GB2109697A - Catalysts and method for manufacture of phthalic anhydride - Google Patents
Catalysts and method for manufacture of phthalic anhydride Download PDFInfo
- Publication number
- GB2109697A GB2109697A GB08227280A GB8227280A GB2109697A GB 2109697 A GB2109697 A GB 2109697A GB 08227280 A GB08227280 A GB 08227280A GB 8227280 A GB8227280 A GB 8227280A GB 2109697 A GB2109697 A GB 2109697A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- weight
- rubidium
- calculated
- titanium dioxide
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 30
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 56
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 48
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 150000003298 rubidium compounds Chemical class 0.000 claims abstract description 13
- 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 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- -1 phosphorus compound Chemical class 0.000 claims abstract description 10
- 229910000344 rubidium sulfate Inorganic materials 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 6
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 4
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000005192 partition Methods 0.000 claims description 7
- 229910052701 rubidium Inorganic materials 0.000 description 10
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001339 alkali metal compounds Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 229910001952 rubidium oxide Inorganic materials 0.000 description 2
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 2
- JDJNFUBFHBCSNO-UHFFFAOYSA-L rubidium(1+);sulfonato sulfate Chemical compound [Rb+].[Rb+].[O-]S(=O)(=O)OS([O-])(=O)=O JDJNFUBFHBCSNO-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 150000003682 vanadium compounds Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 125000005402 stannate group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 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 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
-
- 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
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/55—Cylinders or rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for the manufacture of phthalic anhydride by the catalytic oxidation of naphthelene or ortho- xylene which comprises contacting a mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygen-containing gas with a catalyst bed comprising a first catalyst packed on the upstream side of the flow of mixed gas and a second catalyst packed on the downstream side of the flow, wherein the first catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 90% by weight of titanium dioxide, 9 to 30% by weight of vanadium pentoxide and 0.7 to 3% by weight of a rubidium compound (calculated as Rb2SO4), and the second catalyst has carried on the nonporous inactive carrier a catalytically active component composed of 67 to 94% by weight of titanium dioxide, 5 to 30% by weight of vanadium pentoxide and at least one member selected from the group consisting of 0.1 to 1% by weight of a tin compound (calculated as SnO2) and 0.5 to 3% by weight of a phosphorus compound (calculated as P2O5). The individual catalysts are also claimed.
Description
SPECIFICATION
Method for manufacture of phthalic anhydride
This invention relates to a method for the manufacture of phthalic anhydride. More particularly, this invention relates to a method for producing phthalic anhydride by subjecting naphthalene or orthoxylene in a gaseous phase to catalytic oxidation with a molecular oxygen-containing gas.
Phthalic anhydride, as widely known, is produced commercially by passing a mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygen-containing gas at elevated temperatures through a shell- and tube reactor packed with a catalyst thereby causing catalytic oxidation of naphthalene or ortho-xylene. A typical catalyst usable for this method comprises a nonporous inactive carrier and a catalytically active substance comprising 1 to 1 5% by weight of vanadium pentoxide and 99 to 85% by weight of titanium dioxide deposited in a layer of a thickness of 0.02 to 2 mm on the carrier and used in an amount such that the vanadium pentoxide content falls in the range of 0.05 to 3% by weight based on the catalyst (U.S. Patent 3,464,930).There has been proposed another method which has a phosphorus compound further included in the catalytically active substance deposited on the carrier in the aforementioned catalyst (U.S. Patent 3,684,741). A typical catalyst to be used in this method comprises a nonporous inactive carrier and a catalytically active substance consisting of 1 to 40% by weight of vanadium pentoxide and 60 to 99% by weight of titanium dioxide and superposed in a thin layer on the aforementioned carrier, with the catalytically active substance further containing therein rubidium and/or caesium in the form of an oxide in an amount of 0.15 to 1.5% by weight based on the titanium dioxide and having a phosphorus pentoxide content of 0.05 to 4% by weight based on the catalyst (German Offenlegungsschrift P 24 36 009).
