JP2566814B2 - Solid acid catalyst for hydrocarbon conversion and method for producing the same - Google Patents
Solid acid catalyst for hydrocarbon conversion and method for producing the sameInfo
- Publication number
- JP2566814B2 JP2566814B2 JP63114790A JP11479088A JP2566814B2 JP 2566814 B2 JP2566814 B2 JP 2566814B2 JP 63114790 A JP63114790 A JP 63114790A JP 11479088 A JP11479088 A JP 11479088A JP 2566814 B2 JP2566814 B2 JP 2566814B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acid
- molybdenum
- temperature
- tungsten
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 38
- 238000006243 chemical reaction Methods 0.000 title claims description 28
- 239000011973 solid acid Substances 0.000 title claims description 11
- 229930195733 hydrocarbon Natural products 0.000 title claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000002253 acid Substances 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000005078 molybdenum compound Substances 0.000 claims description 13
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- 150000003658 tungsten compounds Chemical class 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 238000006317 isomerization reaction Methods 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000010933 acylation Effects 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、−11.99より強い酸強度（H0）を有する固
体酸触媒及びその整合方法に関する。TECHNICAL FIELD The present invention relates to a solid acid catalyst having an acid strength (H 0 ) higher than −11.99 and a method for matching the same.
［従来の技術及び発明が解決しようとする問題点］ 石油精製、石油化学工業等においては、分解、異性
化、アルキル化、重合、脱水素或いはアシル化等の炭化
水素転化に、酸触媒を利用した反応が行われている。こ
の酸触媒としては、硫酸、塩化アルミニウム、フッ化水
素、リン酸等が広く用いられている。しかし、これらの
酸触媒は、生成物との分離のほか、反応容器等の装置の
腐食対策や廃酸の処理等にコストがかかる等の問題があ
った。このため、固体酸触媒が採用されており、この固
体酸触媒として、シリカ−アルミナ、チタニア−ジルコ
ニア、チタニア−シリカ及びモリブデンやタングステン
のヘテロポリ酸等が用いられているが、酸強度（H0）が
−10.6より弱いものしか得られず、過酷の反応条件を必
要としたり、反応が達成できない等の問題があった。[Problems to be Solved by Conventional Techniques and Inventions] In the petroleum refining and petrochemical industries, an acid catalyst is used for hydrocarbon conversion such as cracking, isomerization, alkylation, polymerization, dehydrogenation or acylation. The reaction has taken place. As the acid catalyst, sulfuric acid, aluminum chloride, hydrogen fluoride, phosphoric acid and the like are widely used. However, these acid catalysts have problems in that, in addition to separation from products, it is costly to take measures against corrosion of equipment such as a reaction vessel and treatment of waste acid. Therefore, a solid acid catalyst is adopted, and as the solid acid catalyst, silica-alumina, titania-zirconia, titania-silica, and a heteropoly acid of molybdenum or tungsten are used, but the acid strength (H 0 ) Was less than -10.6, and there were problems that harsh reaction conditions were required and that the reaction could not be achieved.
また、酸強度の非常に強い固体酸触媒として、フッ化
ホウ素、フッ化アンチモンを無機酸に担持した触媒、さ
らには、本発明者が提案した周期率表第IV属又は鉄の水
酸化物もしくは酸化物を硫酸根含有液で処理した後、焼
成することにより得られる酸強度（H0）が−10.6より強
い固体酸触媒（特公昭59−6181号、同59−40056号公
報）等が知られている。Further, as a solid acid catalyst having very strong acid strength, boron fluoride, a catalyst in which antimony fluoride is supported on an inorganic acid, further, periodic table IV or iron hydroxide or A solid acid catalyst (Japanese Patent Publication Nos. 59-6181 and 59-40056) having an acid strength (H 0 ) of more than -10.6, which is obtained by treating an oxide with a solution containing a sulfate group and then calcining, is known. Has been.
これらの酸強度の非常に強い触媒は、担持した酸性物
質が使用中に消失し、触媒の活性劣化が起こり易いとい
う問題があった。本発明は、このような問題を解決しよ
うとするもので、本発明の目的は、触媒の失活が起こり
難い、固体酸触媒を提供することにある。These catalysts having a very strong acid strength have a problem that the supported acidic substance disappears during use and the activity of the catalyst is likely to deteriorate. The present invention is intended to solve such a problem, and an object of the present invention is to provide a solid acid catalyst in which deactivation of the catalyst hardly occurs.
