CN106881123B - Composite oxide catalysts and its preparation method and application - Google Patents
Composite oxide catalysts and its preparation method and application Download PDFInfo
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- CN106881123B CN106881123B CN201510936834.8A CN201510936834A CN106881123B CN 106881123 B CN106881123 B CN 106881123B CN 201510936834 A CN201510936834 A CN 201510936834A CN 106881123 B CN106881123 B CN 106881123B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000002131 composite material Substances 0.000 title abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 8
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 5
- -1 phosphorus compound Chemical class 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 239000011133 lead Substances 0.000 abstract description 17
- 239000010949 copper Substances 0.000 abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000010931 gold Substances 0.000 abstract description 7
- 239000010948 rhodium Substances 0.000 abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052737 gold Inorganic materials 0.000 abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 4
- 239000011733 molybdenum Substances 0.000 abstract description 4
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 abstract description 3
- 239000010937 tungsten Substances 0.000 abstract description 3
- 125000004429 atom Chemical group 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000012153 distilled water Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000002002 slurry Substances 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000011964 heteropoly acid Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000011268 mixed slurry Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000004254 Ammonium phosphate Substances 0.000 description 8
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 8
- 235000019289 ammonium phosphates Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- 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
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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)
- Catalysts (AREA)
Abstract
Disclose composite oxide catalysts and its preparation method and application.The composition that there is following formula to indicate for the catalyst agent: Fe1DaEbPcOd·Ze, wherein Fe, P and O respectively indicate iron, phosphorus and oxygen atom；D is indicated selected from least one of copper, nickel, manganese, zinc, cobalt, molybdenum, vanadium or tungsten element；E is indicated selected from least one of palladium, lead, platinum, gold, silver, rhodium, ruthenium or rhenium element；Z is carrier diluent, is selected from SiC, SiO2、MoO3、Al2O3、CeO2Or TiO2One of or a variety of mixtures；A, b, c, d, e are indicated with Fe1Meter, the molar ratio of each component: a=0.01~2.0；B=0.01~2.0；C=0.3~3.0；E=5~100；D is the atom ratio of oxygen required for meeting the chemical valence of above-mentioned each component.
Description
Technical Field
The invention relates to a composite oxide catalyst which is suitable for catalyzing the oxidation reaction of unsaturated aldehyde to prepare unsaturated acid. The invention also relates to a preparation method of the catalyst and application of the catalyst in the reaction of preparing unsaturated acid by oxidizing unsaturated aldehyde.
Background
Methacrylic acid (MAA) is an important organic chemical raw material and is widely applied to the production of common products such as organic glass, environment-friendly coatings, lubricants, binders and the like. The process for preparing MAA by isobutene oxidation method is currently concerned by the advantages of wide raw material source, high atom utilization rate, small environmental pollution and the like. The process is generally that isobutene is partially oxidized to generate Methacrolein (MAL) under the action of a catalyst, and then the MAL is further oxidized to generate MAA under the action of the catalyst.
The MAA reaction generated by oxidizing the MAL mainly adopts a heteropoly acid compound containing phosphor and molybdenum as a catalyst at present. Patent WO2013172414A, US6498270B, JP2012030212A and the like show that the heteropoly acid compound has good conversion rate in oxidation of MAL and excellent selectivity to MAA, and thus most researchers are working on the study of the heteropoly acid compound at present to expect further improvement of the activity and selectivity of the catalyst.
Although the heteropoly acid compound has excellent activity and selectivity, the characteristics of complicated preparation process and easy decomposition at high temperature are fatal defects, which reduce the service life and the catalytic stability of the catalyst, so researchers have conducted a great deal of research on the composition, the preparation method and the use method of the heteropoly acid compound catalyst to improve the service life and the stability of the catalyst.
In patent CN104001542A, researchers have extended catalyst life by introducing metal oxides during the preparation of heteropolyacid catalysts.