Generally it is known that in a catalyst for the oxidation of naphthalene which has vanadium pentoxide and titanium dioxide as main catalytic components, an alkali metal compound added to the catalytic components prevents naphthalene from excessive oxidation and improved selectivity for phthalic anhydride or for phthalic anhydride and naphthoquinone. Since the alkali metal compound is added in a large amount, however, the catalytic activity is notably lowered and the yield is lowered.
Thus, it has been customary to add this compound only in a small amount as in the methods of the aforementioned patents. Particularly in the case of rubidium, even when it is added in a small amount, it exhibits a notably high effect as compared with potassium and other alkali metals. Thus, it has been held not advantageous to add rubidium in a large amount.
Besides, the conventional methods such as described above have proved unsatisfactory in terms of repression of by-products, life of catalyst, yield of phthalic anhydride, etc. These problems become quite conspicuous when naphthalene is used as the raw material. These problems gain in seriousness in proportion as the concentration of naphthalene or ortho-xylene in the feed gas increases. Economically, however, it is desirable that the concentration of naphthalene or ortho-xylene should be so high as to exceed the lower explosive limit. In the meantime, the formation of by-products can be decreased by carrying out the oxidation at as high a temperature, at as low a gas feed volume (for as long a retention time), and in as low a concentration of naphthalene or ortho-xylene as possible.Under the conditions satisfying all these requirements, however, the productivity of phthalic anhydride is low.
With a view to eliminating the drawbacks mentioned above, there has been proposed a method of effecting the gaseous-phase oxidation of naphthalene or ortho-xylene by using on the up-stream side of the flow of a mixed gas of raw materials a first catalyst carrying thereon a catalytically active substance consisting of vanadium pentoxide and titanium dioxide and containing rubidium in an amount of 0.01 to 0.3% by weight based on the titanium dioxide and containing no phosphorus and on the downstream side of the flow a second catalyst carrying therein a catalytically active substance consisting of vanadium pentoxide and titanium dioxide and containing phosphorus in an amount of 0.02 to 0.8% by weight based on the titanium dioxide and containing no rubidium (German Offenlegungsschrift
P 25 46 268).Even this method has a problem that the yield of phthalic anhydride is not sufficient as a whole. This problem is particularly conspicuous when naphthalene is used as the raw material.
According to a first aspect of the present invention, there is provided a method for the
manufacture of phthalic anhydride by the catalytic oxidation of naphthalene or ortho-xylene which comprises contacting a mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygencontaining gas with a catalyst bed comprising a first catalyst packed on the upstream side of the aforementioned flow of mixed gas and a second catalyst packed on the downstream side of the flow, wherein the first catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 90% by weight of titanium dioxide, 9 to 30% by weight of vanadium pentoxide and
0.7 to 3% by weight of a rubidium compound (calculated as Rb2SO4), and the second catalyst has carried on the nonporous inactive carrier a catalytically active component composed of 67 to 94% by weight of titanium dioxide, 5 to 30% by weight of vanadium pentoxide and at least one member selected from the group consisting of 0.1 to 1% by weight of a tin compound (calculated as SnO2) and 0.5 to 3% by weight of a phosphorus compound (calculated as P205).
This invention therefore enables the provision of an improved method for the manufacture of phthalic anhydride.
This invention also enables the provision of a method for producing phthalic anhydride in high yield and with high productivity.
According to a second aspect of the invention, there is provided a catalyst suitable for use in the manufacture of phthalic anhydride, which catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 90% by weight of titanium dioxide, 9 to 30% by weight of vanadium pentoxide, and 0.7 to 3% by weight of a rubidium compound calculated as rubidium sulphate.