［問題点を解決するための手段］ 本発明は、酸化ジルコニウムにタングステン又はモリ
ブデン化合物の１種以上を当該金属量として１〜40重量
％添加又は担持し、実質的に硫酸分を含有せず、かつ−
11.99より強い酸強度（Ho）としたことからなる固体酸
触媒であり、さらに水酸化ジルコニウム又は非晶質の酸
化ジルコニウムに、タングステン化合物又はタングステ
ン化合物とモリブデン化合物の混合物を当該金属量とし
て１〜40重量％添加又は担持した場合は500〜1000℃の
温度で焼成し、モリブデン化合物のみをモリブデン金属
量として１〜２重量％添加又は担持した場合は500〜900
℃の温度で焼成し、モリブデン化合物のみをモリブデン
金属量として２重量％を超えて40重量％まで添加又は担
持した場合は500〜850℃の温度で焼成し、かつ実質的に
硫酸分を含有しない固体酸触媒の製造方法である。ここ
で、実質的に硫酸分を含有しないとは、触媒調整時に硫
酸分を遊離する成分を含まない、言い換えれば−11.99
より強い酸強度（H0）の発現に関与する硫酸分を含まな
いということである。[Means for Solving Problems] In the present invention, 1 to 40 wt% of zirconium oxide is added or supported as a metal amount, and substantially no sulfuric acid content is contained. And-
A solid acid catalyst having a stronger acid strength (Ho) than 11.99, further containing zirconium hydroxide or amorphous zirconium oxide, a tungsten compound or a mixture of a tungsten compound and a molybdenum compound as the metal amount of 1 to 40. When added or supported by weight%, it is fired at a temperature of 500 to 1000 ° C, and when only 1 to 2% by weight of molybdenum metal is added or supported, it is 500 to 900.
Calcination at a temperature of ℃, when only molybdenum compound is added or supported up to 40 wt% as a molybdenum metal content, it is calcined at a temperature of 500 to 850 ℃ and contains substantially no sulfuric acid. It is a method for producing a solid acid catalyst. Here, substantially free of sulfuric acid content does not include a component that liberates sulfuric acid content during catalyst preparation, in other words, -11.99.
That is, it does not contain the sulfuric acid content that is involved in the expression of stronger acid strength (H 0 ).
本発明の原料として用いられる実質的に硫酸分を含有
しない水酸化ジルコニウム又は非晶質の酸化ジルコニウ
ムは、市販品をそのまま用いてもよいが、塩化ジルコニ
ル〔ZnOCl2・8H2O〕、硝酸ジルコニル〔ZnO（NO3）２・
2H2O〕、酢酸ジルコニル〔ZrO（CH3COO）２〕硫酸ジル
コニル〔Zr（SO4）〕等をアンモニア水等で加水分解
し、得られる水酸化ジルコニウムを乾燥して用いてもよ
い。この場合、水酸化ジルコニウムは、350℃以下の温
度で乾燥させることが好ましい。乾燥温度が350℃を超
えると酸化ジルコニウムが結晶化し始め、このような原
料を用いると酸強度を十分に強くすることができず好ま
しくない。Zirconium hydroxide or amorphous zirconium oxide containing substantially no sulfuric acid used as a raw material of the present invention may be a commercially available product as it is, zirconyl chloride [ZnOCl 2 · 8H 2 O], zirconyl nitrate. [ZnO (NO 3 ) 2・
2H 2 O], zirconyl acetate [ZrO (CH 3 COO) 2 ] zirconyl sulfate [Zr (SO 4 )] and the like may be hydrolyzed with aqueous ammonia and the resulting zirconium hydroxide may be used by drying. In this case, zirconium hydroxide is preferably dried at a temperature of 350 ° C. or lower. When the drying temperature exceeds 350 ° C., zirconium oxide begins to crystallize, and the use of such a raw material is not preferable because the acid strength cannot be sufficiently increased.
本発明では、上記水酸化ジルコニウム又は非晶質の酸
化ジルコニウムに実質的に硫酸分を含有しないタングス
テン又はモリブデンの化合物を添加、又は担持するが、
これは、前記水酸化又は非晶質の酸化ジルコニウムにタ
ングステン又はモリブデン化合物をそのままあるいは溶
液の形態で添加するか、前記水酸化又は非晶質の酸化ジ
ルコニウムを所定の形態に成型し、タングステン又はモ
リブデン化合物の溶液に浸漬して担持する方法が簡便で
好ましい。尚、このときのタングステン又はモリブデン
化合物の添加又は担持量は、当該化合物の金属量、すな
わちタングステン又はモリブデンの元素として、１〜40
重量％とする必要がある。タングステン又はモリブデン
の量が、１重量％未満であれば、酸強度が十分に強くな
らず、また40重量％を超えても酸強度が弱くなる。上記
タングステン化合物としては、タングステン酸やメタタ
ングステン酸アンモニウム、酸化タングステン等を用い
ることができ、またモリブデン化合物としては、モリブ
デン酸、メタモリブデン酸アンモニウム、酸化モリブデ
ン、塩化モリブデン等を用いることができる。In the present invention, a compound of tungsten or molybdenum containing substantially no sulfuric acid is added to or supported on the zirconium hydroxide or the amorphous zirconium oxide,
This is because the tungsten or molybdenum compound is added to the hydroxide or amorphous zirconium oxide as it is or in the form of a solution, or the hydroxide or amorphous zirconium oxide is molded into a predetermined form, and then tungsten or molybdenum is formed. A method of supporting by immersing in a solution of a compound is simple and preferable. The amount of the tungsten or molybdenum compound added or supported at this time is 1 to 40 as the metal amount of the compound, that is, as the element of tungsten or molybdenum.