In patent CN101679180A, researchers achieve the purpose of prolonging the service life of the catalyst by changing the pressure control of the reaction in stages or continuously during the reaction and by adjusting the molar ratio of the molecular oxygen in the reaction gas to the raw material.
However, the above-mentioned patent methods can only extend the catalyst life within a limited range, and cannot greatly increase the service life of the catalyst. In addition, in order to improve the catalyst selectivity, the above heteropoly acid catalysts mostly contain arsenic element, and precursor compounds of arsenic generally have strong corrosivity and are high in price, which increases the production cost of the catalyst.
In view of the above problems, there is a need in the art to develop a non-heteropoly acid system catalyst suitable for the preparation of methacrylic acid by the oxidation of methacrolein. The catalyst is required to have the advantages of low price, simple and convenient preparation, good stability and the like, and solves the problems of the heteropoly acid system catalyst in the reaction of preparing methacrylic acid by oxidizing methacrolein.
Disclosure of Invention
The invention aims to provide a catalyst suitable for the reaction of synthesizing methacrylic acid (MAA) by oxidizing Methacrolein (MAL), which has the advantages of simple preparation, low price and good stability.
It is another object of the present invention to provide a method for preparing the catalyst.
Accordingly, one aspect of the present invention provides a catalyst having a composition represented by the formula:
Fe1DaEbPcOd·Ze
wherein,
d represents at least one element selected from copper (Cu), nickel (Ni), manganese (Mn), zinc (Zn), cobalt (Co), molybdenum (Mo), vanadium (V) or tungsten (W);
e represents at least one element selected from palladium (Pd), lead (Pb), platinum (Pt), gold (Au), silver (Ag), rhodium (Rh), ruthenium (Ru) or rhenium (Re);
z is carrier diluent selected from SiC and SiO2、MoO3、Al2O3、CeO2Or TiO2A mixture of one or more of;
a. b, c, d and e are Fe1Counting the moles of other corresponding components;
a＝0.01～2.0；
b＝0.01～2.0；
c＝0.3～3.0；
e＝5～100；
d is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
Another aspect of the present invention relates to a process for preparing the catalyst of the present invention, comprising the steps of:
(i) dissolving a phosphorus compound in a solvent according to the composition of the catalyst to prepare a solution A; dissolving an iron compound in a solvent to prepare a solution B; dissolving a compound containing D and a compound containing E in a solvent, and adding a carrier diluent Z into the solvent to prepare a solution C;
(ii) mixing the A, B, C liquid at 30-150 ℃;
(iii) pre-roasting at 150-300 ℃ for 60-600 minutes under the flow of oxygen-containing gas to obtain a catalyst precursor;
(iv) shaping the pre-roasted catalyst, and roasting at 300-600 ℃ for 120-1440 minutes in an oxygen-containing atmosphere, wherein the volume space velocity of the oxygen-containing gas is 200-1500 h-1。
A further aspect of the invention relates to the use of the catalyst of the invention in the synthesis of methacrylic acid by oxidation of methacrolein.
Detailed Description
Iron phosphate materials have been widely studied as methacrylic acid catalysts prepared by oxidative dehydrogenation of isobutyric acid, and the catalysts show good selectivity to methacrylic acid in the reaction, and do not have the phenomenon similar to the decomposition of heteropolyacid salt catalysts at high temperature. The prior art has never been concerned with the use of such dehydrogenation catalysts in the oxidation of methacrolein to produce methacrylic acid.
The present inventors have found that an iron phosphate-based catalyst having a specific composition is suitable for catalyzing a reaction for producing methacrylic acid by oxidizing methacrolein. The present invention has been completed based on this finding.
1. Catalyst and process for preparing same
The present invention provides a heteropolyacid salt catalyst having a composition represented by the following formula:
Fe1DaEbPcOd·Ze
wherein, Fe1DaEbPcOdReferred to as the procatalyst; z is carrier diluent selected from SiC and SiO2、MoO3、Al2O3、CeO2Or TiO2A mixture of one or more of;
fe. P and O represent iron, phosphorus and oxygen atoms, respectively.
