JPS6278A - Production of maleic anhydride - Google Patents
Production of maleic anhydrideInfo
- Publication number
- JPS6278A JPS6278A JP61040260A JP4026086A JPS6278A JP S6278 A JPS6278 A JP S6278A JP 61040260 A JP61040260 A JP 61040260A JP 4026086 A JP4026086 A JP 4026086A JP S6278 A JPS6278 A JP S6278A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- mol
- catalyst
- active substance
- content
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 239000013543 active substance Substances 0.000 claims abstract description 51
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 44
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 23
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims description 28
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 19
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052701 rubidium Inorganic materials 0.000 claims description 8
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 229910001882 dioxygen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052716 thallium Inorganic materials 0.000 claims description 7
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000012808 vapor phase Substances 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910001948 sodium oxide Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 102220029906 rs907610 Human genes 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
-
- 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
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はベンゼンを固定床プロセスで空気または分子状
酸素含有ガスにより接触気相酸化して無水マレイン酸を
製造するに際して、より高められたベンゼン負荷条件下
で安定に且つ高収率で無水マレイン酸の得られる方法お
よびそのための触媒を提供するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention is directed to the production of maleic anhydride by catalytic gas phase oxidation of benzene with air or molecular oxygen-containing gas in a fixed bed process. The present invention provides a method for obtaining maleic anhydride stably and in high yield under loaded conditions, and a catalyst for the same.
〈従来の技術〉
ベンゼンの接触気相酸化による無水マレイン酸の製造を
工業的に有利に実施するために、触媒に対して高い選択
性と長期耐久性とが最大要件として課せられてきたが、
最近ではプロセスの省エネルギー化と生産効率向上の要
求からより大間のベンゼンをより少量の空気で酸化可能
な性能を有すること、すなわち、供給ガス中のベンゼン
濃度を高めて操業しても選択性および耐久性のすぐれて
いることが第3の要件として要求されるようになった。<Prior Art> In order to industrially advantageously produce maleic anhydride by catalytic gas-phase oxidation of benzene, high selectivity and long-term durability have been imposed on catalysts as the greatest requirements.
Recently, due to the demand for energy saving and improved production efficiency in processes, it has become increasingly important to have the ability to oxidize benzene with a smaller amount of air.In other words, it has become possible to oxidize benzene with a smaller amount of air, which means it has better selectivity and durability even when operating with a higher concentration of benzene in the supply gas. Excellent quality has become the third requirement.
このような第3の要件要求に対してこれまで提案されて
いる触媒は必ずしも十分に応えきれていない。例えば特
公昭55−5379号および同56−1933号各公報
では無水マレイン酸が95〜100重量%の好収率で得
られる旨の記載があるが、それらの実施例によればその
ような高い収率は供給ガス中のベンゼンの濃度が40a
−ベンゼン/NM −空気(以下40111/NM
と略記)という比較的低い条件で達成されているにす
ぎず、本発明者らの追試結果においてもベンゼン濃度を
50g/NM 程度に高めた酸化条件下では触媒層の
熱点(hot 5pot)の湿度は500℃を超え85
〜90重量%の収率で無水マレイン酸が得られたのに止
まった。また50g/NM3以上の高いベンゼン濃度で
の反応では触媒層の熱点付近で制御不可能な異常過度酸
化が生じ触媒が半融して失活した。一方、ベンゼンの負
荷量の増加とともに長期連続使用において触媒活性物質
の担体表面からのハタ落が大きくなり、この点において
もこれ等の触媒を高濃度プロセスに採用することは不可
能である。Catalysts that have been proposed so far have not always been able to fully meet this third requirement. For example, Japanese Patent Publications No. 55-5379 and No. 56-1933 state that maleic anhydride can be obtained at a high yield of 95 to 100% by weight, but according to their examples, such high yields can be obtained. The yield is when the concentration of benzene in the feed gas is 40a
- Benzene/NM - Air (hereinafter 40111/NM
This was achieved only under relatively low conditions (abbreviated as ), and the inventors' follow-up test results show that under oxidizing conditions where the benzene concentration was increased to about 50 g/NM, the hot 5pot of the catalyst layer was Humidity exceeds 500℃ and 85
A yield of ˜90% by weight of maleic anhydride was obtained, but only. Further, in the reaction at a high benzene concentration of 50 g/NM3 or more, uncontrollable abnormal excessive oxidation occurred near the hot spot of the catalyst layer, resulting in half-melting of the catalyst and deactivation. On the other hand, as the loading of benzene increases, the amount of catalytically active material falling off the surface of the carrier increases during long-term continuous use, and in this respect as well, it is impossible to employ these catalysts in high-concentration processes.
〈発明が解決しようとする問題点〉
従って、本発明の目的はベンゼンの空気または分子状酸
素含有ガスによる接触気相酸化で無水マレイン酸を製造
する固定床プロセスにおいて、高いベンゼン/空気また
は分子状酸素含有ガス比で操業し、
1) 単位生産量あたりの空気または分子状酸素含有ガ
スの送風量を減じ送風に要するエネルギーを低減するこ
と、
2) 単位生産量あたりの送風】を減じることにより酸
化反応器からのガス待人り熱量を減じその反応器での回
収熱量を増加せしめ利用度の高い高圧蒸気回収聞を増加
させること、
3) 生成ガス中の無水マレイン酸濃度を高めることに
より無水マレイン酸捕集器でその液体捕集率を高め後部
スフラッパーでのマレイン酸としての捕集量を減じマレ
イン酸から無水マレイン酸への無水化エネルギーを低減
することおよびスフラッパー排水量を低減すること、
4) 生産効率を高め単位生産量あたりの酸化反応器お
よび付帯設備の大きさを縮小すること等の省エネルギー
および生産性の向上面でのメリットを生みだすような高
いベンゼン負荷性の有する触媒を提供し、あわせてその
使用方法を確立することである。<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide a fixed-bed process for producing maleic anhydride by catalytic gas phase oxidation of benzene with air or molecular oxygen-containing gas. By operating at an oxygen-containing gas ratio, 1) reducing the amount of air or molecular oxygen-containing gas blown per unit of production to reduce the energy required for blowing; 2) reducing the amount of air blown per unit of production. 3) To reduce the amount of heat waiting for gas from the reactor, increase the amount of heat recovered in the reactor, and increase the amount of high-pressure steam recovery space that is highly utilized; 3) maleic anhydride by increasing the concentration of maleic anhydride in the produced gas 4. To increase the liquid collection rate in the collector and reduce the amount of maleic acid collected in the rear flapper, thereby reducing the dehydration energy from maleic acid to maleic anhydride and reducing the drainage volume of the flapper. ) To provide a catalyst having a high benzene loading property that brings about benefits in terms of energy saving and productivity improvement such as increasing production efficiency and reducing the size of the oxidation reactor and ancillary equipment per unit production amount, It is also important to establish how to use it.
