CN111068701A - Catalyst for producing acrylic acid and use thereof - Google Patents
Catalyst for producing acrylic acid and use thereof Download PDFInfo
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- CN111068701A CN111068701A CN201811218652.7A CN201811218652A CN111068701A CN 111068701 A CN111068701 A CN 111068701A CN 201811218652 A CN201811218652 A CN 201811218652A CN 111068701 A CN111068701 A CN 111068701A
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- catalyst
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- acrylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 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 33
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 10
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 3
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052730 francium Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052745 lead Inorganic materials 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 83
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 52
- 239000000203 mixture Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052705 radium Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 40
- 239000011734 sodium Substances 0.000 description 38
- 238000011156 evaluation Methods 0.000 description 31
- 238000011068 loading method Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 23
- 239000012018 catalyst precursor Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 19
- 239000010948 rhodium Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 230000035484 reaction time Effects 0.000 description 11
- 229910015667 MoO4 Inorganic materials 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 235000010344 sodium nitrate Nutrition 0.000 description 10
- 239000004317 sodium nitrate Substances 0.000 description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 9
- 239000011609 ammonium molybdate Substances 0.000 description 9
- 229940010552 ammonium molybdate Drugs 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 8
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910000457 iridium oxide Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 4
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for producing acrylic acid and application thereof, and the technical scheme is as follows: a catalyst for producing acrylic acid, comprising a carrier and an active component supported on the carrier, the active component being represented by the general formula: VMoaCobWcXdQeZfOgWherein X is at least one element selected from the group consisting of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is at least one element selected from the group consisting of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is at least one element selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and RaAt least one of (1).
Description
Technical Field
The present invention relates to a catalyst for producing acrylic acid, a preparation method thereof and an application thereof in preparing acrylic acid by oxidizing acrolein.
Background
Acrylic acid is an important organic chemical raw material, is mainly used for manufacturing multifunctional high polymer materials such as acrylates, and is widely applied to the fields of papermaking, leather, coating, textile, plastics, rubber, oil additives, petroleum exploitation and the like. In recent years, the market demand for acrylic acid has increased worldwide, and the production of acrylic acid has been a focus of research. Acrolein is the simplest unsaturated aldehyde and is also an important chemical synthesis intermediate, and is widely used for synthesizing important chemical products such as picoline, pyridine, glutaraldehyde, acrylic acid and the like, so that the production of acrylic acid by acrolein is in the trend. The synthesis of acrylic acid by the acrolein oxidation process is currently used on a large industrial scale.
The catalyst used for synthesizing acrylic acid by acrolein oxidation method is generally Mo-V series oxide, the basic elements of the catalyst are Mo and V, and other elements used for improving the performance of the catalyst, such as Nb, Sn, Cr, W, Fe, Co, Ni, Sb and the like, are added. US Pat7220698B2 describes the introduction of a trace amount of a catalyst poison into the catalyst preparation process to inhibit thermal degradation of the catalyst and provide stability to the catalyst. US Pat7456129B2 describes varying acid content, controlling acid strength, and improving catalyst performance during catalyst support preparation. CN 16997701 and CN1210511 propose a preparation method of a composite oxide catalyst, which is to Co-precipitate mixed liquor of various element components (containing Fe, Co, Mo, V, Bi, Ni, etc.), dry into powder, perform tabletting, extrusion molding, and finally bake to obtain the composite oxide catalyst. The acrylic acid catalyst can be successfully prepared by the methods and the performance of the catalyst is improved, but the catalyst has poor mechanical strength and low catalytic activity ratio, so that the practical application is limited.
The catalyst carrier can enable the catalyst to have proper shape, size and mechanical strength, so that the mechanical strength of the catalyst can be increased by loading the active components of the catalyst on the carrier with large specific surface area, the loading amount of the active components is greatly increased, and the active components of the catalyst are exerted to a great extent through synergistic action. CN1130172 (preparation method of acrylic acid) describes a preparation method of a spherical catalyst, in which a carrier is added into an active component mixed solution, and is evaporated and dried, so that the active component is deposited on the surface of the carrier. However, the catalytic activity, selectivity and yield of the acrylic acid catalyst obtained in the prior art need to be further improved.
Disclosure of Invention
The invention aims to solve the technical problems of low acrolein conversion rate and low acrylic acid yield of the existing catalyst, and provides a novel catalyst for producing acrylic acid, which has the characteristics of high acrolein conversion rate and high acrylic acid yield.
