CN114471529A - 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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- CN114471529A CN114471529A CN202011164243.0A CN202011164243A CN114471529A CN 114471529 A CN114471529 A CN 114471529A CN 202011164243 A CN202011164243 A CN 202011164243A CN 114471529 A CN114471529 A CN 114471529A
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- acrylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 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 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012798 spherical particle Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 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 36
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound 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 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- 150000002751 molybdenum Chemical class 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 11
- 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
- 238000007493 shaping process Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002250 absorbent Substances 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 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
- 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
- 238000001694 spray drying Methods 0.000 description 1
Images
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 invention provides a catalyst for synthesizing acrylic acid, which comprises Mo with a general formula12VaWbOgWherein a is 0.5 to 10.0; b is 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 having a surface with protruding rod-like grains. The invention also provides a preparation method of the catalyst. The catalyst with the stable active component of the rod-like 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
The acrylic acid and the ester thereof are widely applied to the fields of building, electronics, automobile industry and the like, the synthetic coating, the adhesive, the water-absorbent resin and the like, the global acrylic acid productivity exceeds 300 million tons/year, and the Chinese acrylic acid productivity reaches 180 million tons/year.
At present, the industrial production of acrylic acid uses a two-step oxidation method of propylene, in which propylene is oxidized to form acrolein under the action of Mo-Bi composite oxide catalyst in a first reactor, and acrolein is oxidized to form acrylic acid under the action of Mo-V composite oxide catalyst in a second reactor, and CO are simultaneously formed2Acetaldehyde and acetic acid, and the like, and gives off a large amount of heat.
The catalyst obtained by the preparation methods usually lacks stable crystal morphology, has short service life, low conversion rate and selectivity of the catalyst and low yield of products.
Recently, those skilled in the art have attempted to improve the performance of catalysts by changing the method of forming the catalyst in order to extend the service life thereof. For example, currently, cylindrical or hollow cylindrical catalysts have the advantages of higher strength and abrasion of the catalyst, more active components of the catalyst, and longer service life. However, in the actual production process of acrylic acid, hot spots frequently appear on the catalyst bed layer, which causes the activity of the catalyst to be reduced, and the catalyst needs to be regenerated frequently, thereby reducing the production period of the acrylic acid device. The spherical catalyst has the advantages of higher effective utilization factor of the active components of the catalyst and capability of effectively removing reaction heat, but the spherical catalyst is greatly influenced by a forming process, and the loss of the specific surface of the catalyst is larger, 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 which can obtain a stable rod-shaped crystal structure, and has long service life and high product yield and a preparation method thereof.
In a first aspect of the present invention, there is provided a catalyst for the synthesis of acrylic acid comprising Mo having the general formula12VaWbOgThe active ingredient of (1), wherein,
a＝0.5-10.0，
b＝0.1-6.0，
g is a number determined by the total valence of the elements in the formula other than oxygen,
wherein the active component is spherical particles, and the surfaces of the active component are provided with raised rod-shaped grains.
According to some embodiments of the invention, the spherical particles have a diameter of 5 to 50 microns.
According to some embodiments of the invention, the rod-like grains have a diameter of 0.1 to 5 microns and the rod-like grains have a length of 1 to 15 microns.
According to some embodiments of the invention, the rod-like grains have an aspect ratio of 10 to 150.
According to some embodiments of the invention, the crystalline phase of the rod-like crystals is Mo3VO11。
According to some embodiments of the invention, the catalyst further comprises a support supporting the active component, preferably the support is selected from SiO2、Al2O3、ZrO2And TiO2One or more of (a).
According to some embodiments of the invention, the catalyst comprises 20 to 90 parts by mass of the active component and 10 to 80 parts by mass of the carrier.
A second aspect of the present invention provides a method for preparing a catalyst for synthesizing acrylic acid, comprising the steps of:
s1: pre-roasting powder of raw material compounds containing Mo, V and W elements to obtain a catalyst precursor (I);
s2: dipping the catalyst precursor (I) in dipping liquid containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
s3: and (3) mixing the catalyst precursor (II) with a carrier, and then molding 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 compounds comprise oxy-salts of Mo, V and W elements.