〈発明の構成および作用〉
本発明者らは五酸化バナジウムV205 、三酸化モリ
ブデンMo Osおよび酸化ナトリウムNa2Oを主成
分とする組成に特定の助触媒を添加せしめて得た活性物
質をシリコンカーバイドSiCを主体とする多孔性無機
不活性担体に担持せしめた触媒において、とくにその活
性物質中に適当量の無機ウィスカーを混在させることに
より触媒活性物質の担体表面からの機械的および触媒層
で熱負荷を受けてのハタ落が著しく改善されることを見
い出し、また、触媒層の供給ガス入口側部分にはカリウ
ム、セシウム、タリウムおよびルビジウムよりなる群か
ら選ばれた少なくとも1種の成分を助触媒として添加す
ることにより活性を制御した触媒を、または五酸化リン
P205の添加量を減少せしめることにより活性を制御
した触媒(以下、前段触媒という)を充填し、触媒層の
ガス出口側部分には前段触媒にくらべてカリウム。<Structure and operation of the invention> The present inventors added silicon carbide SiC to an active material obtained by adding a specific promoter to a composition mainly composed of vanadium pentoxide V205, molybdenum trioxide MoOs, and sodium oxide Na2O. In a catalyst supported on a porous inorganic inert carrier, in particular, by mixing an appropriate amount of inorganic whiskers in the active substance, it is possible to prevent the catalytically active substance from receiving mechanical stress from the carrier surface and heat load in the catalyst layer. They have also found that at least one component selected from the group consisting of potassium, cesium, thallium and rubidium is added as a co-catalyst to the feed gas inlet side of the catalyst layer. A catalyst whose activity is controlled by reducing the amount of phosphorus pentoxide P205 added or a catalyst whose activity is controlled by reducing the added amount of phosphorus pentoxide P205 (hereinafter referred to as the front stage catalyst) is filled, and the gas outlet side portion of the catalyst layer is filled with a catalyst whose activity is controlled by reducing the amount of phosphorus pentoxide P205 added. Compared to potassium.
セシウム、タリウム、ルビジウム、マグネシウム。Cesium, thallium, rubidium, magnesium.
カルシウム、ストロンチウムおよびバリウムよりなる群
から選ばれた少なくとも1種の成分の添加量を減じたり
または添加しないことにより活性を高めた触媒を、また
は前段触媒に較べて五酸化リンP2O5の添加量を増加
せしめることにより活性を高くした触媒(以下、後段触
媒という)を配置した積層触媒を使用することにより、
ベンゼンの単位触媒量あたりへの負荷性の大巾な増加お
よび触媒の耐久性のすぐれて改善されることを見い出し
本発明触媒を完成せしめた。A catalyst whose activity is increased by reducing or not adding at least one component selected from the group consisting of calcium, strontium, and barium, or an increased amount of phosphorus pentoxide P2O5 compared to the preceding catalyst. By using a stacked catalyst that has a catalyst with increased activity (hereinafter referred to as a post-catalyst),
We have completed the catalyst of the present invention by discovering that the loading of benzene per unit catalyst amount is greatly increased and the durability of the catalyst is significantly improved.
本発明触媒の活性物質は、基本的には五酸化バナジウム
V2O5を主成分とし、さらにこの1モルに対して、三
酸化モリブデンMOO30,3〜1.0−Eル、酸化ナ
トリウムN8200.03〜0.2モル、五酸化リンP
2O50〜0.4モルおよびカリウム、セシウム、タリ
ウム、ルビジウム、マグネシウム、カルシウム、ストロ
ンチウムおよびバリウムよりなる群から選ばれた少なく
と61成分を酸化物として0〜0.5モルの範囲含有せ
しめてその組成をそれぞれ前段および後段触媒に応じて
前述の如く、五酸化リン、カリウム、セシウム。The active substance of the catalyst of the present invention basically consists of vanadium pentoxide V2O5 as a main component, and furthermore, per mole of vanadium pentoxide V2O5, molybdenum trioxide MOO30.3~1.0-El, sodium oxide N8200.03~0 .2 mol, phosphorus pentoxide P
The composition contains 50 to 0.4 mole of 2O and at least 61 components selected from the group consisting of potassium, cesium, thallium, rubidium, magnesium, calcium, strontium and barium in the range of 0 to 0.5 mole as an oxide. and phosphorus pentoxide, potassium, and cesium as previously described depending on the front and rear catalysts, respectively.
タリウム、ルビジウム、マグネシウム、カルシウム、ス
トロンチウムおよび/またはルビジウムの組成割合を適
宜変更せしめたものである。The composition ratios of thallium, rubidium, magnesium, calcium, strontium and/or rubidium are changed as appropriate.
担体としては、シリコンカーバイドSiC含有量が50
重伍%以上、好ましくは80重量%以上であり、かつ酸
化アルミニウム含有聞が10重ω%以下、好ましくは3
重量%以下であるものであって、見掛気孔率10〜70
%、とくに15〜40%、比表面積1 tri/Q以下
の高熱伝導性多孔性無機化合物が使用される。担体の形
状はとくに限定されないが大きさが3〜15mm程度の
球、リング、サドル、円柱1円錐等から適宜選択して用
いられる。As a carrier, silicon carbide SiC content is 50
5% by weight or more, preferably 80% by weight or more, and the aluminum oxide content is 10% by weight or less, preferably 3% by weight.
% by weight or less, and the apparent porosity is 10 to 70
%, especially from 15 to 40%, and a high thermal conductivity porous inorganic compound with a specific surface area of 1 tri/Q or less is used. The shape of the carrier is not particularly limited, but may be appropriately selected from spheres, rings, saddles, cylinders and cones, etc. each having a size of about 3 to 15 mm.
触媒活性物質を良好に担体上に担持せしめるために用い
られるウィスカーとしては、金属ウィスカーに限らず耐
火物ウィスカーも好適に使用される。例えば、タングス
テン、鉄、ニッケル等の金属ウィスカーやシリコンカー
バイド、窒素硅素。The whiskers used to properly support the catalytically active substance on the carrier are not limited to metal whiskers, but refractory whiskers are also suitably used. For example, metal whiskers such as tungsten, iron, and nickel, silicon carbide, and nitrogen silicon.
酸化アルミニウム、チタンカーバイド、リン酸カルシウ
ム等の耐火物ウィスカーである。大きさとしては、平均
直径が5ミクロン以下、好ましくは1ミクロン以下、長
さ1,000ミクロン以下、好ましくは500ミクロン
以下そのアスペクト比が10〜500、とくに20〜3
00の範囲のものである。Refractory whiskers such as aluminum oxide, titanium carbide, and calcium phosphate. As for size, the average diameter is 5 microns or less, preferably 1 micron or less, the length is 1,000 microns or less, preferably 500 microns or less, and the aspect ratio is 10 to 500, especially 20 to 3.
00 range.
活性物質の担体への担持は従来公知の方法で行なわれる
。すなわち、活性成分の含む触媒液またはスラリー液を
予め150〜250℃に加熱せしめた担体表面に噴霧せ
しめ担持せしめる方法とか、触媒液またはスラリー液中
に担体を含浸せしめ濃縮付着せしめる方法とかである。The active substance is supported on the carrier by a conventionally known method. That is, there are methods in which a catalyst liquid or slurry liquid containing the active ingredient is sprayed onto the surface of a carrier preheated to 150 to 250° C., and a method in which the carrier is impregnated in the catalyst liquid or slurry liquid and concentrated and deposited.
この際、触媒液またはスラリー中に完成触媒活性物質に
対してウィスカーが1〜20重量%、好ましくは3〜1
0重」%含有するべく相応量の上記ウィスカーが分散さ
れる。活性物質は見掛容fi100ccの担体に対して
3〜40g1好ましくは5〜25CIの割合で担持され
る。At this time, whiskers are present in the catalyst liquid or slurry in an amount of 1 to 20% by weight, preferably 3 to 1% by weight based on the finished catalyst active material.
A suitable amount of the above whiskers is dispersed so as to contain 0% by weight. The active substance is supported at a ratio of 3 to 40 g, preferably 5 to 25 CI, per carrier having an apparent volume fi of 100 cc.
