EP1171237A1 - Vanadium-phosphoroxid-katalysator mit einem thermisch leitfähigen träger - Google Patents
Vanadium-phosphoroxid-katalysator mit einem thermisch leitfähigen trägerInfo
- Publication number
- EP1171237A1 EP1171237A1 EP00923307A EP00923307A EP1171237A1 EP 1171237 A1 EP1171237 A1 EP 1171237A1 EP 00923307 A EP00923307 A EP 00923307A EP 00923307 A EP00923307 A EP 00923307A EP 1171237 A1 EP1171237 A1 EP 1171237A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- vanadium
- catalyst
- thermally conductive
- conductive material
- phosphorus oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000004020 conductor Substances 0.000 claims abstract description 40
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 35
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- -1 vanadium (IV) phosphate compound Chemical class 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001298 alcohols Chemical class 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000013019 agitation Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000000184 acid digestion Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000011066 ex-situ storage Methods 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 37
- 229910052582 BN Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- WWDQUBKFDJXHAH-UHFFFAOYSA-B vanadium(4+);tetraphosphate Chemical compound [V+4].[V+4].[V+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WWDQUBKFDJXHAH-UHFFFAOYSA-B 0.000 claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000006872 improvement Effects 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- 239000001273 butane Substances 0.000 abstract description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002243 precursor Substances 0.000 description 18
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 11
- 229910010271 silicon carbide Inorganic materials 0.000 description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JIVYCRGHMCUGSH-UHFFFAOYSA-D [V+5].[V+5].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O Chemical compound [V+5].[V+5].OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O.OP([O-])([O-])=O JIVYCRGHMCUGSH-UHFFFAOYSA-D 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 241000208199 Buxus sempervirens Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
- BEWOAKBGXRYCFD-UHFFFAOYSA-N O.[Si].[Si] Chemical compound O.[Si].[Si] BEWOAKBGXRYCFD-UHFFFAOYSA-N 0.000 description 1
- 229910000540 VOPO4 Inorganic materials 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- CAUHCBDRRFADDB-UHFFFAOYSA-A [V+5].[V+5].[V+5].[V+5].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[V+5].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CAUHCBDRRFADDB-UHFFFAOYSA-A 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 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
- 239000012688 phosphorus precursor Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Definitions
- It is an object of this invention is to further advance the technology of NPO catalysis by providing for a NPO catalyst combined with a thermally conductive material particularly effective for hydrocarbon oxidation.
- Figure 1 is a plot of the yield of maleic anhydride versus reaction temperature for the oxidation of n-butane using vanadium phosphorus oxide catalysts combined with boron nitride compared to phosphorus treated boron nitride and vanadium phosphorus oxide. Data from Comparative Example 2 (vanadium phosphorus oxide) and Examples 1 (vanadium phosphorus oxide supported on boron nitride are shown in this figure.
- a comparison is also made to the comparative catalyst (Comparative Example 1), vanadium phosphorus oxide supported on silicon carbide and Comparative Example 2 (vanadium phosphorus oxide).
- the catalyst of this invention comprises vanadium phosphorus oxide combined with a thermally conductive material.
- vanadium phosphorus oxide it is meant a compound containing the elements vanadium, phosphorus and oxygen, and which is catalytically active in exothermic catalytic reactions, especially hydrocarbon oxidations. Vanadium pyrophosphate is an example of such compounds that may be useful.
- the vanadium phosphorus oxide may contain promoters, especially those known to improve activity in hydrocarbon oxidations, such as those described in G. J. Hutchings, Applied Catalysis, 72 (1991), Elsevier Science Publishers B. V. -Amsterdam, pages 1-31.
- the amount of vanadium phosphorus oxide in the catalyst should be in the range of 0.1 to 90 wt %, based on the total weight of the catalyst.
- the vanadium phosphorus oxide is present in an amount of 5 to 50 wt %, and most preferably 10 to 40 wt %.
- thermally conductive materials can be used. These include silicon nitride, and boron nitride. As described in this invention, preferably boron nitride is boron nitride treated with a phosphorous containing compound.
- the catalysts can be in any form wherein vanadium phosphorus oxide is combined with, for example, or intimately associated with, the thermally conductive support. Preferably, the catalyst will comprise a "core" of the thermally conductive material, a "shell" of the vanadium phosphorus oxide compound and a transition phase intermediate between the core and the shell which contains the elements of the thermally conductive material, and vanadium, phosphorus and oxygen. However, the catalysts may also be in a form wherein the vanadium phosphorus oxide is bound to the thermally conductive material, in such a manner where no transition phase can be seen.