D represents at least one element selected from copper (Cu), nickel (Ni), manganese (Mn), zinc (Zn), cobalt (Co), molybdenum (Mo), vanadium (V), or tungsten (W), preferably at least one element selected from copper (Cu), cobalt (Co), or vanadium (V).
E represents at least one element selected from palladium (Pd), lead (Pb), platinum (Pt), gold (Au), silver (Ag), rhodium (Rh), ruthenium (Ru), or rhenium (Re), preferably at least one element selected from palladium (Pd), lead (Pb), gold (Au), ruthenium (Ru), or rhenium (Re).
a. b, c, d and e represent the atomic ratios of the respective elements:
a is 0.01 to 2.0, preferably 0.05 to 1.5, more preferably 0.1 to 1.2, and most preferably 0.2 to 1.0.
In a preferred embodiment of the present invention, a is a numerical range formed by any two of 0.01, 2.0, 0.05, 1.5, 0.1, 1.2, 0.2 and 1.0 as endpoints.
b is 0.01 to 2.0, preferably 0.03 to 1.5, more preferably 0.05 to 1.0, most preferably 0.08 to 0.8, most preferably 0.1 to 0.5.
In one example of the present invention, b is a numerical range formed by any two of 0.01, 2.0, 0.03, 1.5, 0.05, 1.0, 0.08, 0.8, 0.1 and 0.5 as endpoints.
c is 0.3 to 3.0, preferably 0.5 to 2.5, more preferably 0.8 to 2.0, and most preferably 1.0 to 1.5.
In one example of the present invention, c is a numerical range formed by any two of 0.3, 3.0, 0.5, 2.5, 0.8, 2.0, 1.0, and 1.5 as endpoints.
e is 5 to 100, preferably 10 to 80, more preferably 15 to 70, and most preferably 20 to 65.
In one example of the present invention, e is a numerical range formed by any two of 5, 100, 10, 80, 15, 70, 20, and 65 as endpoints.
d is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
In a preferred embodiment of the present invention, the catalyst is selected from the group consisting of: fe1Cu0.5Pb0.2Ru0.05P1.5·Ze、Fe1Co0.5Ni0.3Pd0.03P2·Ze、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·Ze、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·ZeOr a mixture of two or more thereof, wherein Z and e are both as defined above.
In a preferred embodiment of the invention, the catalyst is selected from the group consisting of Fe1Cu0.5Pb0.2Ru0.05P1.5·(Al2O3)5、Fe1Co0.5Ni0.3Pd0.03P2·(Al2O3)5、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(Al2O3)5、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(SiO2)5Or a mixture of two or more thereof.
2. Preparation method of the catalyst of the invention
The above-mentioned catalyst of the present invention can be prepared by a conventional method known in the art. In a preferred embodiment of the present invention, the catalyst is prepared by the following method:
(i) dissolving precursor compounds of corresponding component elements to respectively serve as solution A, solution B and solution C;
(ii) mixing the three kinds of feed liquids at 30-150 ℃ to prepare a suspension dispersion slurry of the catalyst precursor containing all the catalyst components;
(iii) and the dried catalyst precursor is subjected to pre-roasting and roasting processes to obtain the finished catalyst.
In one embodiment of the invention, a carrier diluent is also added to liquor C at the time of preparation of liquor C to form a suspension, followed by drying, pre-firing and firing steps.
In a preferred embodiment of the present invention, the preparation method of the present invention comprises the steps of:
(i) dissolving a phosphorus compound in a solvent according to the composition of the catalyst to prepare a solution A; dissolving an iron compound in a solvent to prepare a solution B; dissolving the compound containing D and the compound containing E in a solvent, and adding a carrier diluent Z into the solvent to prepare a solution C.