反応は触媒を内径15〜4Qms、とくに20〜30m
mの管に充填して行なわれるが、全触媒層高のガス流れ
方向の最初の30〜70%の部分に前段触媒を、後部7
0〜30%の部分に後段触媒を積層に配置して行なわれ
る。The reaction is carried out using a catalyst with an inner diameter of 15 to 4 Qms, especially 20 to 30 m.
The first 30 to 70% of the total catalyst bed height in the gas flow direction is filled with the front stage catalyst, and the rear 7
This is carried out by arranging post-stage catalysts in a stacked manner in the 0 to 30% portion.
前段触媒としては(A)五酸化バナジウムv205とそ
の1モルに対して、三酸化モリブデンMOO30,3〜
1.0モル、酸化ナトリウムNa 200.03〜0.
2モル、五酸化リンP2050.01〜0,05モルお
よびカリウム、セシウム。As a first-stage catalyst, (A) vanadium pentoxide v205 and molybdenum trioxide MOO30.3 to 1 mole thereof.
1.0 mol, sodium oxide Na 200.03-0.
2 mol, phosphorus pentoxide P205 0.01-0.05 mol and potassium, cesium.
タリウムおよびルビジウムよりなる群から選ばれた少な
くとも1成分が酸化物として0.0001〜0.5モル
とよりなる活性物質または(B)五酸化バナジウムV2
O5とその1モルに対して三酸化モリブデンMOO30
,3〜1.0モル、酸化ナトリウムNa 200.03
〜0゜2モルおよび五酸化リンP2O50〜0.01モ
ルとよりなる活性物質を、上記多孔性担体上に担持せし
てなるものであり、とくに活性物質に対してウィスカー
を1〜20重量%含有甘しめせ持せしめた触媒が好適に
用いられる。An active substance consisting of 0.0001 to 0.5 mol of at least one component selected from the group consisting of thallium and rubidium as an oxide, or (B) vanadium pentoxide V2
Molybdenum trioxide MOO30 per mole of O5
, 3-1.0 mol, sodium oxide Na 200.03
The active substance consisting of ~0.2 mol and 50~0.01 mol of phosphorus pentoxide P2O is supported on the above porous carrier, and in particular, the whisker content is 1 to 20% by weight based on the active substance. Preferably, sweetened catalysts are used.
後段触媒としては、
(C)上記活性物質組成Aに対しP2O5をO,OS超
え0.4以下のモル範囲とせしめた活性物質(C−1)
および上記活性物質組成Aに対しP205を0.01〜
0.4モルとし、さらにマグネシウム、カルシウム、ス
トロンチウムおよびバリウムよりなる群から選ばれた少
なくとも1成分が酸化物として0.0001〜0.5モ
ルの範囲添加せしめてなる活性物質(C−2)および(
D)上記活性物質組成りに対しP205を0.01超え
0.2以下のモル範囲とせしめた活性物質よりなる組成
のうちのいずれかを上記多孔性担体に担持せしてなるも
のであり、とくに活性物質に対してウィスカーを1〜2
0重量%含有せしめ担持せしめた触媒が好適に用いられ
る。As the second-stage catalyst, (C) an active substance (C-1) having P2O5 in a molar range exceeding O, OS and 0.4 or less for the above active substance composition A;
and P205 from 0.01 to the above active substance composition A
an active substance (C-2) containing 0.4 mol and further adding at least one component selected from the group consisting of magnesium, calcium, strontium and barium as an oxide in the range of 0.0001 to 0.5 mol; (
D) The porous carrier supports any one of the active substances having a molar range of P205 of more than 0.01 and less than 0.2 for the active substance composition; 1-2 whiskers especially for active substances
A supported catalyst containing 0% by weight is preferably used.
前・後段触媒ともに350〜600℃、とくに400〜
500℃の温度において空気流通下または不活性ガス流
通12〜10時間焼成して完成触媒とされる。350-600℃ for both front and rear catalysts, especially 400-600℃
The catalyst is calcined at a temperature of 500° C. for 12 to 10 hours under air or inert gas flow to obtain a finished catalyst.
このようにして調製された触媒は、たとえば溶融塩浴に
浸された反応管に、先ず後段触媒を全触媒層高の30〜
70%の高さに充填され、次いでその上に前段触媒を全
触媒層高の70〜30%の高さに充填され、溶融塩浴温
度330〜400℃の条件下で空気または分子状酸素含
有ガスにベンゼンを20〜100g/NM 1とくに
50〜80g/NM の割合で混合せしめ、且つ10
0〜150℃に予熱せられた原料ガスを管の上部より空
間速度1500〜6000Hr 、とくに2000〜
4000Hr−1の速さで導通し反応が行なわれる。The catalyst prepared in this way is prepared by first placing the latter stage catalyst in a reaction tube immersed in a molten salt bath, for example, and placing it in a reaction tube immersed in a molten salt bath.
70% of the height of the catalyst layer, and then a pre-catalyst was packed on top of it to a height of 70-30% of the total catalyst bed height, and air or molecular oxygen-containing was added at a molten salt bath temperature of 330-400°C. Benzene is mixed with the gas at a ratio of 20 to 100 g/NM 1, especially 50 to 80 g/NM, and 10
The raw material gas preheated to 0 to 150°C is fed from the top of the tube at a space velocity of 1500 to 6000 Hr, especially 2000 to 6000 Hr.
The conduction reaction takes place at a rate of 4000 Hr-1.
このような高負荷条件下で無水マレイン酸は95〜10
0重量%の収率(対100%純度ベンゼン)で長期に安
定して得られ、またベンゼン高負荷による活性物質の担
体からのハタ落の度合も長期運転において反応温度の変
化の割合が小さいことおよび経時的な触媒層の圧力上昇
がほとんど認められないことから大きく改善されること
が知られた。Under such high loading conditions, maleic anhydride is 95-10
It can be obtained stably over a long period of time with a yield of 0% by weight (based on 100% pure benzene), and the degree of dropout of the active substance from the carrier due to high benzene loading is small, as is the rate of change in reaction temperature during long-term operation. It was also found that the pressure increase in the catalyst layer over time was hardly observed, indicating a significant improvement.
以下、実施例を以って本発明触媒について、さらに具体
的に説明する。Hereinafter, the catalyst of the present invention will be explained in more detail with reference to Examples.
実施例1
水1500cc中に蓚酸260gを溶解し、これにメタ
バナジン酸アンモニウム234(1,モリブデン酸アン
モニウム123.6g、炭酸ナトリウム6.36g、リ
ン酸二水素ナトリウム4.6gおよび硫酸セシウム72
.4gを加え加熱溶解させ触媒液とした。さらに直径0
.5ミクロン、平均長さ180ミクロンの窒化硅素ウィ
スカー210を添加し、乳化機により30分間攪拌して
均一分散させた。Example 1 260 g of oxalic acid was dissolved in 1500 cc of water, and ammonium metavanadate 234 (1, ammonium molybdate 123.6 g, sodium carbonate 6.36 g, sodium dihydrogen phosphate 4.6 g and cesium sulfate 72
.. 4 g was added and dissolved by heating to obtain a catalyst liquid. Furthermore, the diameter is 0.
.. Silicon nitride whiskers 210 having a diameter of 5 microns and an average length of 180 microns were added and stirred for 30 minutes using an emulsifier to uniformly disperse the mixture.
シリコンカーバイド(SiC)92重量%、アルミナ(
AJ203)2重量%およびシリカ(SiO2)6重量
%よりなり外径7 ++ua、内径3.5IIIIIl
および長さ7mmの見掛気孔率30%、比表面積0.0
4 rrt/Qの多孔性リング担体、1800CCを外
部加熱装置付の回転ドラムに入れ200〜250℃の温
度に保ちつつ上記触媒スラリーを噴霧させ、担体100
ccにつき15gの活性物質を担持せしめ空気中400
℃にて5時間焼成して触媒−八を得た。このようにして
得られた活性物質の組成比はV205 :MO03:N
a 20:P20s : Cs 20−1 : 0.