According to a third aspect of the invention, there is provided a catalyst suitable for use in the manufacture of phthalic anhydride, which catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 94% by weight of titanium dioxide, 5 to 30% by weight of vanadium pentoxide and 0.1 to 1 R6 by weight of a tin compound (calculated as SnO2).
The first catalyst to be used as packed on the upstream side of the flow of the mixed gas of raw materials in the present invention is formed by having carried on a nonporous inactive carrier 20 to 200 g, preferably 40 to 1 50 g, per litre of the carrier of a catalytically active component composed of 67 to 90% by weight, preferably 70 to 85% by weight, of titanium dioxide, 9 to 30% by weight, preferably 1 5 to 25% by weight, of vanadium pentoxide, 0.7 to 3% by weight, preferably 1.0 to 2.0% by weight, of rubidium (calculated as Rb2SO4). The aforementioned catalytically active component substantially does not contain either a tin compound or a phosphorus compound. Optionally, it may contain compounds such as K, Cs and/or Fe in small amounts.This catalyst may be produced by dissolving vanadium pentoxide or any of vanadium compounds such as, for example, ammonium vanadate, and sulphate, oxalate, formate, acetate and tartrate of vanadium which are converted by heating to vanadium pentoxide in water or a mixed solvent of an organic solvent such as alcohol with water, combining the resultant solution with a suitable rubidium compound and finely divided titanium dioxide, then, either spraying an inactive carrier with the resultant slurry-like mixture, or immersing the inactive carrier in the slurry-like mixture, and heating the carrier with the slurry-like mixture, or spraying the slurry-like mixture on the carrier heated in advance to a stated temperature.
Examples of the rubidium compound advantageously usable herein include rubidium sulphate, rubidium oxide, rubidium carbonate, rubidium acetate and rubidium nitrate. Rubidium sulphate is preferred to the other rubidium compounds cited above. These rubidium compounds except rubidium sulphate are converted into their corresponding oxides at relatively high temperatures. In the catalyst, rubidium exists as rubidium sulphate, rubidium oxide or rubidium vanadate, for example. The most desirable form is the oxy-acid salt of sulphur such as rubidium sulphate or rubidium pyrosulphate.
The second catalyst to be used, as packed on the downstream side of the flow of the mixed gas of raw materials is formed by having carried on a nonporous inactive carrier 20 to 200 g, preferably 40 to 1 50 g, per litre of the aforementioned carrier of a catalytically active component composed of 67 to 94% by weight, preferably 70 to 85% by weight, of titanium dioxide, 9 to 30% by weight, preferably 1 5 to 25% by weight, of vanadium pentoxide, and 0.1 to 1% by weight, preferably 0.2 to 0.6% by weight, of a tin compound (calculated as SnO2) and/or 0.5 to 3% by weight, preferably 1 to 2% by weight, of a phosphorus compound (calculated as P205). The aforementioned catalytically active component substantially does not contain an alkali metal compound such as a rubidium compound. Optionally, it may contain compounds of Fe, Cr, Mo and/or W in small amounts.
This catalyst may be produced by an ordinary method, for example. To be specific, it may be produced by dissolving vanadium pentoxide or any of the aforementioned vanadium compounds capable of being converted by heating into vanadium pentoxides in water or in the aforementioned organic solvent, combining the resultant solution with either or both of a suitable tin compound and a suitable phosphorus compound and with finely divided titanium dioxide, then either spraying an inactive carrier with the resultant slurry-like mixture or immersing the inactive carrier in the slurry-like mixture, and heating the carrier wet with the slurry-like mixture, or spraying the slurry-like mixture on the carrier heated in advance to a stated temperature.
Examples of the tin compound advantageously usable herein include tin oxide, stannic chloride and tin acetate. These tin compounds are converted into tin oxides when they are calcined. Examples of the phosphorus compound advantageously usable herein are ammonium phosphate, phosphoric acid, phosphorous acid and phosphoric esters.