The second technical problem to be solved by the invention is a preparation method of the catalyst.
The invention solves the technical problem of the prior art, and the other technical problem is the application of the catalyst.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
a catalyst for producing acrylic acid, comprising a carrier and an active component supported on the carrier, the active component being represented by the general formula: VMoaCobWcXdQeZfOgWherein X is at least one selected from the group consisting of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is at least one selected from the group consisting of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and Ra; a is the molar ratio of Mo to V, and the value of a is 2.0-8.0; b is the molar ratio of Co to V, and the value of b is 0.1-1.0; c is the molar ratio of W to V, and the value of c is 0.1-1.0; d is the molar ratio of X to V, and the value of d is 0.1-1.0; e is the molar ratio of Q to V, and the value of e is 0.1-1.0; f is the molar ratio of Z to V, and the value of f is 0.1-1.0; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.
In the above-mentioned embodiments, as one of preferable embodiments, Q preferably includes Sc and Rh together, and Sc and Rh have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a second preferred technical solution, Q preferably includes Sc and Ir at the same time, and Sc and Ir have a synergistic effect in improving the yield of acrylic acid.
In the above technical solution, as a third preferred technical solution, Q preferably includes Sc and Pr at the same time, and Sc and Pr have a synergistic effect in improving the yield of acrylic acid.
In the above technical solutions, as one of more preferable technical solutions, Q preferably includes Sc, Rh, and Ir at the same time, and the three have a synergistic effect of ternary combination in improving the yield of acrylic acid.
In the above-mentioned technical solution, as a second more preferable technical solution, Q preferably includes Sc, Rh and Pr at the same time, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.
In the above technical solutions, as a third more preferable technical solution, Q preferably includes Sc, Ir and Pr at the same time, and the three have a synergistic effect of ternary combination in the aspect of improving the yield of acrylic acid.
In the above technical scheme, the molar ratio of Mo to V may be, but not limited to, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 7.0, and the like.
In the above technical scheme, the molar ratio of Co to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.
In the above technical scheme, the molar ratio of W to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.
In the above technical scheme, the molar ratio of Sn to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.
In the above technical scheme, the molar ratio of Na to V may be, but not limited to, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.70, and the like.
In the above technical scheme, the molar ratio of Sc to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and the like.
In the above technical scheme, the molar ratio of Rh to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and the like.
In the above technical scheme, the molar ratio of Ir to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, etc.
In the above technical scheme, the molar ratio of Pr to V may be, but not limited to, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, and the like.
In the above technical scheme, more specific examples of the general formula of the active ingredient can be, but are not limited to:
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Rh0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Ir0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.05～0.50Pr0.05～0.50Na0.1～1.0Og；
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Rh0.03～0.30Ir0.03～0.30Na0.1～1.0Og；
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Rh0.03～0.30Pr0.03～0.30Na0.1～1.0Og；
VMo2.0～8.0Co0.1～1.0W0.1～1.0Sn0.1～1.0Sc0.04～0.40Ir0.03～0.30Pr0.03～0.30Na0.1～1.0Og；
wherein g is the mole number of oxygen atoms required to satisfy the valence of each element in the active component.
In the technical scheme, the content of the active component in the catalyst is preferably 10-80 w% by weight.
In the technical scheme, the content of the carrier in the catalyst is preferably 20-90 w% by weight.
In the above technical solutions, the shape and size of the carrier are not particularly limited, and all the carriers can obtain comparable technical effects, for which the skilled person can reasonably select. For convenience of comparison, the carriers of the embodiments of the present invention are all spherical.
In the above technical solution, the support is preferably at least one of alumina, lithium oxide, magnesia, zirconia, silica and titania.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing a catalyst according to any of the preceding technical problems, comprising:
preparing mixed liquid of active component elements;
mixing the active component element mixed solution with a carrier;
and (4) roasting.
In the above technical solution, the mixed solution may be a solution, a suspension, or a mixture of a solution and a suspension.
In the above technical solution, the conditions for calcination are not particularly limited as long as the conditions are such that the specific compound forms of all the active elements present in the above mixed solution can be calcined into oxide forms, and those skilled in the art can select the conditions for calcination appropriately without creative efforts.