7: 0.06 :0.02 : 0.2モル比で
あり、ウィスカー含有率は活性物質に対し6重量%であ
った。Silicon carbide (SiC) 92% by weight, alumina (
AJ203) 2% by weight and 6% by weight of silica (SiO2), outer diameter 7++ua, inner diameter 3.5IIIl
and length 7mm, apparent porosity 30%, specific surface area 0.0
A porous ring carrier of 4 rrt/Q, 1800 CC, was placed in a rotating drum equipped with an external heating device, and the above catalyst slurry was sprayed while maintaining the temperature at 200 to 250 °C.
Carrying 15g of active substance per cc, 400% in air
C. for 5 hours to obtain Catalyst-8. The composition ratio of the active substance thus obtained is V205:MO03:N
a20:P20s: Cs20-1: 0.
The molar ratio was 7:0.06:0.02:0.2, and the whisker content was 6% by weight based on the active substance.
リン酸二水素アンモニウムの添加量を80.512とし
た以外は触媒−八と全く同様にして活性物質の組成比が
V205:Mo Os :Na 20:P205 :C
S20=1 : 0.7: Q、06 :0.35
: O12モル比である触媒−Bが調製された(ウ
ィスカー含量6重量%)。The composition ratio of the active substance was V205:MoOs:Na20:P205:C in exactly the same manner as Catalyst-8 except that the amount of ammonium dihydrogen phosphate was 80.512.
S20=1:0.7:Q,06:0.35
: Catalyst-B was prepared with a molar ratio of O12 (whisker content 6% by weight).
溶融塩浴に浸された内径2511長さ3.5メートルの
管に触媒−Bを1.5メートルの高さに充填し、次いで
その上に触媒−Aを1メートルの高さに積層して充填し
、温度を355℃に保った。A tube with an inner diameter of 2511 and a length of 3.5 meters immersed in a molten salt bath was filled with catalyst-B to a height of 1.5 meters, and then catalyst-A was layered on top of it to a height of 1 meter. It was filled and the temperature was maintained at 355°C.
ベンゼン濃度65(1/NM3のベンゼン−空気混合ガ
スを反応管上部より空間速度3000Hr”(STP)
で導通したところ、100%純度ベンゼンに対し98.
5型口%の収率で無水マレイン酸が得られた。A benzene-air mixed gas with a benzene concentration of 65 (1/NM3) is introduced from the top of the reaction tube at a space velocity of 3000 Hr” (STP).
When conduction was conducted with 100% pure benzene, the voltage was 98.
Maleic anhydride was obtained with a yield of 5%.
実施例2
水1200cc中に12規定塩酸300ccを溶解し、
これにメタバナジン酸アンモニウム160g、モリブデ
ン酸アンモニウム96.6(1、炭酸ナトリウム8.7
gおよびリン酸二水素アンモニウム6.7BQを溶解さ
せ、さらに直径0.2ミクロン、長さ20ミクロンのシ
リコンカーバイドウィスカー10.5gを添加し30分
間十分攪拌して触媒スラリー液とした。Example 2 Dissolve 300 cc of 12N hydrochloric acid in 1200 cc of water,
To this, 160 g of ammonium metavanadate, 96.6 g of ammonium molybdate (1, 8.7 g of sodium carbonate)
g and 6.7 BQ of ammonium dihydrogen phosphate were dissolved, and 10.5 g of silicon carbide whiskers having a diameter of 0.2 microns and a length of 20 microns were added, and the mixture was thoroughly stirred for 30 minutes to obtain a catalyst slurry liquid.
88重量%のSt C,4重量%のA、i!203およ
び8重量%の8102よりなる平均直径の6mm見掛気
孔率35%、比表面積0.03rtt/Qの多孔性球状
担体2000ccを上記触媒スラリーに浸漬し、外部よ
り加熱濃縮し活性物質を担持せしめた。担持率は8g/
100cc担体であった。これを430℃にて空気流通
下6時間焼成して触媒−Cを得た。このようにして調製
された触媒の活性物質の組成比はV2O5:MOO3:
Na2O:P2O5=1 : 0.8: 0.12
: 0.005モル比であり、ウィスカー含量は5
重過%であった。88% by weight St C, 4% by weight A, i! 2000 cc of porous spherical carrier made of 203 and 8% by weight of 8102, having an average diameter of 6 mm, an apparent porosity of 35%, and a specific surface area of 0.03 rtt/Q was immersed in the above catalyst slurry, and heated and concentrated from the outside to support the active substance. I forced it. The loading rate is 8g/
It was a 100cc carrier. This was calcined at 430° C. for 6 hours under air circulation to obtain catalyst-C. The composition ratio of the active substance of the catalyst thus prepared is V2O5:MOO3:
Na2O:P2O5=1: 0.8: 0.12
: 0.005 molar ratio, whisker content is 5
The weight was %.
一方、リン酸二水素アンモニウムの添加量を23.4a
とした以外は触媒−Cと全く同様にして触媒−りを調製
した。触媒活性物質の組成比はV205 :MO03:
Na2O:P20s =1 :0.8: 0.12
: 0.15モル比であった(ウィスカー金山5重量
%)。On the other hand, the amount of ammonium dihydrogen phosphate added was 23.4a.
A catalyst was prepared in exactly the same manner as Catalyst-C except that: The composition ratio of the catalytic active material is V205:MO03:
Na2O:P20s = 1:0.8: 0.12
: 0.15 molar ratio (5% by weight of whisker Kanayama).
溶融塩浴に浸された内径25mm、長さ3.5メートル
の管に先ず触媒−〇を1.5メートルの高さに充填し、
次いでその上に触媒−Cを0.8メートルの高さに積層
して充填し、350℃の温度に保った。ベンゼン濃度6
(1/NM3で120℃に予熱されたベンゼン−空気混
合ガスを反応管上部より空間速度3500Hr−1(S
TP)で導通したところ100%純度ベンゼンに対し9
6,5重量%の収率で無水マレイン酸が得られた。A tube with an inner diameter of 25 mm and a length of 3.5 meters immersed in a molten salt bath was first filled with catalyst-〇 to a height of 1.5 meters.
Catalyst-C was then packed thereon in a layered manner to a height of 0.8 meters and maintained at a temperature of 350°C. Benzene concentration 6
(Benzene-air mixed gas preheated to 120℃ with 1/NM3 is introduced from the top of the reaction tube at a space velocity of 3500Hr-1 (S
9 for 100% pure benzene when conducting with TP)
Maleic anhydride was obtained with a yield of 6.5% by weight.
実施例3
水1500cc中に蓚酸260Qを溶解し、これにメタ
バナジン酸アンモニウム234111、モリブデン酸ア
ンモニウム70.6a 、炭酸ナトリウム8.48a
、リン酸二水素アンモニウム9.2g、硝酸カリウム2
0.2aおよび硝酸ルビジウム44.30を溶解させた
のち直径0.3ミクロン、長さ80ミクロンのタングス
テンウィスカー20(]を加え攪拌機で分散させて触媒
スラリー液を得た。Example 3 Oxalic acid 260Q was dissolved in 1500 cc of water, and ammonium metavanadate 234111, ammonium molybdate 70.6a, and sodium carbonate 8.48a were added to the solution.
