CN112774673B - Catalyst for preparing acrylic acid by acrolein air oxidation and preparation method and application thereof - Google Patents
Catalyst for preparing acrylic acid by acrolein air oxidation and preparation method and application thereof Download PDFInfo
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- CN112774673B CN112774673B CN202110160339.8A CN202110160339A CN112774673B CN 112774673 B CN112774673 B CN 112774673B CN 202110160339 A CN202110160339 A CN 202110160339A CN 112774673 B CN112774673 B CN 112774673B
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- catalyst
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- acrolein
- acrylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 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 45
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 38
- 239000010931 gold Substances 0.000 claims abstract description 36
- 229910052737 gold Inorganic materials 0.000 claims abstract description 33
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 22
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 11
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 27
- 239000012018 catalyst precursor Substances 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000009495 sugar coating Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 15
- 150000002344 gold compounds Chemical class 0.000 claims description 15
- 238000007792 addition Methods 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 125000003158 alcohol group Chemical group 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229940114077 acrylic acid Drugs 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229960000304 folic acid Drugs 0.000 description 1
- 235000019152 folic acid Nutrition 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 229960000587 glutaral Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 229960004452 methionine Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002562 thickening agent Substances 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing acrylic acid by air oxidation of acrolein, which consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the content of each component is as follows in percentage by mass of the catalyst: 0.5 to 5 percent of gold, 0.5 to 20 percent of auxiliary agent and the balance of carrier; the auxiliary agent is at least one of palladium, silver, chromium and manganese; the carrier is prepared by the following method: adding aluminum oxide into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 0.5-1 h, filtering, drying and roasting to obtain the carrier. Meanwhile, the invention also provides a preparation method of the catalyst and application of the catalyst in preparation of acrylic acid through acrolein air oxidation. The catalyst has stable catalytic performance and good repeatability.
Description
Technical Field
The invention belongs to the technical field of catalytic oxidation, and particularly relates to a catalyst for preparing acrylic acid by air oxidation of acrolein, and a preparation method and application thereof.
Background
Acrolein is an important intermediate for preparing fine chemical products, and is mainly used for producing D, L-methionine, folic acid, acrylic acid, glutaraldehyde required by animal feed additives, pyrimidine drugs for treating asthma and the like. In the industrial production of acrolein, a propylene air oxidation method is mainly used, and a multi-component composite oxide containing oxides of Bi, mo, te, etc. as main components is used as a catalyst. Propylene (PA)The product of aldehyde oxidation, acrylic acid, is a very important basic raw material and intermediate in modern chemical industry. Acrolein is mainly used for preparing important chemical products such as acrylic acid, methionine, 1, 3-propanediol and the like. Unrefined acrylic acid is mainly used for producing acrylic ester, refined acrylic acid is used for producing super absorbent resin, other acrylic acid is used for detergent polymers, and produced polyacrylate is used as a thickening agent, a dispersing agent, a rheological control agent and the like. The nanogold catalyst is concerned by pioneering work of Hamta et al. It has been found that the gold catalyst shows good catalytic performance in reactions such as low-temperature oxidation of CO, preparation of propylene oxide by epoxidation of propylene, water-vapor shift, liquid-phase selective oxidation and the like. However, the use of nanogold catalysts in the reaction of producing acrylic acid by air oxidation of propylene has been studied little. Gasior et al, mgO, siO prepared by deposition-precipitation 2 ，SnO 2 Equi-carrier supported Au catalysts were used for propylene air oxidation and a small amount of acrolein product was found to be formed. Au/SiO prepared by dipping method 2 The catalyst has a ratio Au/Al in the air oxidation reaction of propylene 2 O 3 Higher acrolein selectivity of the catalyst. In the acrylic acid industry, four major foreign technologies that have independent propylene oxidation and acrylic acid separation technologies are Mitsubishi chemical corporation (NSKK), mitsubishi catalytic chemical corporation (MCC), basf, germany, and Nippon Chemicals corporation (NKC). Among them, mitsubishi chemical company and catalytic chemical company have their own acrylic acid production kits, and domestic acrylic acid manufacturers must introduce their kits to use their catalysts. At present, the domestic research units engaged in acrylic acid catalysts mainly comprise the China Petroleum Lanzhou chemical research center, shanghai Huayi acrylic acid Co., ltd and Zhonghai oil Tianjin chemical research design institute. It is reported that the Shanghai Hua Yi acrylic acid Co., ltd is developed on the basis of the localization of acrylic acid production technology in cooperation with the national petroleum Lanzhou chemical research center. The Zhonghai oil Tianjin chemical research design institute is the research in the field only in recent years and still is in the beginning stage, and domestic catalysts and equipment for oxidizing acrolein into acrylic acid mainly depend on imported foreign technologies.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly provides a catalyst for preparing acrylic acid by air oxidation of acrolein and a preparation method and application thereof.