According to some embodiments of the invention, the feedstock compound further comprises an oxy-salt of one or more elements selected from Cu, Sb, Ca, Fe, Te and Nb.
According to some embodiments of the invention, the starting compounds comprise 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 oxysalt of the Mo element is added after the oxysalt of the 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 SiO2、Al2O3、ZrO2、TiO2And their precursors.
According to some embodiments of the present invention, the molar ratio of the oxysalt of the Mo, V, and W elements in the starting compound is 12 (0.5-10.0) to (0.1-6.0) in terms of the Mo, V, and W elements.
According to some embodiments of the present invention, the catalyst comprises 20 to 90 parts by weight of the catalyst precursor (II) and 10 to 80 parts by weight of the carrier.
According to some embodiments of the present invention, in S1, the powder is obtained by spraying a dispersion of the raw material compounds containing 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 its hydrate in the dispersion is 1 to 50 wt%.
According to a preferred embodiment of the invention, the concentration of ammonium heptamolybdate and/or its hydrate in the dispersion is 2 to 15 wt.%.
According to some embodiments of the invention, in S2, the impregnating is with an equal volume of impregnation.
According to some embodiments of the invention, the concentration of the soluble molybdenum salt in the impregnation solution is between 1 and 50 wt%.
According to a preferred embodiment of the invention, the concentration of soluble molybdenum salt in the impregnation solution is between 10 and 25 wt.%.
According to some embodiments of the invention, the impregnation fluid 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 solution is from 2 to 50: 1, for example, can 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 in between.
According to some embodiments of the invention, the molar ratio of the soluble molybdenum salt in the dispersion to the impregnation solution is from 2 to 20: 1.
according to a preferred embodiment of the invention, the molar ratio of the soluble molybdenum salt in the dispersion to the impregnation solution is from 2 to 10: 1.
according to a further preferred embodiment of the present invention, the molar ratio of the soluble molybdenum salt in the dispersion to the impregnation solution is 3-5: 1.
according to some embodiments of the present invention, the pre-firing temperature is 200-1000 ℃ in S1.
According to some embodiments of the invention, the pre-baking time in S1 is 0.5 to 100 hours.
According to some embodiments of the present invention, the pre-firing temperature is 300-600 ℃ in S1.
According to some embodiments of the present invention, the pre-baking temperature in S1 may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, the pre-baking time in S1 is 4-30 hours.
According to some specific embodiments of the present invention, in S1, the pre-baking 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 present invention, the temperature of the firing is 200-1000 ℃ in S3.
According to some embodiments of the invention, in S3, the calcination time is 0.5 to 100 hours.
According to some embodiments of the present invention, the temperature of the firing is 400-700 ℃ in S3.
According to some embodiments of the present invention, in S3, the temperature of the firing may be 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and any value therebetween.
According to some embodiments of the invention, in S3, the calcination time is 1 to 30 hours.
According to some specific embodiments of the present invention, in S3, the calcination is performed for 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 calcination time is 3 to 10 hours.
According to some embodiments of the invention, the pre-firing temperature in S1 is lower than the firing temperature in S3.
A third aspect of the present invention provides a use of the catalyst according to the first aspect or the catalyst obtained by the production method according to the second aspect in the synthesis of acrylic acid.
According to some embodiments of the invention, the applying comprises contacting the catalyst with acrolein.
According to some embodiments of the invention, the temperature of the contacting is 240-.
According to the inventionIn some embodiments, the volume space velocity of the propylene is 100-150 mL-h-1·g-1。
According to some embodiments of the invention, the conditions of the contacting comprise: the temperature is 270 ℃, and the volume space velocity of propylene is 110mL h-1·g-1。
The invention has the beneficial effects that: the catalyst prepared by the preparation method disclosed by the invention has stable active components with rod-like crystal structures, and is higher in catalytic efficiency, longer in service life, better in selectivity, high in product yield, simple in preparation method process and convenient to operate.