- a chemical reaction of the vanadium phosphorus oxide catalyst onto the thermally conductive material is preferred. Mechanical mixing of the vanadium phosphorus oxide with the thermally conductive material is also possible. Process to Prepare Catalyst
- a suspension of vanadium (IV) phosphate in a liquid medium is formed.
- the liquid medium comprises with at least one substantially anhydrous unsubstituted alcohol having 1-10 carbon atoms, 1-3 hydroxyl groups and free from olefinic double bonds.
- Vanadium phosphorus oxide precursor is prepared by mixing vanadium pentoxide with the alcohol-containing medium, and heating the mixture to form a feed of vanadium oxide reduced to a valence of between 4 and 4.6.
- the vanadium oxide feed is then contacted with a solution comprising orthophosphoric acid and at least one substantially anhydrous unsubstituted alcohol having 1-10 carbon atoms, 1-3 hydroxyl groups and free from olefinic double bonds.
- the liquid medium comprises water and vanadium (IV) phosphate can be formed by the hydrochloric acid digestion of V 2 O 5 and H3PO4 in an aqueous solvent, as described, for example, in U.S. Patent 3,985,775, the disclosure of which is incorporated herein by reference.
- vanadium pentoxide, orthophosphoric acid and anhydrous alcohol of the type described above can be used in the practice of this process.
- a thermally conductive material is added to a suspension containing the vanadium phosphorus oxide precursor (formed by refluxing the mixture of V2O5 and orthophosphoric acid for 1-4 hours) under agitation.
- the thermally conductive material is maintained between a temperature between 40°C and 120°C to form vanadium (IV) phosphate combined with the thermally conductive material.
- the rapid crystallization of the vanadium (IV) phosphate should be avoided, as that would result in a mixture of crystallized vanadium (IV) phosphate and the thermally conductive material, rather than the of this invention.
- the catalysts of this invention may be further processed to impart attrition resistance by methods known in the art, such as, for example, by applying a coating of Si ⁇ 2 in accordance with U.S. Patent 4,677,084, the disclosure of which is incorporated herein by reference. This further process is particularly applied when the thermally conductive material is in the form of a fine powder.
- the catalysts of this invention are well suited for use as catalysts in exothermic reactions, especially hydrocarbon oxidations, in any type of reactor, for example, fixed bed, fluidized bed and recirculating solids reactor.
- the thermally conductive support acts as a heat sink
- the catalysts of this invention can be utilized at higher temperatures than the corresponding catalyst in the absence of thermally conductive material. More specifically, the catalyst is well suited to be efficiently utilized in fixed bed reactors with improved selectivity at high butane concentrations.
- Silicon carbide was provided in the form of grains having a particle size of ⁇ 0.3 mm. Under vigorous agitation, 10 g of silicon carbide at 80°C was added to the solution (10 g of silicon carbide) prepared according to U.S. 5,460,759 and 5,427,761 was added as a hot powder to the hot reflux containing the vanadium hydrogen phosphate hemihydrate suspension in the solvent. The temperature was increased to 130°C for approximately 15 minutes, which led to some evaporation of the solvent. When the temperature of the mixture reaches about 135°C the drying process was engaged under partial vacuum to obtain a suspension having a " mud" -like consistency, which was placed in a glass vessel and dried at 150°C for 12-15 hours in air.
- Patent 4,132,670 by heating the material to a temperature of 380°C at 3°C per minute under air flow rate of 1.5 cc per minute and held at 380°C for 2 hours. The material was then heated to a temperature of 480°C at 3°C per minute under air/butane (1.5% by volume of butane) flow rate of 3 cc per minute and held at 480°C for 15 hours. The material was allowed to cool to 420°C under air/butane (1.5% by volume of butane) flow of 17 cc per minute for 100 hours. This produced an " activated catalyst" . The activated catalyst was further stabilized by subjecting the catalyst to 200 hours of the air butane flow at 420°C. The activated catalyst contained 30 wt % vanadium phosphorus oxide; 30 wt % (VO) 2 P 2 O7, 70 wt % SiC; based on V, P determined by atomic absorption (AA).