The chemical names used in this specification to designate the components for the catalytically active substances are intended solely for the convenience of calculation. As is well known, actually in the catalyst, vanadium is present in the form of VOx (x = 1 to 5) or a vanadate and rubidium in the form of rubidium sulphate or rubidium pyrosulphate, for example. By the same token, tin is present in the form of SnOx or a stannate and phosphorus in the form of POX or a phosphate, for example.
Titanium dioxide in the form of anatase, titanium dioxide hydrate, etc. is available as a source for titanium oxide in the catalyst to be used in the present invention.
Examples of the nonporous inactive carrier to be used for the catalyst of the present invention are sintered or fused masses of silicates, steatite, ceramics, alumina and silicon carbide. To be effectively used in this invention, the aforementioned catalyst is desired to be in the shape of spheres, cylinders or rings, for example, which have an equivalent diameter of about 3 to 1 2 mm, preferably about 6 to 10 mm. The cylinders or rings of the catalyst have a height of about 3 to 10 mm, more desirably about 4 to 8 mm, and most desirably about 70 to 80% of the equivalent diameter. Among other shapes, the shape of rings proves desirable.Particularly the shape of Lessing rings which, as disclosed in Japanese
Patent Application Disclosure SHO 56(1981 )-1 55,653, are a carrier of the shape of tubes each divided into two substantially equal cells by a partition wall disposed substantially perpendicularly to a plane in the diametric direction of the tube, with the tubes each measuring 6 to 10 mm in outside diameter, 4 to 8 mm in inside diameter, and 4 to 10 mm in height, the ratio of the thickness, b mm, of the partition wall to the thickness, a mm, of the peripheral wall of the tube, b/a, falling in the range of 0.4 to 0.8 (providing that b is larger than 0.5), and the thickness of the padding, C mm, of the peripheral wall at the joint between the peripheral wall and the partition wall and the length of the padding, d mm, in the circumferential direction from the intersection between the peripheral wall and the partition wall satisfying the formula, C = e x 0.1 -- 0.3 - d x 0.5 Y 1.5 (providing that C is equal to or larger than 0 and e denotes the inside diameter in mm) proves particularly desirable because it suffers only a little pressure loss and permits oxidation in a high concentration. In the case of the carrier in the shape of rings, the inside diameter of each ring is suitably 2 to 10 mm, preferably about 4 to 8 mm. In the case of the carrier in the shape of Lessing rings, it is proper that the rings should be provided with a partition wall substantially in the centre and possessed of a wall thickness of 0.5 to 2 mm, preferably 0.6 to 1 mm.
After the catalytically active substance has been deposited on the carrier, the resultant composite is heated to complete a catalyst. This heating is carried out at a temperature in the range of 3000 to 6000C, preferably in an atmosphere of oxygen for a period of 4 to 10 hours to effect required thermal decomposition.
The catalyst completed as described above is used to pack a shell-and-tube reactor. Then, a mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygen-containing gas such as air is passed through this reactor to effect catalytic oxidation of naphthalene or ortho-xylene. When the two catalysts are used as described above, the volumetric ratio of the first catalyst to the second catalyst generally is such that the second catalyst has a volume of 30 to 300 parts, preferably 30 to 1 50 parts, more preferably 30 to 95 parts, based on 100 parts of the first catalyst. Within the shell-and-tube reactor, the second catalyst is packed in a lower layer of a prescribed volume and the first catalyst is packed in an upper layer of a prescribed volume.Downwardly from the upper side of the reactor, the mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygen-containing gas such as air is passed to effect the catalytic oxidation. The reaction temperature is 3000 to 4000 C, preferably 3300 to 3800C, the concentration of naphthalene or ortho-xylene is 30 to 80 g/m3 of air at NTP preferably 40 to 60 g/m3 of air at NTP, and the space velocity of the feed gas is 1 ,000 to 8,000 her~, preferably 2,000 to 5,000 her~1.