, ammonium dihydrogen phosphate 9.2 g, potassium nitrate 2
After dissolving 0.2a and 44.30 rubidium nitrate, tungsten whiskers 20 (0.3 microns in diameter and 80 microns in length) were added and dispersed with a stirrer to obtain a catalyst slurry.
90重量%のsr C,3重量%のfvlooおよび7
型口%の8102よりなる見掛気孔率28%、比表面積
0.05rd/u 、直径5fllI11および長さ5
mmのベレット状多孔性担体に実施例1と同様な方法で
活性物質を1217/100cc担体の担持率で担持さ
せ、450℃で空気流通下4時間焼成して触媒−Eを得
た。なお、活性物質の組成比は、V2O5:MOO3:
Na2O:P2O5:に20:Rb20=1 : 0
.4: 008 : 0.04 :0、1 :
0.15モル比であり、活性物質中のウィスカー含量は
7重量%であった。90% by weight sr C, 3% by weight fvloo and 7
The apparent porosity is 28%, the specific surface area is 0.05rd/u, the diameter is 5flI11, and the length is 5.
The active substance was supported on a pellet-like porous carrier of 1.0 mm in diameter in the same manner as in Example 1 at a loading ratio of 1217/100 cc of carrier, and was calcined at 450° C. for 4 hours under air circulation to obtain Catalyst-E. The composition ratio of the active substance is V2O5:MOO3:
Na2O:P2O5:20:Rb20=1:0
.. 4: 008: 0.04: 0, 1:
The molar ratio was 0.15, and the whisker content in the active substance was 7% by weight.
一方、硝酸カリウムおよび硝酸ルビジウムは全く添加し
ないでリン酸二水素アンモニウムの添加量を41.41
1と変更した以外は触媒−Fと全く同様にして触媒組成
比がV205 :MOOs :Na2O:P2O5=1
: 0.4+ 0.08 : 0.18モル比
、ウィスカー含量が7重量%の触媒−Fが調製された。On the other hand, potassium nitrate and rubidium nitrate were not added at all, and the amount of ammonium dihydrogen phosphate added was 41.41.
The catalyst composition ratio was V205:MOOs:Na2O:P2O5=1 except that it was changed to 1.
:0.4+0.08:0.18 molar ratio and whisker content of 7% by weight Catalyst-F was prepared.
溶融塩浴に浸された内径20mm、長さ3.5メートル
の管に先ず触媒−Fを1メートルの高さに充填し、次い
でその上に触媒−Eを1.8メートルの高さに充填し、
365℃の温度に保った。ベンゼン濃度70a /NM
3で120℃に予熱されたベンゼン−分子状酸素含有ガ
ス(酸素12%。A tube with an inner diameter of 20 mm and a length of 3.5 meters immersed in a molten salt bath was first filled with catalyst-F to a height of 1 meter, and then filled with catalyst-E to a height of 1.8 meters above it. death,
The temperature was maintained at 365°C. Benzene concentration 70a/NM
Benzene-molecular oxygen-containing gas (12% oxygen) preheated to 120°C at 3.
水蒸気10%、窒素78%)混合ガスを反応管上部より
空間速度2800Hr ” (STP>で導通したとこ
ろ、100%純度ベンゼンに対して97重缶%の収率で
無水マレイン酸が得られた。When a mixed gas (10% water vapor, 78% nitrogen) was introduced from the top of the reaction tube at a space velocity of 2800 Hr''(STP>), maleic anhydride was obtained at a yield of 97% based on 100% pure benzene.
実施例4
1500ccの水に蓚酸260oを溶解し、これにメタ
バナジン酸アンモニウム234(+、モリブデン酸アン
モニウム106g、炭酸ナトリウム3.18(]および
リン酸酸二水素アンモラム、23gを溶解し、直径0.
4ミクロン、長さ15ミクロンのシリコンカーバイドウ
ィスカー110を添加し攪拌して触媒スラリー液とした
。この触媒スラリー液を用い、見掛気孔率25%、比表
面積0.03ゴ/Q 、純度98.5%のsrc自焼結
担体く直径5.5mm、球状)に実施例1と同様な方法
で活性物質を担持せしめ、420℃の温度にて空気流通
下6時間焼成して触媒−Gを得た。Example 4 Oxalic acid 260°C was dissolved in 1500cc of water, and ammonium metavanadate 234 (+), ammonium molybdate 106g, sodium carbonate 3.18g (], and ammonium dihydrogen phosphate, 23g were dissolved in the solution, and a diameter of 0.25g was dissolved in 1500cc of water.
Silicon carbide whiskers 110 of 4 microns and 15 microns in length were added and stirred to form a catalyst slurry. Using this catalyst slurry liquid, an SRC self-sintering carrier (diameter 5.5 mm, spherical) with an apparent porosity of 25%, a specific surface area of 0.03 G/Q, and a purity of 98.5% was prepared in the same manner as in Example 1. An active substance was supported on the catalyst, and the mixture was calcined at 420° C. for 6 hours under air flow to obtain Catalyst-G.
活性物質の担持率は10(J/100CC担体であり、
組成比はV20s :MOO3:Na2O:P20s
: = 1 : 0.6: 003 : 0.
001−Eル比rあった。また、SiCウィスカー含有
率は活性物質に対して4重量%であった。The loading rate of the active substance is 10 (J/100CC carrier,
The composition ratio is V20s:MOO3:Na2O:P20s
: = 1 : 0.6: 003 : 0.
There was a 001-E ratio. Moreover, the SiC whisker content was 4% by weight based on the active substance.
一方、硝酸タリウム53.30を添加し、またリン酸二
水素アンモニウムの添加量を57.5+I+とした以外
は触媒−Gと全く同様にして活性物質の組成比がV20
s :MOO3:Na2 Q:P20s :T120=
1 : 0.6: 0.03 : 0.25 :
0.1モル比、ウィスカー含有率が4重量%の触媒−H
が調製された。On the other hand, the composition ratio of the active substance was adjusted to V20 in the same manner as Catalyst-G except that 53.30% of thallium nitrate was added and the amount of ammonium dihydrogen phosphate was 57.5+I+.
s :MOO3:Na2 Q:P20s :T120=
1: 0.6: 0.03: 0.25:
Catalyst-H with 0.1 molar ratio and whisker content of 4% by weight
was prepared.
溶融塩浴に浸された内径25−ffl、長さ3.5メー
トルの管に先ず触媒−Hを1.4メートルの高さに充填
し、次いでその上に触媒−Gを1.4メートルの高さに
積層充填し温度を355℃に保った。ベンゼン濃度60
(1/NM で120℃に予熱されたベンゼン−空気
混合ガスを反応管上部より空間速度3000Hr ”(
STP)で通じたところ100%純度ベンゼンに対し9
9重量%の収率で無水マレイン酸が得られた。A 25-ffl inner diameter, 3.5 meter long tube immersed in a molten salt bath was first filled with Catalyst-H to a height of 1.4 meters and then topped with Catalyst-G to a height of 1.4 meters. The containers were stacked and packed to the same height, and the temperature was maintained at 355°C. Benzene concentration 60
(Benzene-air mixed gas preheated to 120°C at 1/NM was pumped from the top of the reaction tube at a space velocity of 3000 Hr.
According to STP), it is 9 for 100% pure benzene.
Maleic anhydride was obtained with a yield of 9% by weight.
実施例5
1500ccの水に蓚酸260gを溶解し、これにメタ
バナジン酸アンモニウム234g、モリブデン酸アンモ
ニウム141g、硝酸ナトリウム8.5g、リン酸二水
素アンモラム4.6+I+、硝酸カリウム20.2(+
および硝酸セシウム39C1を溶解させたのち直径0.