(a) The solution A is prepared by dissolving at least a phosphorus compound in a solvent. Besides phosphorus, the solution A may also contain O atoms and ammonium groups. In one embodiment of the present invention, as the catalyst raw material for preparing the liquid A, non-limiting examples of the phosphorus-containing compound include phosphorus pentoxide, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and the like, preferably ammonium phosphate.
The solvent and temperature required for dissolving the material in solution A are not particularly limited as long as the compound used can be completely dissolved or uniformly mixed, and examples of the solvent include water and ethanol, and water is preferably used. The amount of water is about 100 to 1000 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by weight of the total amount of the compounds for preparing the slurry.
(b) The solution B is prepared by dissolving an iron compound in a solvent, and non-limiting examples of the iron compound include iron oxide, iron chloride, iron nitrate, iron acetate, and the like, and preferably iron nitrate.
The solvent and temperature required for dissolving the material in the solution B are not particularly limited as long as the compound to be used can be completely dissolved or uniformly mixed, and examples of the solvent include water and ethanol, and water is preferably used. The amount of water is about 100 to 300 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the total amount of the compounds for preparing the slurry.
(c) The solution C is prepared by dissolving compounds of D and E in a solvent, and non-limiting examples of the compounds containing D and E include oxides, chlorides, nitrates, acetates, oxoacids or oxoacid salts, etc., preferably nitrates; after the D, E-containing compound is dissolved in the solvent, the carrier Z is immersed.
The solvent and temperature required for dissolving the material in the solution C are not particularly limited as long as the compound to be used can be completely dissolved or uniformly mixed, and examples of the solvent include water and ethanol, and water is preferably used. The amount of water is about 100 to 300 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of the total amount of the compounds for preparing the slurry.
The ratio of each active component in the catalyst of the invention is based on the iron atom ratio of 1, and the phosphorus ratio is 0.3-3.0, preferably 0.5-2.5, more preferably 0.8-2.0, and most preferably 1.0-1.5. The kind and use ratio of other active components required are determined according to the use conditions of the catalyst and the like to obtain a catalyst having the most appropriate performance. In general, the proportion of the element D is 0.01 to 2.0, preferably 0.05 to 1.5, more preferably 0.1 to 1.2, and most preferably 0.2 to 1.0; the proportion of the element E is 0.01 to 2.0, preferably 0.03 to 1.5, more preferably 0.05 to 1.0, most preferably 0.08 to 0.8, most preferably 0.1 to 0.5.
The amount of the carrier diluent Z added is 5 to 100, preferably 10 to 80, more preferably 15 to 70, and most preferably 20 to 65 moles of the carrier based on the iron atom ratio of 1.
(ii) Mixing the A, B, C solution at 30-150 deg.C
And when the mixed slurry is prepared, mixing the solution A, the solution B and the solution C at the temperature of 30-150 ℃ to obtain the high-activity catalyst. The mixing temperature of the solution A, the solution B and the solution C is preferably 40 to 130 ℃, more preferably 50 to 100 ℃, and most preferably 60 to 90 ℃. In a preferred embodiment of the present invention, the mixing temperature is a temperature range formed by taking any two of 30 ℃, 150 ℃, 40 ℃, 130 ℃, 50 ℃, 100 ℃, 60 ℃ and 90 ℃ as endpoints.
The mixing sequence has no special requirements, and the method can be suitable for mixing the A + B mixed solution obtained by mixing the A solution and the B solution with the C solution; mixing the A + C mixed solution obtained by mixing the A solution and the C solution with the B solution; and a method of mixing the liquid A with a liquid B + C mixture obtained by mixing the liquid B and the liquid C. Among them, a preferable method is a method of mixing a liquid A + B mixed solution obtained by mixing the liquid A and the liquid B with the liquid C. Mixing is usually carried out while stirring to obtain a homogeneous suspension slurry.