In the above technical scheme, the roasting temperature is 300-600 ℃ by way of example only.
In the above technical scheme, the roasting time is 1-15 hours, which is only an example.
In the above technical scheme, the roasting atmosphere is an inert atmosphere or an atmosphere containing O by way of example only2Of the atmosphere (c). However, the atmosphere for the calcination is preferably air from the economical viewpoint. If not specifically noted, the invention is practiced by calciningThe atmosphere of (A) is air.
In the above technical scheme, the catalyst can be prepared in the following manner:
1. preparation of active element solution
Dissolving a compound of the required active component elements to obtain a mixed solution of the active elements; the dissolution step is not particularly limited, and the specific dissolution procedure and process conditions may be appropriately selected by those skilled in the art.
2. Active element loading
And (2) mixing the carrier particles with the mixed liquid of the active elements obtained in the step (1) (wherein the dosage of the mixed liquid of the active elements is 10-80 w% of the content of the catalyst), and drying to obtain a catalyst precursor I. The drying temperature can be but is not limited to 50-120 ℃, and the drying time can be but is not limited to 1-15 hours.
3. Roasting
Calcining the catalyst precursor I to obtain the catalyst. The roasting temperature is, for example, but not limited to, 300-600 ℃, and the roasting time is, for example, but not limited to, 1-15 hours.
The catalyst prepared in this way is surprisingly good in terms of acrolein conversion and acrylic acid yield.
To solve the third technical problem, the technical scheme of the invention is as follows: use of a catalyst according to any of the preceding claims for the preparation of acrylic acid by oxidation of acrolein.
The technical key of the invention is the selection of the catalyst, which can be reasonably selected by the skilled person for the specific application method and process conditions without creative efforts, such as:
a process for producing acrylic acid by oxidizing acrolein, which comprises reacting acrolein with an oxygen-containing oxidizing gas in the presence of the catalyst according to any one of the above-mentioned technical problems.
In the above technical scheme, in order to make the reaction more stable and controllable, the reaction is preferably carried out in the presence of a dilute gas phase material.
In the above embodiment, the oxidizing gas may be pure oxygen or oxygen-rich, but air is preferred from the economical viewpoint.
In the above technical solution, the dilute gas phase material is preferably steam.
In the technical scheme, the reaction temperature can be selected from 100-500 ℃.
In the above technical solution, in the raw material gas composed of acrolein, air and water vapor, in terms of volume ratio, it is preferable that acrolein: air: the steam is 1 (1-6) and 0.5-5.
In the technical scheme, the airspeed of the feed gas is 800-2000 ml.h-1·g-1。
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The catalyst of the present invention has acrolein converting rate up to 99% and acrylic acid yield up to 91%, and may be used in industrial production of acrylic acid.
Detailed Description
[ example 1 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.04 mol of Sc (molecular formula: sc (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.4Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 2 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Will containAmmonium molybdate (molecular formula is (NH)) of 0.4 mol Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Rhodium nitrate containing 0.04 mol of Rh (formula: rh (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Rh0.4Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Rh0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 3 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Iridium oxide containing 0.04 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Ir0.4Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Ir0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 4 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Praseodymium nitrate containing 0.04 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Pr0.4Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Pr0.4Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 5 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.02 mol of Rh (formula: rh (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.2Rh0.2Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.2Rh0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 6 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Iridium oxide containing 0.02 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.2Ir0.2Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.2Ir0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 7 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding ammonium tungstate (molecular weight) in an amount of 0.04 mol WThe formula is as follows: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.02 mol of Sc (molecular formula: sc (NO)3)3) Praseodymium nitrate containing 0.02 mol of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.2Pr0.2Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.2Pr0.2Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 8 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.015 mol of Rh (formula: rh (NO)3)3) Iridium oxide containing 0.01 mol of Ir (molecular formula: IrO2) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.15Rh0.15Ir0.1Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.15Rh0.15Ir0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 9 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Rhodium nitrate containing 0.015 mol of Rh (formula: rh (NO)3)3) Praseodymium nitrate containing 0.01 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate (molecular formula: Co (NO): containing 0.04 mol Co3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.15Rh0.15Pr0.1Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.15Rh0.15Pr0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
[ example 10 ]
1. Preparation of active element solution
Ammonium metavanadate (molecular formula: NH) containing 0.1 mol of V4VO3) Dissolved in hot water (200 g) at 80 ℃. Ammonium molybdate (molecular formula is (NH)) containing 0.4 mol of Mo4)2MoO4) Adding the mixture, and respectively adding ammonium tungstate (molecular formula: (NH)4)10W12O41) Tin dioxide containing 0.04 mol of Sn (formula: SnO2) Scandium nitrate containing 0.015 mol of Sc (molecular formula: sc (NO)3)3) Iridium oxide containing 0.015 mol of Ir (molecular formula: IrO2) Praseodymium nitrate containing 0.01 mole of Pr (molecular formula: pr (NO)3)3) Sodium nitrate (molecular formula of NaNO) containing 0.04 mol of Na3) And stirred to dissolve the whole solution to obtain a solution I. Cobalt nitrate containing 0.04 mol of Co(formula: Co (NO))3)2) Adding the aqueous solution into the above solutions respectively, mixing, evaporating at 80 deg.C until the mixed solution is equivalent to VMo containing active component4Co0.4W0.4Sn0.4Sc0.15Ir0.15Pr0.1Na0.4OgWas 0.4g/g, to obtain a solution II.