3ミクロン、長さ50ミクロンのシリコンカーバイドウ
ィスカー11(+を添加し攪拌して触媒スラリー液をと
した。この触媒スラリー液を用い、実施例1と同じ担体
に同様な方法で活性物質を担持せしめ、空気中450℃
にて8時間焼成して触媒■を得た。このようにしぞ得ら
れた活性物質の組成比は
V2 0s :Mo Os :Na 2 0
: P2 0s:C320:に2 0=1 :
0.8: 005 : 0.02 :0.1:
0.1モル比でありウィスカー含有率は活性物質に
対して4重間%であった。Example 5 260 g of oxalic acid was dissolved in 1,500 cc of water, and 234 g of ammonium metavanadate, 141 g of ammonium molybdate, 8.5 g of sodium nitrate, 4.6+I+ ammorum dihydrogen phosphate, and 20.2(+) potassium nitrate were dissolved in 1500 cc of water.
After dissolving cesium nitrate 39C1, the diameter is 0.
Silicon carbide whiskers 11 (+) having a diameter of 3 microns and a length of 50 microns were added and stirred to obtain a catalyst slurry. Using this catalyst slurry, an active substance was supported on the same carrier as in Example 1 in the same manner. , 450℃ in air
The catalyst was calcined for 8 hours to obtain catalyst (2). The composition ratio of the active substance thus obtained is V20s:Moos:Na20
: P2 0s: C320: 2 0=1 :
0.8: 005: 0.02: 0.1:
The molar ratio was 0.1 and the whisker content was interquadruple % with respect to the active substance.
リン酸二水素アンモニウムの添加量を230とし、硝酸
カリウムの代りに硝酸バリウムを26.1gとした以外
は触媒層と全く同様にして活性物質の組成比がV205
:MOO3:Na2O:P205 :C320:Ba
O=1 : 0.8: 0.05 :0.10
: 0.1: 0.1モル比である触媒−Jが得ら
れた。The active substance composition ratio was V205 in exactly the same manner as the catalyst layer except that the amount of ammonium dihydrogen phosphate added was 230 and barium nitrate was 26.1 g instead of potassium nitrate.
:MOO3:Na2O:P205 :C320:Ba
O=1: 0.8: 0.05: 0.10
:0.1:0.1 molar ratio of catalyst-J was obtained.
溶融塩浴に浸された内径25mn+、長さ3.5メート
ルの管に触媒Jを1.25メートルの高さに充填し、次
いでその上に触媒−■を1.25メートルの高さに充填
し温度を355℃に保った。ベンゼン濃度6!M/NM
のベンゼン−空気混合ガスを空間速度3000Hr
−’(STP)で導通したところ100%純度ベンゼン
に対し99.5重1%の収率で無水マレイン酸が得られ
た。A tube with an inner diameter of 25 m+ and a length of 3.5 m immersed in a molten salt bath was filled with catalyst J to a height of 1.25 m, and then catalyst -■ was filled on top of it to a height of 1.25 m. The temperature was maintained at 355°C. Benzene concentration 6! M/NM
benzene-air mixed gas at a space velocity of 3000 Hr.
-' (STP), maleic anhydride was obtained at a yield of 99.5% by weight based on 100% pure benzene.
比較例1
水150OId中に蓚酸272gを溶解してメタバナジ
ン酸アンモニウム230Q、モリブデン酸アンモニウム
69.4g、リン酸三ナトリウム11.2CIおよび硝
酸ナトリウム6.7gを順次溶解させて触媒液とした。Comparative Example 1 272 g of oxalic acid was dissolved in 150 OId of water, and 230 Q of ammonium metavanadate, 69.4 g of ammonium molybdate, 11.2 CI of trisodium phosphate, and 6.7 g of sodium nitrate were sequentially dissolved to prepare a catalyst liquid.
担体として見掛気孔率38%、比表面積0.05d/Q
でSiC純度が98.7重量%である直径7〜8闘のS
iCの自焼結型球状品を1800cc用い、実施例1と
同様な方法で活性物質を担持せしめた。えられた担持体
は空気流通下で8時間焼成して触媒−にとされた。活性
物質の担持率は8a/100cc担体であり、その組成
比はV205 :Mo Os :Na2O:P205−
1 :0.40 : 006 : 0.015モル
比であった。Apparent porosity 38%, specific surface area 0.05d/Q as carrier
S with a diameter of 7 to 8 mm and a SiC purity of 98.7% by weight.
An active substance was supported in the same manner as in Example 1 using 1800 cc of iC's self-sintering spherical product. The obtained support was calcined for 8 hours under air circulation to form a catalyst. The loading rate of the active substance is 8a/100cc carrier, and the composition ratio is V205:MoOs:Na2O:P205-
The molar ratio was 1:0.40:006:0.015.
溶融塩浴に浸された内径25 mn+1長さ385メー
トルの管に触媒−Kを2.5メートルの高さに充填し、
温度を365℃に保った。ベンゼン濃度50o/NM
で120℃に予熱されたベンゼン−空気混合ガスを空
間速度3006Hr”で触媒層に通じたところ、熱点の
温度は520℃に達し、100%純度ベンゼンに対し、
86重」%の収率で無水マーイン酸が得られたにすぎな
かった。A tube with an internal diameter of 25 m + 1 and a length of 385 meters, immersed in a molten salt bath, was filled with catalyst-K to a height of 2.5 meters,
The temperature was maintained at 365°C. Benzene concentration 50o/NM
When a benzene-air mixture gas preheated to 120°C was passed through the catalyst layer at a space velocity of 3006 hours, the temperature at the hot spot reached 520°C, which was 100% pure benzene.
Only a yield of 86% by weight of maric anhydride was obtained.
実施例6
実施例1による触媒(A、B積層充填)と実施例1の触
媒においてウィスカーを添加せしめないで得た触媒しお
よびM(活性物質の担持はそれぞれ15および12o
/100cc担体)とを実施例1記載の積層形式ならび
に反応条件下で長期酸化反応比較を行なった。結果を表
1に示す。Example 6 The catalysts according to Example 1 (A, B stacked packing) and the catalysts of Example 1 obtained without the addition of whiskers and M (active substance loadings of 15 and 12 o, respectively)
A long-term oxidation reaction comparison was conducted under the stacking format and reaction conditions described in Example 1. The results are shown in Table 1.
触媒(A+8)は触tIi層圧力損失の経時上昇は全く
認められず、無水マレイン酸収率の変化も殆とんど認め
られなかった。一方、触媒(L+M)のほうではウィス
カー不使用ゆえに幾分担持率を低くせざるをえなかった
にもかかわらず経時的な触媒層圧力損失の上昇が認めら
れ、それとともに無水マレイン酸収率の低下が観測され
た。これはベンゼンの高負荷による活性物質の担体表面
からのハク落劣化によるものである。また、初期の圧力
損失値に差があるのは触媒を管に充填する際の活性物、
質のハク落度の差によるものである。For catalyst (A+8), no increase in pressure loss over time in the tIIi layer was observed, and almost no change in maleic anhydride yield was observed. On the other hand, in the case of catalyst (L+M), although the retention rate had to be lowered somewhat due to the non-use of whiskers, an increase in the pressure loss in the catalyst layer over time was observed, and at the same time, the yield of maleic anhydride decreased. A decrease was observed. This is due to deterioration in which the active substance flakes off the surface of the carrier due to the high loading of benzene. In addition, the reason for the difference in the initial pressure drop value is due to the active material when filling the catalyst into the tube.
This is due to the difference in the degree of peeling of the quality.