In accordance with this invention, the selectivity of the conversion to phthalic anhydride is improved and the overall yield of phthalic anhydride is improved without entailing any notable drop of activity by using the catalyst which incorporates rubidium in an amount of 0.7 to 3% by weight calculated as Rb2SO4. Owing to the use of the two catalysts described above, the first catalyst causes the oxidation with a relatively high selectivity to permit selective conversion of naphthalene or orthoxylene to phthalic anhydride and the second catalyst effects the oxidation with a high activity and decreases the amount of unreacted hydrocarbon to the fullest possible extent. As a whole, they permit phthalic anhydride to be obtained in a high yield, with the formation of by-products decreased.The effect of the two catalysts is particularly conspicuous when naphthalene is used as the raw material.
Now this invention will be described more specifically below with reference to working examples.
Whenever "%" is mentioned in the following working examples, it is meant to be % by weight unless otherwise specified.
EXAMPLES 1-22 (A) Preparation of first catalyst
Powdered titanium dioxide (containing anatase type titanium dioxide) was combined with an aqueous solution having ammonium metavanadate and rubidium sulphate dissolved in advance therein.
The resultant mixture was thoroughly stirred and emulsified into a slurry liquid. In a rotary furnace, a ceramic carrier of the shape of Lessing rings having 8 mm of outer diameter, 5 mm of inner diameter, 6 mm of height and 1 mm of thickness of partition wall was placed and preheated therein to temperature of 200 to 2500C. Now with the rotary furnace kept in rotation, the preheated carrier was sprayed with the aforementioned slurry liquid so that the carrier would carry 80 g of the catalyst components per litre of carrier. Under a sweeping flow of air, the resultant composite was calcined at 5500C for 6 hours to produce a catalyst.
The aforementioned treatments were so controlled that the catalytically active component of the produced catalyst would be composed of 1 8% of V205, 0.5 to 2.5% of Rb2SO4, and the balance to make up 100% of TiO2.
(B) Preparation of second catalyst
Similarly to the first catalyst, powdered titanium dioxide, ammonium metavanadate, tin chloride or ammonium phosphate were added to deionized water. The resultant mixture was stirred and emulsified to produce a catalyst of the form of slurry liquid. By following the procedure used in the preparation of the first catalyst, this liquid catalyst was sprayed on a carrier of the shape of Lessing rings so that the carrier would carry 80 g of the catalyst component per litre of carrier. Under a sweeping flow of air, the resultant composite was calcined at 5500C for 6 hours to produce a catalyst.The treatment mentioned above were so controlled that the catalytically active component of the produced catalyst would be composed of 20% of V205, 0.3 to 2.5% of SnO2 or P20s, and the balance to make up 100% of TiO2.
(C) Production of phthalic anhydride
A reaction tube 25 mm in inside diameter immersed in a nitre bath was packed with a bed of the first catalyst and a bed of the second catalyst downwardly in the order mentioned. A mixed gas of naphthalene and air was passed through this reaction tube. The concentration of naphthaiene was 50 g/m3 at NTP, the space velocity was 3,000 hF1, and the temperature of nitre was in the optimum range of 3400 to 3600C. The results were as shown in Table 1.