Next, the slurry obtained above is dried, and there is no particular requirement for the drying method and temperature, and spray drying, evaporation drying, drum drying, and the like can be selected, and spray drying is preferable.
(iii) Pre-roasting at 150-300 ℃ for 60-600 minutes in the presence of oxygen-containing gas to obtain a catalyst precursor
The method comprises pulverizing the obtained dried catalyst precursor as required, and pre-calcining at 150-300 deg.C, preferably 200-280 deg.C, under the circulation of oxygen-containing gas such as air. The pre-roasting time is 60-600 minutes, preferably 120-300 minutes.
(iv) Shaping the pre-roasted catalyst, and roasting at 300-600 ℃ for 120-1440 minutes in an oxygen-containing atmosphere, wherein the volume space velocity of the oxygen-containing gas is 200-1500 h-1。
In the present invention, there is no particular requirement for the catalyst molding method, and known dry and wet molding methods such as a tablet molding method, an extrusion molding method, a pellet molding method and the like can be used. The shape of the molded article is not particularly limited, and a desired shape such as a cylindrical shape, a ring shape, or a spherical shape can be selected.
The roasting of the catalyst needs to be carried out in an oxygen-containing atmosphere, and the roasting temperature is selected to be 300-600 ℃, preferably 350-550 ℃, and preferably 380-500 ℃. The baking time is 120 to 1440 minutes, preferably 240 to 1200 minutes, more preferably 300 to 720 minutes. Oxygen-containing atmosphere with oxygen concentration of not less than 10% by mass, preferablyNot less than 20%, preferably air. During roasting, the circulation speed of gas is measured by a volume airspeed meter and is 200-1500 h-1Preferably 400 to 1200h-1Preferably 500 to 1000 hours-1。
3. Use of the catalyst of the invention
The catalyst prepared by the above method can be used for synthesizing methacrylic acid by gas phase oxidation of methacrolein. In one embodiment of the present invention, the gas phase oxidation reaction comprises the steps of: raw materials of methacrolein, air or a diluted gas mixture containing molecular oxygen and steam are preheated and then introduced into a fixed bed tubular reactor filled with a catalyst for selective oxidation reaction to synthesize methacrylic acid. The molecular oxygen in the diluent gas mixture can be pure oxygen, oxygen-enriched oxygen or air, and the diluent gas can be N2、CO、CO2Or H2O or a mixture of O and O in any proportion.
The oxidation reaction conditions are as follows: the temperature is 220-290 ℃, and preferably 230-280 ℃; the pressure is 0.05-0.5 MPa, and the normal pressure is preferred; the total airspeed of the mixed gas of the reaction raw materials is 600-5000 h-1Preferably 1000 to 3000 hours-1(ii) a The molar concentration of the methacrolein is 1-20%, preferably 3-10%; o is2The molar ratio of the methyl acrolein to the methyl acrolein is 1-8, preferably 2-4; the molar ratio of the water vapor to the methacrolein is 2 to 10, preferably 3 to 8.
The preparation of the high performance catalyst and its performance in catalyzing the selective oxidation of methacrolein to methacrylic acid will now be illustrated by the following specific examples, but the scope of the present invention is not limited to these examples.
Examples
In the following examples, the conversion and selectivity of the synthesis of methacrylic acid by oxidation of methacrolein were calculated using the following formulas:
methacrolein conversion (%) [ (amount of methacrolein before reaction-amount of methacrolein after reaction)/amount of methacrolein before reaction ] × 100%
Methacrylic acid selectivity (%) - (amount of methacrylic acid formed by reaction/amount of methacrolein reacted) × 100%
Example 1
1. Preparation of the catalyst
Dissolving 37.7 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 15 g of copper nitrate, 8.2 g of lead nitrate and 1.28 g of ruthenium trichloride were dissolved in 50 g of distilled water, and 63.1 g of Al was added2O3And stirring and mixing uniformly to obtain slurry C.