実施例7〜10
下記に示した以外は実施例1におけると同様に調製され
た触媒を用い、実施例1におけると同様に反応を行い、
表2に示す結果を得た。Examples 7 to 10 The reaction was carried out in the same manner as in Example 1 using a catalyst prepared in the same manner as in Example 1 except as shown below.
The results shown in Table 2 were obtained.
(実施例7)
触媒Aにおいて、硫酸セシウム72.lの代わりに、硝
酸タリウム106.fl添加したく触媒−N)。(Example 7) In catalyst A, cesium sulfate was 72. Instead of thallium nitrate 106. fl Add catalyst-N).
(実施例8)
触媒Bにおいて、リン酸二水素アンモニウムの添加量を
230とし、かつ、硫酸セシウムの添加量を54.31
11とし、加えて、硫酸カルシウム27.2aを添加し
た(触媒−〇)。(Example 8) In catalyst B, the amount of ammonium dihydrogen phosphate added was 230, and the amount of cesium sulfate added was 54.31.
11, and in addition, calcium sulfate 27.2a was added (catalyst-○).
(実施例9)
触媒Bにおいて、リン酸二水素アンモニウムの添加量を
23(Jとし、かつ、硫酸セシウムの代わりに硫酸カリ
ウムを17.4g添加し、加えて硫酸マグネシウム18
.10および硝酸ストロンチウム6.3gを添加した(
触媒−P)。(Example 9) In catalyst B, the amount of ammonium dihydrogen phosphate added was 23 (J), 17.4 g of potassium sulfate was added instead of cesium sulfate, and 18 g of magnesium sulfate was added.
.. 10 and 6.3 g of strontium nitrate were added (
Catalyst-P).
(実施例10)(Example 10)
Claims (8)
分子状酸素含有ガスにより接触気相酸化して無水マレイ
ン酸を製造する方法において、該反応器の触媒充填層が
、ガス入口側から全触媒層高の30〜70%の高さの部
分の触媒が、 A:五酸化バナジウム(V_2O_5)とその1モルに
対して三酸化モリブデン(MoO_3)0.3〜1.0
モル、酸化ナトリウム(Na_2O)0.03〜0.2
モル、五酸化リン(P_2O_5)0.01〜0.05
モルおよびカリウム、セシウム、タリウムおよびルビジ
ウムよりなる群から選ばれた少なくとも1成分が酸化物
として0.0001〜0.5モルとよりなる活性物質ま
たは B:五酸化バナジウム(V_2O_5)とその1モルに
対して三酸化モリブデン(MoO_3)0.3〜1.0
モル、酸化ナトリウム(Na_2O)0.030.2モ
ルおよび五酸化リン(P_2O_)0〜0.01モルと
よりなる活性物質を、シリコンカーバイド(SiC)含
有量50重量%以上および酸化アルミニウム(Al_2
O_3)含有量10重量%以下の多孔性不活性担体に担
持せしめられたものからなり、続く残りの70〜30%
の高さ部分の触媒が、 C:上記活性物質組成Aに対しP_2O_5を0.05
を超え0.4以下のモル範囲とせしめた活性物質(C−
1)、上記活性物質組成Aに対しP_2O_5を0.0
1〜0.4モルとし、さらにマグネシウム、カルシウム
、ストロンチウムおよびバリウムよりなる群から選ばれ
た少なくとも1成分が酸化物として 0.0001〜0
.5モルの範囲添加せしめてなる活性物質(C−2)お
よび D:上記活性物質組成Bに対しP_2O_5を0.01
を超え0.2以下のモル範囲とせしめた活性物質よりな
る組成のうちのいずれかをシリコンカーバイド(SiC
)含有量50重量%以上および酸化アルミニウム(Al
_2O_3)含有量10重量%以下の多孔性不活性担体
に担持せしめられてなるものであることを特徴とする無
水マレイン酸の製造方法。(1) In a method for producing maleic anhydride by catalytic gas phase oxidation of benzene with air or molecular oxygen-containing gas in a shell-and-tube heat exchanger type reactor, the catalyst packed bed of the reactor is placed on the gas inlet side. A: Vanadium pentoxide (V_2O_5) and molybdenum trioxide (MoO_3) 0.3 to 1.0 per mole of vanadium pentoxide (V_2O_5).
Mol, sodium oxide (Na_2O) 0.03-0.2
Mol, phosphorus pentoxide (P_2O_5) 0.01-0.05
active substance consisting of 0.0001 to 0.5 mole of at least one component selected from the group consisting of potassium, cesium, thallium and rubidium as an oxide; or B: vanadium pentoxide (V_2O_5) and 1 mole thereof; On the other hand, molybdenum trioxide (MoO_3) 0.3 to 1.0
mol, 0.030.2 mol of sodium oxide (Na_2O) and 0 to 0.01 mol of phosphorus pentoxide (P_2O_) with a silicon carbide (SiC) content of at least 50% by weight and aluminum oxide (Al_2
O_3) Consists of a material supported on a porous inert carrier with a content of 10% by weight or less, followed by the remaining 70-30%
C: P_2O_5 is 0.05 for the above active material composition A.
The active substance (C-
1), P_2O_5 is 0.0 for the above active substance composition A
1 to 0.4 mol, and at least one component selected from the group consisting of magnesium, calcium, strontium, and barium is 0.0001 to 0 as an oxide.
.. Active substances (C-2) and D added in a range of 5 mol: P_2O_5 is 0.01 to the above active substance composition B.
silicon carbide (SiC
) content of 50% by weight or more and aluminum oxide (Al
_2O_3) A method for producing maleic anhydride, characterized in that the maleic anhydride is supported on a porous inert carrier having a content of 10% by weight or less.
および酸化アルミニウム含有量3重量%以下の多孔性不
活性担体であることを特徴とする特許請求の範囲(1)
記載の方法。(2) Claim (1) characterized in that the carrier is a porous inert carrier having a silicon carbide content of 80% by weight or more and an aluminum oxide content of 3% by weight or less.
Method described.
の自焼結型多孔性不活性担体であることを特徴とする特
許請求の範囲(1)記載の方法。(3) The method according to claim (1), wherein the carrier is a self-sintering porous inert carrier having a silicon carbide content of 98% by weight or more.
たは塊状であることを特徴とする特許請求の範囲(1)
記載の方法。(4) Claim (1) characterized in that the shape of the carrier is spherical, ring, cylindrical, saddle-shaped, conical, or block-shaped.
Method described.
分子状酸素含有ガスにより接触気相酸化して無水マレイ
ン酸を製造する方法において、該反応器の触媒充填層が
、ガス入口側から全触媒層高の30〜70%の高さの部
分の触媒が、 A:五酸化バナジウム(V_2O_5)とその1モルに
対して三酸化モリブデン(MoO_3)0.3〜1.0
モル、酸化ナトリウム(Na_2O)0.03〜0.2
モル、五酸化リン(P_2O_5)0.01〜0.05
モルおよびカリウム、セシウム、タリウムおよびルビジ
ウムよりなる群から選ばれた少なくとも1成分が酸化物
として0.0001〜0.5モルとよりなる活性物質ま
たは B:五酸化バナジウム(V_2O_5)とその1モルに
対して三酸化モリブデン(MoO_3)0.3〜1.0
モル、酸化ナトリウム(Na_2O)0.03〜0.2
モルおよび五酸化リン(P_2O_5)0〜0.01モ
ルとよりなる活性物質を、該活性物質に対して1〜20
重量%の量の、平均直径が5ミクロン以下であり、かつ
アスペクト比が10〜500であるウィスカーとともに
、シリコンカーバイド(SiC)含有量50重量%以上
および酸化アルミニウム(Al_2O_3)含有量10
重量%以下の多孔性不活性担体に担持せしめられたもの
からなり、続く残りの70〜30%の高さ部分の触媒が
、 C:上記活性物質組成Aに対しP_2O_5を0.05
を超え0.4以下のモル範囲とせしめた活性物質(C−
1)、上記活性物質組成Aに対しP_2O_5を0.0
1〜0.4モルとし、さらにマグネシウム、カルシウム
、ストロンチウムおよびバリウムよりなる群から選ばれ
た少なくとも1成分が酸化物として0.0001〜0.