Drawings
Fig. 1 shows the microstructure of a 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 invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
The catalyst evaluation methods used in the following examples were:
introducing a reactant acrolein into a fixed bed reactor filled with a catalyst to be detected, absorbing a product after reaction by using dilute acid at 0 ℃, analyzing by using a 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:
a reactor: 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 raw materials is as follows: acrolein, air, 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)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 800g of an aqueous solution, stirred for 10min, spray-dried, and the resulting powder was calcined in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) is added into the obtained precursor (I)4)6Mo7O24·4H2O) 200g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The microstructure of the obtained catalyst is observed by a scanning electron microscope SEM, as shown in attached figures 1 and 2, the active component in the obtained catalyst is catalyst particles with special new appearance, the surface of the spherical particles is provided with raised rod-shaped crystal grains, the diameter of the spherical particles is about 20 microns, the length of the rod-shaped crystal grains is 1-5 microns, and the diameter of the rod-shaped crystal grains is 0.5-1 micron.
FIG. 3 is an XRD pattern of the precursor (II) showing that the precursor is amorphous without crystallization, and FIG. 4 is an XRD pattern of the catalyst with the crystal form of Mo3VO11Showing the crystal structure of the crystalline rod.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 2 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 500g of an aqueous solution, stirred for 10min, spray-dried, and the resulting powder was calcined in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) is added into the obtained precursor (I)4)6Mo7O24·4H2O) 500g of water solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 3 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 900g of an aqueous solution, stirred for 10min, spray-dried, and the resulting powder was calcined at 395 ℃ for 8 hours in a muffle furnace to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) was added to the obtained precursor (I)4)6Mo7O24·4H2O) 100g of aqueous solution, evenly stirring, drying for 24 hours at 80 ℃,to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 4 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 950g of an aqueous solution, stirred for 10min, spray-dried, and calcined at 395 ℃ in a muffle furnace for 8 hours to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) is added into the obtained precursor (I)4)6Mo7O24·4H2O) 50g of aqueous solution, uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained, 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 5 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 975g of an aqueous solution, stirred for 10min, spray-dried, and calcined at 395 ℃ for 8 hours in a muffle furnace to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) is added into the obtained precursor (I)4)6Mo7O24·4H2O) water solution 25g, evenly stirring, drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 6 ]
43.9 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 987.5g of an aqueous solution, stirred for 10min, spray-dried, and calcined at 395 ℃ in a muffle furnace for 8 hours to obtain a precursor (I).
Then, 20 wt% of ammonium heptamolybdate ((NH) is added into the obtained precursor (I)4)6Mo7O24·4H2O) water solution 12.5g, evenly stirred and dried for 24 hours at 80 ℃ to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 7 ]
22 g of ammonium metavanadate (NH)4VO3) 38.2 g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of an aqueous solution, stirred for 10min, spray-dried, and the resulting powder was calcined at 395 ℃ for 8 hours in a muffle furnace to obtain a precursor (I).
And adding 21.9g of 20 wt% ammonium metavanadate aqueous solution into the obtained precursor (I), uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained, 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
The microstructure of the obtained catalyst is observed by a scanning electron microscope SEM, and as shown in figure 5, spherical particles of the active component in the obtained catalyst can be seen. Figure 6 is an XRD pattern of the catalyst.
The obtained catalyst was evaluated by the catalyst evaluation method described above, and the results are shown in table 1.
[ example 8 ]
43.9 g of ammonium metavanadate (NH)4VO3) 19.1g of ammonium tungstate ((NH)4)5H5[H2(WO4)6]·H2O) was dissolved in 1000ml of deionized water, and 20 wt% of ammonium heptamolybdate ((NH) was added thereto4)6Mo7O24·4H2O) 1000g of an aqueous solution, stirring for 10min, spray-drying, and calcining the obtained powder in a muffle furnace at 395 ℃ for 8 hours to obtain a precursor (I).
And then adding 19.1g of 20 wt% ammonium tungstate aqueous solution into the obtained precursor (I), uniformly stirring, and drying at 80 ℃ for 24 hours to obtain a precursor (II).
360 g of the precursor (II) obtained and 40 g of SiO21.6g of graphite and 3.2g of deionized water are uniformly mixed, the tabletting pressure is set to be 3kN by a tabletting machine, the round flaky shaped catalyst with the diameter of 5mm and the flake thickness of 4mm is obtained by tabletting and shaping, and finally the catalyst for synthesizing the acrylic acid is obtained by roasting at 405 ℃ for 4 hours.