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 0.5 to 5 percent of gold, 0.5 to 20 percent of auxiliary agent and the balance of carrier;
the auxiliary agent is at least one of palladium, silver, chromium and manganese;
the carrier is prepared by the following method: adding aluminum oxide into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 0.5-1 h, filtering, drying and roasting to obtain the carrier; the mass ratio of the aluminum oxide to the mixed aqueous solution of sodium nitrate and zinc nitrate is 1. .
Preferably, the content of each component is as follows: 5% of gold, 20% of an auxiliary agent and the balance of a carrier; the auxiliary agent is palladium, silver, chromium and manganese.
Preferably, the drying condition is drying at 100-120 ℃ for 4-8h, and the roasting condition is roasting at 300-500 ℃ for 4-8h.
Preferably, the particle size of the alumina is 1.0mm-2.0mm, and the specific surface area is 300m 2 /g-800m 2 /g。
The preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound in a solvent, adjusting the pH value of the soluble gold compound to 3.0-8.0, then adding soluble salt of an auxiliary agent into the solution, and stirring the solution to obtain a precursor solution; the solvent is water or alcohol;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar-coating machine, then adding the atomized liquid drops into the carrier in batches, stirring uniformly after each addition, coating, and drying after each coating to obtain a catalyst precursor;
(4) And roasting the catalyst precursor in an air atmosphere.
Preferably, the soluble gold compound is chloroauric acid.
Preferably, the soluble salt of the auxiliary agent is a chloride or nitrate of the auxiliary agent.
Preferably, the dividing in step (3) is divided into 3 to 4 times.
Preferably, the drying temperature is 120 ℃, and the drying time is 4-12h; the roasting condition under the air atmosphere is that roasting is carried out for 2-6h at the temperature of 300-600 ℃.
Preferably, in the step (1), the pH is adjusted by using anhydrous sodium carbonate or anhydrous potassium carbonate.
The catalyst of the invention is applied to the preparation of acrylic acid by air oxidation of acrolein.
The catalyst of the invention is applied to the application of acrolein in air oxidation to prepare acrylic acid to evaluate the performance of the catalyst, and the specific conditions of the application are as follows:
the catalyst is filled in a stainless steel tube reactor with the inner diameter of 6mm, the filling amount is 1mL, the flow rate of acrolein is 0.05 mL/min, the air flow is 24mL/min, the reaction temperature is 250 ℃, and the raw material acrolein is preheated by a preheating furnace at 200 ℃ before reaction and then is introduced into the reactor. And after the reaction, performing qualitative and quantitative analysis on the product by using gas chromatography.
The invention has the advantages that:
1. the catalyst prepared by the invention takes specially processed alumina as a carrier, noble metal gold and auxiliary metal elements are highly dispersed on the carrier, and gold metal particles in the catalyst are uniformly distributed on the alumina carrier, so that the catalyst has good catalytic activity and selectivity;
2. the invention utilizes ultrasonic atomization equipment and sugar-coating machine equipment, and the preparation process can uniformly disperse and coat the metal components on the surface of the carrier, thereby improving the dispersibility of the metal components and the activity of the catalyst and simultaneously reducing the preparation difficulty of the catalyst;
3. the preparation method is easy to operate, the raw materials are easy to obtain, and large-scale industrial production is easy to realize. The prepared catalyst is convenient to recover after use, can realize the production-recovery-reproduction of noble metals, has less loss in the recovery process, and greatly reduces the production cost of the catalyst;
4. the catalyst prepared by the invention is suitable for preparing acrylic acid by acrolein oxidation, has high raw material conversion rate and selectivity, greatly improves the product yield, greatly reduces the production cost, and belongs to a high-efficiency green environment-friendly technology;
5. the catalytic method has the advantages of simple steps, mild conditions and environmental protection, and provides favorable conditions for large-scale application of the catalyst.
Detailed Description
The particle size of the alumina adopted in the embodiment of the invention is 1.0mm-2.0mm, and the specific surface area is 300m 2 /g-800m 2 The same alumina was used in each example.
Example 1
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the content of each component in percentage by mass of the catalyst is as follows: 5% of gold, 5% of assistant palladium and the balance of carrier;
the carrier is prepared by the following method: adding alumina into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 1h, filtering, drying at 120 ℃ for 4h, then placing in a muffle furnace, and roasting at 500 ℃ for 4h to obtain the carrier; the mass ratio of the aluminum oxide to the mixed aqueous solution of sodium nitrate and zinc nitrate is 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.5 by using anhydrous potassium carbonate, then adding the chloropalladite, and stirring to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding the carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor at 500 ℃ for 4h in an air atmosphere to obtain the catalyst labeled (5% Au-5% Pd)/Al 2 O 3 A catalyst.