- AA atomic absorption
- Catalytic reactions were carried out using an automated continuous flow fixed-bed microreactor system.
- the reactor consisted of a 6.35 mm o. d. stainless steel tube having an internal diameter of 4.57 mm. Heating the reactor tube was achieved by placing it in an isothermal fluidized sandbath in which silicon carbide was used as the fluidized heat transfer medium. The reactor temperature was controlled by monitoring the external microreactor wall tempreature at the midpoint of the catalyst bed. In a typical experiment, the reactor was packed with about 0.50 g of 0.125 mm to 0.5 mm particles of supported catalyst or catalyst precursor. Catalytic tests were run on the stabilized material and compared to a conventional bulk VPO catalyst, prepared in accordance with the process described in U.S. Patent 4,132,670.
- Catalyst testing was based on performance of the catalysts in the oxidation of n-butane to maleic anhydride.
- the oxidation reactions were performed at temperatures ranging from 310 to 470°C.
- Anhydrous phosphoric acid was prepared in the inert atmosphere drybox by mixing 257.4 g of 85 + % phosphoric acid (J. T. Baker and Co., Phillipsburg, NJ) with 99.6 g of anhydrous phosphorus pentoxide (J. T. Baker). The anhydrous phosphoric acid was then added to the addition funnel, brought outside of the drybox, and attached to the round bottom flask. The vanadium pentoxide and alcohols were held at reflux temperatures for one hour. Anhydrous phosphoric acid was then added dropwise over a period of two hours. Following this procedure, the reflux continued for a period of fifteen additional hours. The precipitated solids were then filtered in a buchner funnel and dried in flowing nitrogen at 80-125°C for a period of 16 hours to yield the catalyst precursor.
- the precursor was calcined and activated in a small, 4 cm fluidized bed reactor. Prior to the activation, fine particles were sieved out on a 400 mesh screen.
- the calcination/activation procedure was accomplished using the following conditions: a) 25-390°C in air b) 390°C, 1 hour in air c) 390°C 1 hour is 1.5% butane/air d) 390-460°C, 20 minutes in 1.5% butane/air e) 460-460°C, 18 hours in 1.5% butane/air f) 460-420°C in 1.5% butane/air g) 420-360°C in 1.5% butane/air h) 360-25°C in 2 .
- the solution was heated to 100°C and maintained at this temperature until all of the phosphoric acid was dissolved.
- the phosphoric acid/boron nitride mixture was stirred for 30 minutes.
- the resulting material was (not filtered) dried at 120°C in air and washed three times in water to extract any excess phosphoric acid.
- the material was calcined at 150°C for 12 hours in air to provide phosphorus-modified boron nitride.
- Vanadium phosphorus oxide precursor in isobutanol was prepared in the same manner as in Comparative Example 1.
- the phosphorus-modified boron nitride was added to the vanadium (IV) phosphate mixture under agitation at a temperature between 100°C and 150°C to form vanadium phosphorus precursor supported on the phosphorus-modified boron nitride (VPO/PIBN).
- the supported vanadium phosphorus oxide precursor was subjected to activation in accordance with the teachings of U.S. Patent 4,132,670, by heating the material to a temperature of 380°C at 3°C per minute under air flow rate of 1.5 cc per minute and held at 380°C for 2 hours. The material was then heated to a temperature of 480°C at 3°C per minute under air/butane (1.5% by volume of butane) flow rate of 3 cc per minute and held at 480°C for 15 hours. The material was allowed to cool to 420°C under air/butane (1.5% by volume of butane) flow of 17 cc per minute for 100 hours. This produced an " activated catalyst" .
- a vanadium phosphorus oxide catalyst was prepared in the same manner with untreated boron nitride.
- the treated and untreated boron nitride catalysts contained 30 wt % vanadium phosphorus oxide. Catalytic testing was carried out as described above in Comparative
- vanadium phosphorus oxide supported on untreated boron nitride also shows improvement in higher temperature performance (above 425°C) compared to vanadium phosphorus oxide (Comparative Example 2), but this improvement is not as pronounced as it is for the vanadium phosphorus oxide supported on phosphated boron nitride (Example 1).
- EXAMPLE 2 Exactly the same procedure was followed to prepare VPO on non- phosphated boron nitride. As shown in Figure 1, this material showed an increase in maleic anhydride yield, but tended to level off at about 20%. It still showed improvement over VPO catalyst (Comparative Example 2), which did not contain boron nitride at temperatures above about 420°C, as indicated in Figure 1 and as described above.