TABLE 1
Rb2SO4 P205 or SnO2 Ratio of
content content of first to Yield of Yield of
of first second second phthalic naphtho
Example catalyst catalyst (%) catalyst bed anhydride quinone
No. (%) P205 SnO2 in length (%) (%)
1 2 1.5 - 3 104.0 1.5
2 2 1.5 - 1.8 104.7 0.8
3 2 1.5 - 1.1 104.5 0.03
4 2 2 - 1.8 104.6 0.4
5 2 2 - 1.1 103.7 0.2
6 1.5 2.5 - 1.1 102.6 0.02
7 1.5 2 - 1.8 104.0 0.2
8 1.5 2 - 1.1 103.8 0.06
9* 1.5 2 - 1.1 103.6 0.25
10 1.5 1.5 - 1.1 103.7 0.03
11 1.5 1.5 - 1.8 103.9 0.21
12 1.0 2 - 1.1 103.0 0.01
13 3 1.5 - 3 103.1 1.3
14 0.7 2 - 1.1 101.0 0.01
15 2 - 0.5 1.1 102.5 0.02
16 2 - 0.5 1.8 103.2 0.2
17 2 - 0.3 3 103.6 1.7
18 2 - 0.3 1.8 104.7 0.8
19 2 - 0.3 1.1 103.5 0.3
20 1.5 - 0.3 3 103.9 0.9
21 1.5 - 0.3 1.8 104.1 0.7
22 1.5 - 0.3 1.1 103.2 0.2
* This Example shows data after six months' operation.
EXAMPLES 23-27 Catalysts were prepared by following the procedure of Example 1, except that the amount of Rb2SOd in the preparation of the first catalyst and the amount of P205 or SnO2 in the preparation of the second catalyst varied. The oxidation of naphthalene performed in Example 1 was repeated, except that the catalysts obtained herein were used instead. The results were as shown in Table 2.
TABLE 2
Rb2SO4 P205 or SnO2 Ratio of
content content of first to Yield of Yield of
of first second second phthalic naphtho
Example catalyst catalyst (%) catalyst bed anhydride quinone
No. (%) P205 SnO2 in length (%) (%)
23 5 0 0 1.1 88.6 0.05
24 5 1.5 0 3 97.0 1.1 25* 2 - - 1/0 94.9 8.2
26 5 - 1.0 3 93.9 0.3
27 0.2 1.5 - 1.1 85.0 0.01
* The reaction in this example used the first catalyst alone.
EXAMPLES 28-33 By following the procedure of Example 1, first catalysts and second catalysts were prepared and oxidation of naphthalene was performed by using these catalysts. In Examples 28-29 the content of V2 5 in the catalytically active component of the second catalyst was 10% and 30% respectively. In
Examples 30-31, the concentration of naphthalene in the reaction conditions was 40 g/m3 at NTP and 60 g/m3 at NTP respectively. In Example 32, a ceramics Rashig ring having 8 mm of outer diameter, 5 mm of inner diameter and 6 mm of height was used as the carrier in a similar procedure of Example 1.
In Example 33, ortho-xyler;e was used as raw material instead of naphthalene and a temperature of nitre was 3800C in a similar procedure of Example 1. The results were shown in Table 3.
TABLE 3 Rb2SO4 P205 Era tic of
content content of first to Yield of Yield of
of first second second phthalic naphtho
Example catalyst catalyst cata.lyst bed anhydride quinone
No. (%) (%) in length (%) (%)
28 2 1.5 1.1 103.5 0.03
29 2 1.5 1.1 104.4 1.7
30 2 1.5 1.1 102.7 0.01
31 2 1.5 1.1 104.4 0.30
32 2 1.5 1.1 102.5 0.01
33 1.5 2.0 1.1 114.4 -
Claims (14)
1. A method for the manufacture of phthalic anhydride by the catalytic oxidation of naphthalene or ortho-xylene which comprises contacting a mixed gas consisting of naphthalene or ortho-xylene and a molecular oxygen-containing gas with a catalyst bed comprising a first catalyst packed on the upstream side of the flow of mixed gas and a second catalyst packed on the down-stream side of the flow, wherein the first catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 90% by weight of titanium dioxide, 9 to 30% by weight of vanadium pentoxide and 0.7 to 3% by weight of a rubidium compound (calculated as Rb2SO4), and the second catalyst has carried on the nonporous inactive carrier a catalytically active component composed of 67 to 94% by weight of titanium dioxide, 5 to 30% by weight of vanadium pentoxide and at least one member selected from the group consisting of 0.1 to 1% by weight of a tin compound (calculated as SnO2) and 0.5 to 3% by weight of a phosphorus compound (calculated as P205).