Example 2
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 5% of gold, 5% of assistant palladium, 5% of assistant silver and the balance of carrier;
the carrier is the same as the carrier in the embodiment 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.5 by using anhydrous potassium carbonate, then adding the chloroauric acid and silver nitrate into the solvent, and stirring the mixture to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in air atmosphere at 500 deg.C for 4h to obtain a catalyst labeled (5% Au-5% 2 O 3 A catalyst.
Example 3
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 5% of gold, 5% of assistant palladium, 5% of assistant chromium and the balance of carrier;
the carrier is the same as the carrier in the embodiment 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.5 by using anhydrous potassium carbonate, then adding chloropalladic acid and chromium nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding the carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in an air atmosphere at 500 deg.C for 4h to obtain a catalyst labeled (5% Au-5% 2 O 3 A catalyst.
Example 4
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 5% of gold, 5% of auxiliary agent palladium, 5% of auxiliary agent manganese and the balance of carrier;
the carrier is the same as the carrier in the embodiment 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.5 by using anhydrous potassium carbonate, then adding chloropalladic acid and manganese nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in an air atmosphere at 500 ℃ for 4h to obtain the catalyst labeled (5% Au-5% by Pd-5% by Mn)/Al 2 O 3 A catalyst.
Example 5
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 5% of gold, 5% of auxiliary agent palladium, 5% of auxiliary agent silver, 5% of auxiliary agent chromium, 5% of auxiliary agent manganese and the balance of carrier;
the carrier is the same as the carrier in the embodiment 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.5 by using anhydrous potassium carbonate, then adding chloropalladic acid, silver nitrate, chromium nitrate and manganese nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in an air atmosphere at 500 ℃ for 4h to obtain the catalyst labeled (5% Au-5% by Pd-5% by Ag-5% 2 O 3 A catalyst.
Example 6
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 0.5% of gold, 0.5% of auxiliary agent silver and the balance of carrier;
the carrier is prepared by the following method: adding aluminum oxide into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 0.5h, filtering, drying at 100 ℃ for 8h, then placing in a muffle furnace, and roasting at 300 ℃ for 8h to obtain the carrier; the mass ratio of the aluminum oxide to the mixed aqueous solution of sodium nitrate and zinc nitrate is 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH of the solvent to 3.0 by using anhydrous potassium carbonate, then adding silver nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is an alcohol;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding the carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 4 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 4 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor at 300 deg.C for 6h in air atmosphere to obtain the catalyst labeled (0.5% Au-0.5% Ag)/Al 2 O 3 A catalyst.
Example 7
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 2% of gold, 0.5% of auxiliary agent chromium and the balance of carrier;
the carrier is prepared by the following method: adding aluminum oxide into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 0.5h, filtering, drying at 120 ℃ for 4h, then placing in a muffle furnace, and roasting at 500 ℃ for 4h to obtain the carrier; the mass ratio of the aluminum oxide to the mixed aqueous solution of sodium nitrate and zinc nitrate is 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH value of the solvent to 8.0 by using anhydrous sodium carbonate, then adding chromium nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is an alcohol;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar coating machine, then adding the atomized liquid drops into the carrier for 4 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 8 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in air atmosphere at 600 deg.C for 2h to obtain a catalyst labeled (2.0% Au-0.5% Cr)/Al 2 O 3 A catalyst.
Example 8
A catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the contents of the components in percentage by mass of the catalyst are as follows: 0.5% of gold, 0.5% of auxiliary agent manganese and the balance of carrier;
the carrier is the same as in example 7;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, adjusting the pH value of the solvent to 8.0 by using anhydrous potassium carbonate, then adding manganese nitrate into the solvent, and stirring to obtain a precursor solution; the solvent is an alcohol;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar coating machine, then adding the atomized liquid drops into the carrier for 4 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 8 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor in air atmosphere at 600 deg.C for 2h to obtain a catalyst labeled (0.5% Au-0.5% Mn)/Al 2 O 3 A catalyst.
Comparative examples 1 to 8
Comparative examples 1 to 8 were provided in the same manner as in examples 1 to 8 except that alumina was used as a carrier without any treatment in each example.
Comparative example 9
The catalyst is prepared by taking a gold/alumina catalyst obtained from a market as a comparative example 1, wherein the mass percent of gold in the catalyst is 5 percent, the particle size of the carrier is 1.0-2.0 mm, and the specific surface area is 500 m 2 The grain diameter of the gold is 10-30nm.