5モルの範囲添加せしめてなる活性物質(C−2)およ
び D:上記活性物質組成Bに対しP_2O_5を0.01
を超え0.2以下のモル範囲とせしめた活性物質よりな
る組成のうちのいずれかを、該活性物質に対して1〜2
0重量%の量の、平均直径が5ミクロン以下であり、か
つアスペクト比が10〜500であるウィスカーととも
に、シリコンカーバイド(SiC)含有量50重量%以
上および酸化アルミニウム(Al_2O_3)含有量1
0重量%以下の多孔性不活性担体に担持せしめられてな
るものであることを特徴とする無水マレイン酸の製造方
法。(5) In a method for producing maleic anhydride by catalytic gas phase oxidation of benzene with air or molecular oxygen-containing gas in a shell-and-tube heat exchanger type reactor, the catalyst packed bed of the reactor is placed on the gas inlet side. A: Vanadium pentoxide (V_2O_5) and molybdenum trioxide (MoO_3) 0.3 to 1.0 per mole of vanadium pentoxide (V_2O_5).
Mol, sodium oxide (Na_2O) 0.03-0.2
Mol, phosphorus pentoxide (P_2O_5) 0.01-0.05
active substance consisting of 0.0001 to 0.5 mole of at least one component selected from the group consisting of potassium, cesium, thallium and rubidium as an oxide; or B: vanadium pentoxide (V_2O_5) and 1 mole thereof; On the other hand, molybdenum trioxide (MoO_3) 0.3 to 1.0
Mol, sodium oxide (Na_2O) 0.03-0.2
mol and 0 to 0.01 mol of phosphorus pentoxide (P_2O_5) in an amount of 1 to 20
a silicon carbide (SiC) content of 50% by weight or more and an aluminum oxide (Al_2O_3) content of 10% by weight, with whiskers having an average diameter of 5 microns or less and an aspect ratio of 10-500.
C: P_2O_5 is 0.05% of the active material composition A above, and the remaining 70-30% of the catalyst is supported on a porous inert carrier by weight % or less.
The active substance (C-
1), P_2O_5 is 0.0 for the above active substance composition A
1 to 0.4 mole, and at least one component selected from the group consisting of magnesium, calcium, strontium, and barium as an oxide of 0.0001 to 0.4 mole.
Active substances (C-2) and D added in a range of 5 mol: P_2O_5 is 0.01 to the above active substance composition B.
1 to 2% of the active substance in a molar range exceeding 0.2 molar range.
0% by weight of whiskers with an average diameter of 5 microns or less and an aspect ratio of 10 to 500, with a silicon carbide (SiC) content of 50% or more and an aluminum oxide (Al_2O_3) content of 1
1. A method for producing maleic anhydride, characterized in that maleic anhydride is supported on a porous inert carrier in an amount of 0% by weight or less.
および酸化アルミニウム含有量3重量%以下の多孔性不
活性担体であることを特徴とする特許請求の範囲(5)
記載の方法。(6) Claim (5) characterized in that the carrier is a porous inert carrier having a silicon carbide content of 80% by weight or more and an aluminum oxide content of 3% by weight or less.
Method described.
の自焼結型多孔性不活性担体であることを特徴とする特
許請求の範囲(5)記載の方法。(7) The method according to claim (5), wherein the carrier is a self-sintering porous inert carrier having a silicon carbide content of 98% by weight or more.
たは塊状であることを特徴とする特許請求の範囲(5)
記載の方法。(8) Claim (5) characterized in that the shape of the carrier is spherical, ring, cylindrical, saddle-shaped, conical, or block-shaped.
Method described.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/842,934 US4760153A (en) | 1985-03-26 | 1986-03-24 | Process for producing maleic anhydride |
EP86104086A EP0196601B1 (en) | 1985-03-26 | 1986-03-25 | Process for producing maleic anhydride |
DE8686104086T DE3676847D1 (en) | 1985-03-26 | 1986-03-25 | METHOD FOR PRODUCING MALEIC ACID ANHYDRIDE. |
CN86102873.2A CN1020453C (en) | 1985-03-26 | 1986-03-26 | Process for producing maleic anhydride |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60-59627 | 1985-03-26 | ||
JP5962785 | 1985-03-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6278A true JPS6278A (en) | 1987-01-06 |
JPH0354944B2 JPH0354944B2 (en) | 1991-08-21 |
Family
ID=13118656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61040260A Granted JPS6278A (en) | 1985-03-26 | 1986-02-27 | Production of maleic anhydride |
Country Status (2)
Country | Link |
---|---|
JP (1) | JPS6278A (en) |
KR (1) | KR870000900B1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0906783A1 (en) * | 1997-10-03 | 1999-04-07 | Nippon Shokubai Co., Ltd. | Catalyst for catalytic oxidation use |
US6858106B1 (en) | 2000-05-26 | 2005-02-22 | Tetra Laval Holdings & Finance S.A. | Process for producing packaging laminate |
WO2010001732A1 (en) | 2008-06-30 | 2010-01-07 | 株式会社日本触媒 | Method of packing solid particulate substance into fixed-bed multitubular reactor |
US7850928B2 (en) | 2001-01-25 | 2010-12-14 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
JP2015196158A (en) * | 2014-04-02 | 2015-11-09 | クラリアント・インターナシヨナル・リミテツド | Alkali metal-modified vanadium-phosphorus oxide (vpo) catalyst |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106311300A (en) * | 2015-06-24 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for preparation of maleic anhydride through oxidation of butane, and preparation and application methods thereof |
-
1986
- 1986-02-27 JP JP61040260A patent/JPS6278A/en active Granted
- 1986-03-26 KR KR1019860002272A patent/KR870000900B1/en not_active IP Right Cessation
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0906783A1 (en) * | 1997-10-03 | 1999-04-07 | Nippon Shokubai Co., Ltd. | Catalyst for catalytic oxidation use |
US6858106B1 (en) | 2000-05-26 | 2005-02-22 | Tetra Laval Holdings & Finance S.A. | Process for producing packaging laminate |
US7850928B2 (en) | 2001-01-25 | 2010-12-14 | Nippon Shokubai Co., Ltd. | Fixed-bed shell-and-tube reactor and its usage |
WO2010001732A1 (en) | 2008-06-30 | 2010-01-07 | 株式会社日本触媒 | Method of packing solid particulate substance into fixed-bed multitubular reactor |
JP2015196158A (en) * | 2014-04-02 | 2015-11-09 | クラリアント・インターナシヨナル・リミテツド | Alkali metal-modified vanadium-phosphorus oxide (vpo) catalyst |
US9931618B2 (en) | 2014-04-02 | 2018-04-03 | Clariant International Ltd. | Alkali metal-modified vanadium-phosphorus oxide (VPO) catalyst |
Also Published As
Publication number | Publication date |
---|---|
KR870000900B1 (en) | 1987-05-04 |
JPH0354944B2 (en) | 1991-08-21 |
KR860007239A (en) | 1986-10-10 |
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Legal Events
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LAPS | Cancellation because of no payment of annual fees |