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-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst for synthesizing acrylic acid, comprising Mo12VaWbOgThe active ingredient of (1), wherein,
a＝0.5-10.0；
b＝0.1-6.0；
g is a number determined by the total valence of the elements in the formula other than oxygen,
wherein the active component is spherical particles, and the surfaces of the active component are provided with raised rod-shaped grains.
2. Catalyst according to claim 1, characterized in that 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, the length of the rod-shaped crystal grains is 1-15 microns, the length-diameter ratio of the rod-shaped crystal is preferably 10-150, and/or the crystal phase of the rod-shaped crystal is Mo3VO11。
3. Catalyst according to claim 1 or 2, characterized in that it further comprises a support supporting the active component, preferably the support is selected from SiO2、Al2O3、ZrO2And TiO2One or more of (a).
4. The catalyst according to any one of claims 1 to 3, 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.
5. A method for preparing a catalyst for synthesizing acrylic acid, comprising the steps of:
s1: pre-roasting powder of raw material compounds containing Mo, V and W elements to obtain a catalyst precursor (I);
s2: dipping the catalyst precursor (I) in dipping liquid containing soluble molybdenum salt, and drying to obtain a catalyst precursor (II);
s3: and (3) mixing the catalyst precursor (II) with a carrier, and then molding and roasting to obtain the catalyst.
6. The production method according to claim 5, wherein the raw material compound comprises an oxysalt of Mo, V and W elements and optionally an oxysalt of one or more elements selected from Cu, Sb, Ca, Fe, Te and Nb; preferably, the raw material compounds include ammonium heptamolybdate and/or a hydrate thereof, ammonium metavanadate and/or a hydrate thereof, and ammonium tungstate and/or a hydrate thereof; more preferably, the oxysalt of the element Mo is added after the oxysalt of the element V, and/or
The soluble molybdenum salt is selected from ammonium heptamolybdate and/or a hydrate thereof; and/or
The carrier is selected from SiO2、Al2O3、ZrO2、TiO2And their precursors.
7. The production method according to claim 5 or 6, wherein the molar ratio of the oxygen-containing salt containing the elements Mo, V and W in the raw material compound is 12 (0.5-10.0) to (0.1-6.0) in terms of the elements Mo, V and W; and/or
The catalyst comprises 20-90 parts of catalyst precursor (II) and 10-80 parts of carrier by weight.
8. The production method according to any one of claims 5 to 7, wherein in S1, a powder is obtained by spraying a dispersion of a raw material compound containing Mo, V and W elements; preferably, the dispersion is an aqueous dispersion; more preferably, the concentration of ammonium heptamolybdate and/or its hydrate in the dispersion is 1 to 50 wt%, more preferably 2 to 15 wt%; and/or
In S2, the impregnation is carried out in an equal volume; preferably, the concentration of the soluble molybdenum salt in the impregnation solution is between 1 and 50 wt%, more preferably between 10 and 25 wt%; further preferably, the impregnation solution is an aqueous solution; and/or
The molar ratio of the dispersion liquid to the soluble molybdenum salt in the impregnation liquid is 2-50: 1, preferably 2-20:1, more preferably 2:10: 1.
9. The method according to any one of claims 5 to 8, wherein in S1, the pre-baking temperature is 200-1000 ℃, and/or the pre-baking time is 0.5-100 hours; preferably, the temperature of the pre-roasting is 300-600 ℃, and/or the time of the pre-roasting is 4-30 hours; and/or
In S3, the roasting temperature is 200-1000 ℃, and/or the roasting time is 0.5-100 hours; preferably, the roasting temperature is 400-700 ℃, and/or the roasting time is 3-10 hours; it is further preferred that the first and second liquid crystal compositions,
in S1, the temperature of the pre-baking is lower than that of the baking in S3.
10. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation process according to any one of claims 5 to 9 in the synthesis of acrylic acid, preferably the use comprises contacting the catalyst with acrolein; preferably, the temperature of the contact is 240-320 ℃, and/or the volume space velocity of the propylene is 100-150 mL-h-1·g-1。
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