and the results are shown in table 1.
TABLE 1
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (20)
1. A catalyst for synthesizing acrylic acid comprises a catalyst having the general formula Mo 12 V a W b O g Wherein the active ingredient of the composition comprises, in the active ingredient,
a=0.5-10.0；
b=0.1-6.0；
g is a number determined by the total valence of the elements other than oxygen in the formula,
wherein the active component is spherical particles, and the surface of the active component is provided with protruding rod-shaped grains;
the crystal phase of the rod-shaped crystal grain is Mo 3 VO 11 ；
The preparation method of the catalyst comprises the following steps:
s1: pre-roasting powder of a raw material compound containing Mo, V and W elements to obtain a catalyst precursor (I);
s2: impregnating the catalyst precursor (I) in impregnating solution containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
s3: mixing the catalyst precursor (II) with a carrier, and then forming and roasting to obtain the catalyst;
the molar ratio of the oxygen-containing salt containing Mo, V and W elements in the raw material compound is 12 (0.5-10.0): 0.1-6.0;
in S1, spraying a dispersion liquid of a raw material compound containing Mo, V and W elements to obtain powder, wherein the mole ratio of the dispersion liquid of the raw material compound to the soluble molybdenum salt in the impregnating solution is 2-50:1.
2. the catalyst according to claim 1, wherein the spherical particles have a diameter of 5-50 microns, and/or
The diameter of the rod-shaped crystal grains is 0.1-5 microns, and the length of the rod-shaped crystal grains is 1-15 microns.
3. The catalyst according to claim 1, wherein the rod-shaped crystallites have an aspect ratio of 10 to 150.
4. The catalyst of claim 1, wherein the support is selected from the group consisting of SiO 2 、Al 2 O 3 、ZrO 2 And TiO 2 One or more of the following.
5. The catalyst according to any one of claims 1 to 4, characterized in that the catalyst comprises 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the carrier.
6. A method for preparing the catalyst for synthesizing acrylic acid according to any one of claims 1 to 5, comprising the steps of:
s1: pre-roasting powder of a raw material compound containing Mo, V and W elements to obtain a catalyst precursor (I);
s2: impregnating the catalyst precursor (I) in impregnating solution containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
s3: and mixing the catalyst precursor (II) with a carrier, and then forming and roasting to obtain the catalyst.
7. The method of claim 6, wherein the starting compound comprises an oxygen-containing salt of Mo, V, and W elements and optionally one or more elements selected from Cu, sb, ca, fe, te and Nb; and/or
The soluble molybdenum salt is selected from ammonium heptamolybdate and/or a hydrate thereof; and/or
The carrier is selected from SiO 2 、Al 2 O 3 、ZrO 2 、TiO 2 And one or more of their precursors.
8. The method according to claim 6, wherein the starting compound comprises ammonium heptamolybdate and/or a hydrate thereof, ammonium metavanadate and/or a hydrate thereof, and ammonium tungstate and/or a hydrate thereof.
9. The method according to claim 6, wherein the oxygen-containing salt of Mo element is added after the oxygen-containing salt of V element.
10. The preparation method according to claim 7, wherein the molar ratio of the oxygen-containing salts of Mo, V and W elements in the raw material compound is 12 (0.5-10.0): 0.1-6.0, based on the Mo, V and W elements; and/or
The catalyst comprises 20-90 parts of a catalyst precursor (II) and 10-80 parts of a carrier in parts by weight.
11. The production method according to any one of claims 6 to 10, wherein in S1, a powder is obtained by spraying a dispersion of a raw material compound containing Mo, V, and W elements; and/or
S2, soaking in an equal volume mode; and/or
The mole ratio of the dispersion liquid to the soluble molybdenum salt in the impregnating liquid is 2-50:1.
12. the method of claim 11, wherein the dispersion is an aqueous dispersion and/or the impregnating solution is an aqueous solution.
13. The method according to claim 11, characterized in that the concentration of ammonium heptamolybdate and/or its hydrate in the dispersion is 1-50wt% and/or the concentration of soluble molybdenum salt in the impregnation is 1-50wt% and/or the molar ratio of the dispersion to soluble molybdenum salt in the impregnation is 2-20:1.
14. The method according to claim 11, characterized in that the concentration of ammonium heptamolybdate and/or its hydrate in the dispersion is 2-15wt% and/or the concentration of soluble molybdenum salt in the impregnation is 10-25wt% and/or the molar ratio of the dispersion to soluble molybdenum salt in the impregnation is 2:10:1.
15. The preparation method according to any one of claims 6 to 10, wherein in S1, the pre-firing temperature is 200 to 1000 ℃ and/or the pre-firing time is 0.5 to 100 hours; and/or
In S3, the roasting temperature is 200-1000 ℃ and/or the roasting time is 0.5-100 hours.
16. The method according to claim 15, wherein in S1, the pre-firing temperature is 300-600 ℃ and/or the pre-firing time is 4-30 hours;
and/or, in S3, the roasting temperature is 400-700 ℃, and/or the roasting time is 3-10 hours.
17. The method of claim 15, wherein in S1, the pre-firing temperature is lower than the firing temperature in S3.
18. Use of a catalyst according to any one of claims 1 to 5 or a catalyst prepared according to the preparation method of any one of claims 6 to 17 in the synthesis of acrylic acid.
19. Use of the catalyst according to claim 18 in the synthesis of acrylic acid, characterized in that the use comprises contacting the catalyst with acrolein.
20. Use of the catalyst according to claim 19 in the synthesis of acrylic acid, characterized in that the temperature of the contact is 240-320 ℃ and/or the volume space velocity of the acrolein is 100-150 ml.h -1 •g -1 。
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| CN111068649A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid and method for synthesizing acrylic acid from acrolein |
| CN111068652A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for acrylic acid synthesis and method for synthesizing acrylic acid from acrolein |
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| DE102012207811A1 (en) * | 2012-05-10 | 2012-07-12 | Basf Se | Heterogeneously catalyzed gas phase partial oxidation of (meth)acrolein to (meth)acrylic acid using a catalytically active multimetal oxide mass |
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