Comparative example 10
The method is the same as example 1 except that no auxiliary agent is contained, and the method comprises the following steps:
a catalyst for preparing acrylic acid by air oxidation of acrolein is composed of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the content of each component in percentage by mass of the catalyst is as follows: 5% of gold and the balance of carrier;
the carrier is the same as the carrier in the embodiment 1;
the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound chloroauric acid in a solvent, and adjusting the pH value of the solution to 3.5 by using anhydrous potassium carbonate to obtain a precursor solution; the solvent is water;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding the carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine for 3 times, uniformly stirring and coating after each addition, and drying at 120 ℃ for 12 hours after each coating to obtain a catalyst precursor;
(4) Calcining the catalyst precursor at 500 ℃ in an air atmosphere4h, i.e. the catalyst obtained was marked 5% Au/Al 2 O 3 A catalyst.
The catalysts provided in the examples of the present invention and the comparative examples were used for the production of acrylic acid by air oxidation of acrolein to evaluate the performance of the catalysts under the following conditions:
the catalyst is filled in a stainless steel tube reactor with the inner diameter of 6mm, the filling amount is 1mL, the flow rate of acrolein is 0.05 mL/min, the air flow is 24mL/min, the reaction temperature is 250 ℃, and the raw material acrolein is preheated by a preheating furnace at 200 ℃ before reaction and then is introduced into the reactor. After the reaction, qualitative and quantitative analysis of the product was performed by gas chromatography.
The evaluation results are shown in Table 1.
TABLE 1 evaluation results of different catalysts for air oxidation of acrolein to produce acrylic acid
In parallel, the same method was used to conduct repetitive tests on the production of acrylic acid by air oxidation of acrolein with each catalyst, and the conversion rate of raw material acrolein is shown in table 2.
TABLE 2 parallel test results of repeated catalysis of catalytic oxidation of acrolein by different catalysts
As is apparent from Table 2, the catalyst prepared by the method of the present invention has stable performance and good reproducibility.
Claims (9)
1. The application of the catalyst in preparing acrylic acid by air oxidation of acrolein is characterized in that: the catalyst consists of a carrier and metal components loaded on the carrier, wherein the metal components comprise gold and an auxiliary agent, and the content of each component is as follows in percentage by mass of the catalyst: 0.5 to 5 percent of gold, 0.5 to 20 percent of auxiliary agent and the balance of carrier;
the auxiliary agent is at least one of palladium, silver, chromium and manganese;
the carrier is prepared by the following method: adding aluminum oxide into a mixed aqueous solution of sodium nitrate and zinc nitrate, boiling, refluxing for 0.5-1 h, filtering, drying and roasting to obtain the carrier; the mass ratio of the aluminum oxide to the mixed aqueous solution of sodium nitrate and zinc nitrate is 1.
2. Use of a catalyst according to claim 1 in the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the contents of the components are as follows: 5% of gold, 20% of an auxiliary agent and the balance of a carrier; the auxiliary agent is palladium, silver, chromium and manganese.
3. Use of a catalyst according to claim 1 in the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the drying condition is drying at 100-120 ℃ for 4-8h, and the roasting condition is roasting at 300-500 ℃ for 4-8h.
4. Use of a catalyst according to claim 1 in the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the particle size of the alumina is 1.0mm-2.0mm, and the specific surface area is 300m 2 /g-800m 2 /g。
5. Use of a catalyst according to any one of claims 1 to 4 for the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the preparation method of the catalyst comprises the following steps:
(1) Dissolving a soluble gold compound in a solvent, adjusting the pH value of the soluble gold compound to 3.0-8.0, then adding soluble salt of an auxiliary agent into the solution, and stirring the solution to obtain a precursor solution; the solvent is water or alcohol;
(2) Ultrasonically atomizing the precursor solution to obtain atomized liquid drops;
(3) Adding a carrier into a sugar-coating machine, then adding the atomized liquid drops into the sugar-coating machine in batches, stirring uniformly after each addition for coating, and drying after each coating to obtain a catalyst precursor;
(4) And roasting the catalyst precursor in an air atmosphere.
6. Use of a catalyst according to claim 5 in the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the soluble gold compound is chloroauric acid.
7. Use of a catalyst according to claim 6 in the preparation of acrylic acid by air oxidation of acrolein, wherein: the soluble salt of the auxiliary agent is chloride or nitrate of the auxiliary agent.
8. Use of a catalyst according to claim 7 in the preparation of acrylic acid by air oxidation of acrolein, characterized in that: the batch in the step (3) is divided into 3 to 4 times.
9. Use of a catalyst according to claim 8 in the preparation of acrylic acid by air oxidation of acrolein, wherein: the drying temperature is 120 ℃, and the drying time is 4-12h; the roasting condition under the air atmosphere is that roasting is carried out for 2-6h at the temperature of 300-600 ℃.
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| CN108607550A (en) * | 2016-12-10 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of gold catalysts producing methyl methacrylate and its application |
| CN109304164B (en) * | 2017-07-28 | 2021-08-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrylic acid by glycerol one-step method |
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| CN110642709A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Method for preparing acrylic acid by acrolein oxidation |
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