2. A method according to Claim 1, wherein said carrier is in the form of masses.
3. A method according to Claim 2, wherein said masses have an equivalent diameter of about 3 to 12 mm.
4. A method according to Claim 2, wherein said masses are in the shape of rings.
5. A method according to Claim 4 wherein said rings are Lessing rings have a height of 3 to 10 mm and the height is about 70 to 80% of the equivalent diameter of the rings.
6. A method according to Claim 5, wherein said Lessing rings are tubes having an inside diameter of 2 to 10 mm, possessing a partition wall substantially in the centre of the ring, and having a wall thickness of 0.5 to 2 mm.
7. A method according to any one of Claims 1 to 6, wherein said reaction is carried out at a temperature of 300C to 4O00C with the concentration of naphthalene or ortho-xylene in the range of 30 to 80 g/m3 of air at NTP.
8. A method according to any one of Claims 1 to 7, wherein the volumetric ratio of the first catalyst to the second catalyst is such that the second catalyst has a volume of 30 to 300 parts based on 100 parts of the first catalyst.
9. A method according to any one of Claims 1 to 8, wherein the catalytically active component of the first catalyst is composed of 70 to 85% by weight of titanium dioxide, 1 5 to 25% by weight of vanadium pentoxide, and 1.0 to 2.0% by weight of a rubidium compound (calculated as Rb2SO4) and the catalytically active component of the second catalyst is composed of 70 to 85% by weight of titanium dioxide, 1 5 to 25% by weight of vanadium pentoxide, and at least one member selected from the group consisting of 0.2 to 0.6% by weight of a tin compound (calculated as SnO2) and 1 to 2% by weight of a phosphorus compound (calculated as P205).
10. A method according to Claim 9, wherein the volumetric ratio of the first catalyst to the second catalyst is such that the second catalyst has a volume of 30 to 90 parts based on 100 parts of the first catalyst.
11. A method according to Claim 7, wherein said rubidium compound is rubidium sulphate.
12. A catalyst suitable for use in the manufacture of phthalic anhydride, which catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 90% by weight of titanium dioxide, 9 to 30% by weight of vanadium pentoxide, and 0.7 to 3% by weight of a rubidium compound calculated as rubidium sulphate.
13. A catalyst according to Claim 12, wherein the rubidium compound is rubidium sulphate.
14. A catalyst suitable for use in the manufacture of phthalic anhydride, which catalyst has carried on a nonporous inactive carrier a catalytically active component composed of 67 to 94% by weight of titanium dioxide, 5 to 30% by weight of vanadium pentoxide and 0.1 to 1% by weight of a tin compound (calculated as SnO2).
1 5. A method for the manufacture of phthalic anhydride substantially as prescribed in any one of
Examples 1 to 24 and 26 to 33.
1 6. A catalyst according to Claim 12 substantially as described in any one of Examples 1 to 33.