Heating the solution A to 80 ℃, pouring the solution B into the solution A under the stirring condition, continuing to stir for 10 minutes, pouring the mixed solution C into the mixed solution AB to obtain mixed slurry ABC, and continuing to stir for 1 hour at 80 ℃ to obtain mixed slurry containing the catalyst precursor.
The slurry was dried at 120 ℃ for 24 hours to give a solid powder. Roasting at 250 ℃ for 3 hours in air atmosphere, adding a proper amount of distilled water into 40 g of solid powder, extruding and molding to prepare 10-20-mesh particles, and roasting at 500 ℃ for 10 hours in air flow with air space velocity of 1000 hours-1And finally obtaining the finished catalyst. The catalyst composition is Fe1Cu0.5Pb0.2Ru0.05P1.5·(Al2O3)5。
2. Evaluation of catalyst Performance
25 g of 10-20 mesh catalyst particles are put into a fixed bed shell-and-tube reactor and are subjected to reaction at 290 ℃ under normal pressure,
MAL:O2:N2:H2O is 1:2.4:8:10, and the space velocity is 1250h-1The selective oxidation reaction is carried out under the conditions. After the reaction was carried out for 80 hours, the reaction product was collected and analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 1
1. Preparation of the catalyst
Dissolving 37.7 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 15 g of copper nitrate was dissolved in 50 g of distilled water, and the solution C was obtained by stirring and mixing the solution.
Heating the solution A to 80 ℃, pouring the solution B into the solution A under the condition of stirring, continuing stirring for 10 minutes, pouring the mixed solution C into the mixed solution AB, and adding 63.1 g of Al2O3Stirring was continued at 80 ℃ for 1 hour to obtain a mixed slurry containing the catalyst precursor.
The slurry was dried at 120 ℃ for 24 hours to give a solid powder. Roasting for 3 hours at 250 ℃ in air atmosphere, then taking 40 g of solid powder and a proper amount of distilled water, extruding and molding to prepare 10-20 mesh particles, and then roasting for 10 hours in 500 ℃ air flow with air airspeed of 1000 hours-1And finally obtaining the finished catalyst. The catalyst composition is Fe1Cu0.5P1.5·(Al2O3)5。
2. Evaluation of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and the reaction results are shown in Table 1.
Comparative example 2
1. Preparation of the catalyst
Dissolving 37.7 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 15 g of copper nitrate and 8.2 g of lead nitrate were dissolved in 50 g of distilled water, and 63.1 g of Al was added2O3Stirring and mixing uniformlyTo obtain a solution C.
And (3) heating the solution A to 80 ℃, pouring the solution B into the solution A under the stirring condition, continuing to stir for 10 minutes, pouring the mixed solution C into the mixed solution AB, and continuing to stir for 1 hour at 80 ℃ to obtain mixed slurry containing the catalyst precursor.
The slurry was dried at 120 ℃ for 24 hours to give a solid powder. Roasting at 250 ℃ for 3 hours in air atmosphere, adding a proper amount of distilled water into 40 g of solid powder, extruding and molding to prepare 10-20 mesh particles, and roasting at 500 ℃ for 10 hours in air flow with air space velocity of 1000 hours-1To obtain the final finished catalyst, wherein the catalyst composition is Fe1Cu0.5Pb0.2P1.5·(Al2O3)5。
2. Evaluation of catalyst Performance
The catalyst evaluation conditions were the same as in example 1, and the reaction results are shown in Table 1.
Example 2
1. Preparation of the catalyst
Dissolving 50.3 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 18 g of cobalt nitrate, 10.8 g of nickel nitrate and 0.66 g of PdCl2Dissolved in 50 g of distilled water, and 63.1 g of Al was added2O3And stirring and mixing uniformly to obtain slurry C.
Heating the solution A to 80 ℃, pouring the solution B into the solution A under the stirring condition, continuing to stir for 10 minutes, pouring the mixed solution C into the AB mixed solution to obtain ABC mixed slurry, and continuing to stir for 30 minutes at 80 ℃ to obtain mixed slurry containing the catalyst precursor.