- Catalytic testing was carried out as described above in Comparative Example 1 for vanadium phosphorus oxide supported on SiC. These testing protocols were applied to conventional VPO catalyst (Comparative Example 2), vanadium phosphorus oxide supported silicon nitride (Example 3) and the catalyst of Comparative Example 1 (vanadium phosphorus oxide supported on silicon carbide). The percentage yield of maleic anhydride versus temperature is shown in Figure 2 for these catalysts. As can be seen from Figure 2, the catalyst of Example 3 exhibits superior higher temperature performance (above 425°C) compared with vanadium phosphorus oxide (Comparative Example 2). This behavior is similar to that observed from catalysts prepared in Example 1 (vanadium phosphorus oxide supported on phosphated boron nitride), in which the percentage yield to maleic anhydride increases with temperature, up to 470°C.
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US12941199P | 1999-04-15 | 1999-04-15 | |
US129411P | 1999-04-15 | ||
PCT/US2000/009905 WO2000062925A1 (en) | 1999-04-15 | 2000-04-14 | Vanadium phosphorus oxide catalyst having a thermally conductive support |
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EP00923307A Withdrawn EP1171237A1 (de) | 1999-04-15 | 2000-04-14 | Vanadium-phosphoroxid-katalysator mit einem thermisch leitfähigen träger |
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EP (1) | EP1171237A1 (de) |
JP (1) | JP2002542016A (de) |
KR (1) | KR20010108505A (de) |
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AU (2) | AU4345800A (de) |
EA (1) | EA200101087A1 (de) |
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Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2301897T3 (es) | 1999-12-21 | 2008-07-01 | Monsanto Technology Llc | Uso de un promotor suplementario junto con un catalizador que contiene un metal noble, con soporte de carbon, en reacciones de oxidacion en fase liquida. |
KR100424674B1 (ko) * | 2001-05-19 | 2004-03-27 | 한국전자통신연구원 | Vopo₄·2h₂o의 초음파 화학적 제조방법 및 리튬2차 전지 양극물질로의 용도 |
US7390920B2 (en) | 2002-02-14 | 2008-06-24 | Monsanto Technology Llc | Oxidation catalyst and process |
AU2003215241B2 (en) | 2002-02-14 | 2008-07-31 | Monsanto Technology Llc | Oxidation catalyst and process for its preparation and process for oxidation using it |
US7008560B2 (en) | 2003-02-10 | 2006-03-07 | Conocophillips Company | Silicon carbide-supported catalysts for partial oxidation of natural gas to synthesis gas |
US7294734B2 (en) * | 2003-05-02 | 2007-11-13 | Velocys, Inc. | Process for converting a hydrocarbon to an oxygenate or a nitrile |
CN1867404B (zh) | 2003-08-14 | 2011-06-22 | 孟山都技术公司 | 含有过渡金属-碳化物和氮化物的催化剂、它们的制备方法和作为氧化和脱氢催化剂的用途 |
AR051926A1 (es) | 2004-09-15 | 2007-02-21 | Monsanto Technology Llc | Catalizadores de oxidacion, procedimientos de preparacion de dichos catalizadores y proceso para la elaboracion de n-( fosfonometil)glicina o una sal de la misma |
MX2007010066A (es) | 2005-02-17 | 2007-11-07 | Monsanto Technology Llc | Catalizadores que contienen metales de transicion y combinaciones de catalizadores que incluyen catalizadores que contienen metales de transicion y procedimientos para su preparacion y uso como catalizadores de oxidacion. |