1 7. A catalyst according to Claim 14 substantially as described in any one of Examples 1 to 24 and 26 to 33.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56155658A JPS6037108B2 (en) | 1981-09-30 | 1981-09-30 | Method for producing phthalic anhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2109697A true GB2109697A (en) | 1983-06-08 |
| GB2109697B GB2109697B (en) | 1985-10-09 |
Family
ID=15610771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08227280A Expired GB2109697B (en) | 1981-09-30 | 1982-09-24 | Catalysts and method for manufacture of phthalic anhydride |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6037108B2 (en) |
| KR (1) | KR870000919B1 (en) |
| GB (1) | GB2109697B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539878A2 (en) * | 1991-10-25 | 1993-05-05 | Nippon Shokubai Co., Ltd. | Method for production of phthalic anhydride by vapor-phase oxidation of mixture of ortho-xylene with naphthalene |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161823U (en) * | 1985-03-26 | 1986-10-07 | ||
| JPH062602B2 (en) * | 1986-03-28 | 1994-01-12 | 日本板硝子株式会社 | Fiber manufacturing method and device |
| JPS62263359A (en) * | 1986-05-09 | 1987-11-16 | 大日本インキ化学工業株式会社 | Carbon fiber heat insulating material |
| JPS6385116A (en) * | 1986-09-26 | 1988-04-15 | Dainippon Ink & Chem Inc | Heat insulating material of carbon fiber |
| JPS63253080A (en) * | 1987-04-10 | 1988-10-20 | Nippon Steel Chem Co Ltd | Production of phthalic anhydride |
| JPH0542564Y2 (en) * | 1987-06-26 | 1993-10-27 | ||
| JPH0472417U (en) * | 1990-10-31 | 1992-06-25 | ||
| TW415939B (en) * | 1996-10-23 | 2000-12-21 | Nippon Steel Chemical Co | Gas-phase oxidization process and process for the preparation of phthalic anhydride |
-
1981
- 1981-09-30 JP JP56155658A patent/JPS6037108B2/en not_active Expired
-
1982
- 1982-09-24 GB GB08227280A patent/GB2109697B/en not_active Expired
- 1982-09-30 KR KR8204435A patent/KR870000919B1/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539878A2 (en) * | 1991-10-25 | 1993-05-05 | Nippon Shokubai Co., Ltd. | Method for production of phthalic anhydride by vapor-phase oxidation of mixture of ortho-xylene with naphthalene |
| EP0539878A3 (en) * | 1991-10-25 | 1993-05-19 | Nippon Shokubai Co., Ltd. | Method for production of phthalic anhydride by vapor-phase oxidation of mixture of ortho-xylene with naphthalene |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2109697B (en) | 1985-10-09 |
| JPS5857374A (en) | 1983-04-05 |
| KR870000919B1 (en) | 1987-05-07 |
| KR840001565A (en) | 1984-05-07 |
| JPS6037108B2 (en) | 1985-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4879387A (en) | Method for manufacture of phthalic anhydride | |
| US4077984A (en) | Manufacture of phthalic anhydride from o-xylene or naphthalene | |
| US4665200A (en) | Method for preparing pyromellitic acid and/or pyromellitic anhydride | |
| US6274763B1 (en) | Shell catalyst for producing acetic acid by gas phase oxidation of unsaturated C4 -hydrocarbons | |
| US4046780A (en) | Preparation of phthalic anhydride | |
| JP3112166B2 (en) | Method for producing acetic acid by gas-phase oxidation of saturated C4-hydrocarbon and a mixture thereof with unsaturated C4-hydrocarbon | |
| GB2109697A (en) | Catalysts and method for manufacture of phthalic anhydride | |
| US4469878A (en) | Method for manufacture of phthalic anhydride | |
| US3870655A (en) | Catalyst for the preparation of anthraquinone | |
| US4007136A (en) | Supported catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride | |
| JP2592490B2 (en) | Aromatic hydrocarbon oxidation method | |
| JPH0354944B2 (en) | ||
| JPH0153853B2 (en) | ||
| JPS6128456A (en) | Catalyst for preparing pyromellitic anhydride | |
| JP3298609B2 (en) | Catalyst for producing phthalic anhydride and method for producing phthalic anhydride using the same | |
| JPS6059235B2 (en) | Method for producing phthalic anhydride | |
| JP2563995B2 (en) | Catalyst | |
| JPH0218900B2 (en) | ||
| JPH0242818B2 (en) | ||
| JPH0731882A (en) | Fluid catalyst for vapor-phase catalytic oxidation of p-cresol | |
| JPS63255274A (en) | Production of phthalic anhydride | |
| JPS63208575A (en) | Production of cyanopyridine | |
| JPS6356821B2 (en) | ||
| JPH0649694B2 (en) | Method for producing naphthalic anhydride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940924 |