The slurry was dried at 150 ℃ for 24 hours to give a solid powder. Roasting at 250 deg.C for 3 hr in air atmosphere, adding 40 g of solid powderAdding a proper amount of distilled water, extruding and molding, preparing into particles of 10-20 meshes, and then roasting in air flow at 500 ℃ for 16 hours at an air space velocity of 800 hours-1And finally obtaining the finished catalyst. The catalyst composition is Fe1Co0.5Ni0.3Pd0.03P2·(Al2O3)5。
2. Evaluation of catalyst Performance
20 g of 10-20 mesh catalyst particles are put into a fixed bed shell-and-tube reactor, and the temperature and the pressure are 280 ℃ and the pressure are normal, and the MAL is O2:N2:H2O is 1:2:8:10, space velocity is 1250h-1The selective oxidation reaction is carried out under the conditions. After the reaction was carried out for 80 hours, the reaction product was collected and analyzed by gas chromatography, and the reaction results are shown in Table 1.
Comparative example 3
1. Preparation of the catalyst
Dissolving 50.3 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 18 g of cobalt nitrate, 10.8 g of nickel nitrate and 0.66 g of PdCl2Dissolved in 50 g of distilled water, and stirred and mixed uniformly to obtain slurry C.
Heating the solution A to 80 ℃, pouring the solution B into the solution A under the stirring condition, continuing to stir for 10 minutes, pouring the mixed solution C into the AB mixed solution to obtain ABC mixed slurry, and continuing to stir for 30 minutes at 80 ℃ to obtain mixed slurry containing the catalyst precursor.
The slurry was dried at 150 ℃ for 24 hours to give a solid powder. Roasting at 250 ℃ for 3 hours in air atmosphere, taking 40 g of solid powder, adding a proper amount of distilled water, extruding and molding to prepare 10-20 mesh particles, roasting at 250 ℃ for 16 hours in air flow with air airspeed of 850 hours-1And obtaining the finished product catalyst. The catalyst composition is Fe1Co0.5Ni0.3Pd0.03P2。
2. Evaluation of catalyst Performance
The catalyst evaluation conditions were the same as in example 2. After the reaction was carried out for 80 hours, the reaction product was collected and analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 3
Dissolving 37.7 g of ammonium phosphate in 300 g of distilled water to obtain a solution A; dissolving 50 g of ferric nitrate in 50 g of distilled water to obtain a solution B; 7.2 g of cobalt nitrate, 4.8 g of ammonium metavanadate, 4.1 g of lead nitrate and 0.44 g of PdCl2Dissolved in 50 g of distilled water, and 63.1 g of Al was added2O3And stirring and mixing uniformly to obtain slurry C.
Heating the solution A to 80 ℃, pouring the solution B into the solution A under the stirring condition, continuing to stir for 10 minutes, pouring the mixed solution C into the AB mixed solution to obtain ABC mixed slurry, and continuing to stir for 30 minutes at 80 ℃ to obtain mixed slurry containing the catalyst precursor.
The slurry was dried at 120 ℃ for 16 hours to give a solid powder. Roasting at 250 ℃ for 3 hours in air atmosphere, adding a proper amount of distilled water into 40 g of solid powder, extruding and molding to prepare 10-20 mesh particles, and roasting at 500 ℃ for 10 hours in air flow with air space velocity of 800h-1And finally obtaining the finished catalyst. The catalyst composition is Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(Al2O3)5。
2. Evaluation of catalyst Performance
20 g of 10-20 mesh catalyst particles are put into a fixed bed shell-and-tube reactor, and the temperature and the pressure are 280 ℃ and the pressure are normal, and the MAL is O2:N2:H2O is 1:2:8:10, space velocity is 1250h-1The selective oxidation reaction is carried out under the conditions. After the reaction was carried out for 80 hours, the reaction product was collected and analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 4
1. Preparation of the catalyst
The catalyst preparation was the same as in example 3, except that in the case of slurry C, 63.1 g of Al was added2O3Changed to 37.2 g SiO2Obtaining the catalyst with the composition of Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(SiO2)5。
2. Evaluation of catalyst Performance
The catalyst evaluation conditions were the same as in example 2. After the reaction was carried out for 80 hours, the reaction product was collected and analyzed by gas chromatography, and the reaction results are shown in Table 1.