US8252953B2 (en) | 2008-05-01 | 2012-08-28 | Monsanto Technology Llc | Metal utilization in supported, metal-containing catalysts |
EP2135671B1 (de) | 2008-06-19 | 2015-03-04 | Mitsubishi Gas Chemical Company, Inc. | Katalysator und Verfahren zur Herstellung von Carboxylsäure und/oder Carboxylanhydrid bei Vorhandensein des Katalysators |
CN101507927B (zh) * | 2009-02-10 | 2011-12-21 | 上海华谊丙烯酸有限公司 | 一种复合氧化物催化剂的制备方法及其在合成丙烯酸工艺中的应用 |
CN102161005A (zh) * | 2011-02-21 | 2011-08-24 | 化学工业第二设计院宁波工程有限公司 | 乙酸和甲醛合成丙烯酸用磷钒催化剂的制备方法 |
CN102151583B (zh) * | 2011-02-21 | 2013-02-20 | 中国化学赛鼎宁波工程有限公司 | 一种乙酸和甲醛合成丙烯酸用磷钒催化剂的制备方法 |
CN104557817B (zh) * | 2013-10-28 | 2017-05-24 | 中国石油化工股份有限公司 | 一种正丁烷制备顺酐的方法 |
CN105381809B (zh) * | 2014-09-09 | 2018-07-17 | 中国石油化工股份有限公司 | 用于烃类选择氧化的钒磷氧催化剂的制备方法 |
CN106565561A (zh) * | 2016-11-11 | 2017-04-19 | 湖北广富林生物制剂有限公司 | 一种2‑硝基‑4‑甲磺酰基苯甲酰氯的合成工艺 |
CN106748919A (zh) * | 2016-11-11 | 2017-05-31 | 湖北广富林生物制剂有限公司 | 一种硝磺草酮的合成工艺 |
CN106565558A (zh) * | 2016-11-11 | 2017-04-19 | 湖北广富林生物制剂有限公司 | 一种2‑硝基‑4‑甲磺酰基苯甲酰氯的合成工艺 |
CN106748918A (zh) * | 2016-11-11 | 2017-05-31 | 湖北广富林生物制剂有限公司 | 一种硝磺草酮的合成工艺 |
CN106565557A (zh) * | 2016-11-11 | 2017-04-19 | 湖北广富林生物制剂有限公司 | 一种2‑硝基‑4‑甲磺酰基苯甲酰氯的合成工艺 |
CN106565556A (zh) * | 2016-11-11 | 2017-04-19 | 湖北广富林生物制剂有限公司 | 一种硝磺草酮的合成工艺 |
CN109731594A (zh) * | 2019-02-28 | 2019-05-10 | 中国科学院过程工程研究所 | 一种磷酸氧钒催化剂的制备及应用 |
CN110624593A (zh) * | 2019-09-30 | 2019-12-31 | 陕西科技大学 | 一种VN@Co电催化剂的制备方法 |
CN111138684A (zh) * | 2019-12-31 | 2020-05-12 | 山东胜伟盐碱地科技有限公司 | 一种从褐煤中提取腐殖酸的方法 |
CN113522329B (zh) * | 2020-04-15 | 2023-11-10 | 中国石油化工股份有限公司 | 一种用于正丁烷氧化制顺酐催化剂及其制备方法和应用 |
CN116060060A (zh) * | 2021-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | 一种负载型钒磷氧催化剂 |
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US4564607A (en) * | 1983-03-24 | 1986-01-14 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Heteropolyacid-type catalyst composition containing whiskers |
DE69121028T3 (de) * | 1990-03-13 | 2001-04-05 | Nippon Shokubai Co. Ltd., Osaka | Verfahren zur herstellung von methacrylsäure |
DE69617556T9 (de) * | 1995-02-17 | 2005-04-07 | Basf Ag | Verfahren zur Herstellung eines Oxidationskatalysators und Verwendung desselben |
DE19519172A1 (de) * | 1995-05-24 | 1996-11-28 | Consortium Elektrochem Ind | Trägerkatalysator für Gasphasenoxidationsreaktoren |
JPH09100179A (ja) * | 1995-07-26 | 1997-04-15 | Sumitomo Electric Ind Ltd | 窒化ケイ素質多孔体およびその製造方法 |
EP0799795B1 (de) * | 1996-04-01 | 2000-08-09 | Nippon Shokubai Co., Ltd. | Vanadium-Phosphoroxid, Verfahren zu dessen Herstellung, aus dem Oxid hergestellter Katalysator für die Dampfphasenoxidation und Verfahren für die Dampfphasenteiloxidation von Kohlenwasserstoffen |
DE19617040C1 (de) * | 1996-04-27 | 1997-10-30 | Degussa | Verfahren zur Herstellung katalytisch wirksamer Beschichtungen für die Synthese von Cyanwasserstoff |
FR2758279B1 (fr) * | 1997-01-13 | 1999-02-26 | Pechiney Recherche | Support de catalyseur a base de carbure de silicium a surface specifique elevee sous forme de granule ayant des caracteristiques mecaniques ameliorees |
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AU4345700A (en) | 2000-11-02 |
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