2. Active element loading
200g of a spherical alumina carrier having a diameter of 5mm was uniformly mixed with 200g of the solution II, and dried at 80 ℃ for 4 hours to obtain a catalyst precursor I.
3. Roasting
Catalyst precursor I was calcined in a muffle furnace at 400 ℃ for 3 hours to give a catalyst of the following composition:
31w％VMo4Co0.4W0.4Sn0.4Sc0.15Ir0.15Pr0.1Na0.4Og+69w％Al2O3。
4. catalyst evaluation
The catalyst evaluation method of the present invention is as follows:
a reactor: a fixed bed reactor with an inner diameter of 25 mm and a reactor length of 750 mm;
catalyst loading: 200 g;
reaction temperature: 280 ℃;
reaction time: 4 hours;
the volume ratio of raw materials is as follows: acrolein: air: water vapor 1: 3.5: 2;
space velocity of raw materials: 1400 ml. h-1·g-1。
The elemental composition of the catalyst and the evaluation results of the catalyst are shown in Table 1 for convenience of comparison.
TABLE 1
Claims (10)
1. Catalyst for producing acrylic acid comprising a support andan active ingredient supported on a carrier, said active ingredient having the general formula: VMoaCobWcXdQeZfOgWherein X is at least one selected from the group consisting of Al, Ga, Ge, In, Sn, Sb, TI, Pb, Bi and Po, Q is at least one selected from the group consisting of Sc, Ti, Y, Zr, Hf, Ta, Tc, Re, Ru, Os, Rh, Ir, Pd, Pt, Ag, Au, Cd, La and Pr, and Z is at least one selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba and Ra; a is the molar ratio of Mo to V, and the value of a is 2.0-8.0; b is the molar ratio of Co to V, and the value of b is 0.1-1.0; c is the molar ratio of W to V, and the value of c is 0.1-1.0; d is the molar ratio of X to V, and the value of d is 0.1-1.0; e is the molar ratio of Q to V, and the value of e is 0.1-1.0; f is the molar ratio of Z to V, and the value of f is 0.1-1.0; g is the mole number of oxygen atoms needed to satisfy the valence of each element in the active component.
2. The catalyst according to claim 1, wherein the active component content in the catalyst is 10 to 80 w% by weight.
3. The catalyst according to claim 1, wherein the carrier content in the catalyst is 20 to 90 w% by weight.
4. The catalyst according to claim 1, wherein the carrier is at least one selected from the group consisting of alumina, lithium oxide, magnesia, zirconia, silica and titania.
5. A method of preparing the catalyst of claim 1, comprising:
preparing mixed liquid of active component elements;
mixing the active component element mixed solution with a carrier;
and (4) roasting.
6. The method according to claim 5, wherein the mixture is a solution, a suspension or a mixture of a solution and a suspension.
7. The method according to claim 5, wherein the calcination temperature is 300 to 600 ℃.
8. The method according to claim 5, wherein the calcination time is 1 to 15 hours.
9. The method according to claim 5, wherein the atmosphere for calcination is an inert atmosphere or an atmosphere containing O2Of the atmosphere (c).
10. Use of the catalyst of claim 1 in the manufacture of acrylic acid by oxidation of acrolein.
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