Example 5
The catalyst and catalyst performance evaluation conditions were the same as in example 3, and the reaction product was collected after 7000 hours of reaction and subjected to gas chromatography analysis, and the reaction results are shown in table 1.
TABLE 1 results of the reaction
Claims (11)
1. A catalyst for the oxidative synthesis of methacrylic acid from methacrolein, having a composition represented by the formula:
Fe1Cu0.5Pb0.2Ru0.05P1.5·Zeor Fe1DaEbPcOd·Ze
Wherein,
fe. P and O represent iron, phosphorus and oxygen atoms, respectively;
d represents at least one element selected from nickel, cobalt and vanadium;
e represents at least one element selected from palladium, lead and ruthenium;
z is carrier diluent selected from SiC and SiO2、MoO3、Al2O3、CeO2Or TiO2A mixture of one or more of;
a. b, c, d, e represent Fe1In terms of mole ratio of each component:
a＝0.2-1.0；
b＝0.03-0.5；
c＝1-1.5；
e＝5-65；
d is an atomic ratio of oxygen required to satisfy the valences of the respective components described above.
2. The catalyst of claim 1, wherein e is 20 to 65 and b is 0.1 to 0.5.
3. The catalyst of claim 1 selected from the group consisting of: fe1Cu0.5Pb0.2Ru0.05P1.5·Ze、Fe1Co0.5Ni0.3Pd0.03P2·Ze、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·ZeOr a mixture of two or more thereof, wherein Z and e are both as defined above.
4. The catalyst of claim 1 selected from the group consisting of: fe1Cu0.5Pb0.2Ru0.05P1.5·(Al2O3)5、Fe1Co0.5Ni0.3Pd0.03P2·(Al2O3)5、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(Al2O3)5、Fe1Co0.2V0.3Pb0.1Pd0.02P1.5·(SiO2)5Or itA mixture of two or more.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, which comprises:
(i) dissolving a phosphorus compound in a solvent according to the composition of the catalyst to prepare a solution A; dissolving an iron compound in a solvent to prepare a solution B; dissolving a compound containing D and a compound containing E in a solvent, and adding a carrier diluent Z into the solvent to prepare a solution C;
(ii) mixing the A, B, C solution at 30-150 ℃;
(iii) pre-roasting under the flow of oxygen-containing gas to obtain a catalyst precursor;
(iv) molding the pre-roasted catalyst;
(v) and roasting in an oxygen-containing atmosphere to obtain the finished catalyst.
6. The process according to claim 5, wherein the mixing temperature in step (ii) is 40 to 130 ℃.
7. The process according to claim 5, wherein the mixing temperature in step (ii) is 50 to 100 ℃.
8. The process according to claim 5, wherein the mixing temperature in step (ii) is 60 to 90 ℃.
9. The process according to any one of claims 5 to 8, wherein step (iii) is pre-baked at 150 to 300 ℃ for 60 to 600 minutes in the presence of a flow of oxygen-containing gas.
10. The method according to any one of claims 5 to 8, wherein the calcination in step (v) is carried out in an oxygen-containing atmosphere at 300 to 600 ℃ for 120 to 1440 minutes at a volumetric space velocity of the oxygen-containing gas of 200 to 1500 hours-1。
11. Use of the catalyst according to any one of claims 1 to 4 in the synthesis of methacrylic acid from methacrolein by oxidation.
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