It is necessary to set it to the weight percent. If the amount of tungsten or molybdenum is less than 1% by weight, the acid strength will not be sufficiently strong, and if it exceeds 40% by weight, the acid strength will be weak. As the tungsten compound, tungstic acid, ammonium metatungstate, tungsten oxide, or the like can be used, and as the molybdenum compound, molybdic acid, ammonium metamolybdate, molybdenum oxide, molybdenum chloride, or the like can be used.
タングステン化合物又はタングステン化合物とモリブ
デン化合物の混合物を添加又は担持した後、500〜1000
℃の温度で焼成するが、この焼成温度が、500℃以下あ
るいは1000℃以上であると酸強度（H0）が弱く、超強酸
触媒が得られない。また、モリブデン化合物のみをモリ
ブデン金属量として１〜２重量％添加又は担持した場合
は500〜900℃、モリブデン化合物のみをモリブデン金属
量として２重量％を超えて40重量％まで添加又は担持し
た場合は500〜850℃の温度で焼成する。焼成温度がこの
範囲を外れると、酸強度（H0）が弱くなる。500-1000 after adding or supporting a tungsten compound or a mixture of a tungsten compound and a molybdenum compound
The calcination is performed at a temperature of ℃, but if the calcination temperature is 500 ° C or lower or 1000 ° C or higher, the acid strength (H 0 ) is weak and a super strong acid catalyst cannot be obtained. In addition, when the molybdenum compound alone is added or supported in an amount of 1 to 2 wt% as a molybdenum compound, the temperature is 500 to 900 ° C, and when the molybdenum compound alone is added or supported in an amount of more than 2 wt% and 40 wt% as an amount of molybdenum compound. Bake at a temperature of 500-850 ° C. If the firing temperature is out of this range, the acid strength (H 0 ) becomes weak.
以上の方法で製造することにより、酸強度（H0）が−
11.99より強い酸強度の触媒を得ることができる。尚、
ここにいう酸強度（H0）とは、触媒表面の酸点が塩基に
プロトンを与える能力あるいは塩基から電子対を受け取
る能力で定義され、pKa値で表わされるものであり、既
知の指示薬法あるいは気体塩基吸着法等の方法で測定す
ることができる。By producing by the above method, the acid strength (H 0 ) is −
A catalyst with an acid strength higher than 11.99 can be obtained. still,
The acid strength (H 0 ) here is defined by the ability of the acid points on the catalyst surface to give a proton to the base or the ability to receive an electron pair from the base, and is represented by a pKa value. It can be measured by a method such as a gas base adsorption method.
本発明で得られる固体酸触媒は、炭化水素等の分解、
異性化、アルキル化、重合、アシル化、脱水、脱水素等
の炭化水素転化反応において、より穏やかな反応条件で
用いることができる。The solid acid catalyst obtained in the present invention is a decomposition of hydrocarbons,
It can be used under milder reaction conditions in hydrocarbon conversion reactions such as isomerization, alkylation, polymerization, acylation, dehydration and dehydrogenation.
［実施例］ 触媒の調整 （１）塩化ジルコニル（ZrOCl2・8H2O）水溶液にアンモ
ニア水を加えて、水酸化ジルコニウムの沈殿物を得た。
この沈殿物を第１表に示す温度でそれぞれ３〜20時間乾
燥し、32〜60メッシュの大きさのものに粉砕、篩別し
た。[Examples] Preparation of catalyst (1) Ammonia water was added to a zirconyl chloride (ZrOCl 2 · 8H 2 O) aqueous solution to obtain a zirconium hydroxide precipitate.
The precipitate was dried at the temperature shown in Table 1 for 3 to 20 hours, crushed to a size of 32 to 60 mesh, and sieved.
次いで、これを５〜20重量％濃度のタングステン酸ア
ンモニウム水溶液中に入れ、加熱して水分を蒸発乾固さ
せてタングステンを担持した。これを第１表の温度で３
〜10時間焼成し、タングステン担持触媒WT−１〜14を調
整した。Then, this was placed in an ammonium tungstate aqueous solution having a concentration of 5 to 20% by weight, and heated to evaporate the water content to dryness to support tungsten. This is 3 at the temperature in Table 1.
The tungsten-supported catalysts WT-1 to 14 were prepared by firing for ~ 10 hours.
（２）塩化ジルコニル（ZrOCl2・8H2O）水溶液にアンモ
ニア水を加えて得られた水酸化ジルコニウムの沈殿物
に、湿潤したタングステン酸を水酸化ジルコニウムに対
してタングステン量として15重量％となるように添加
し、２〜５時間混練した。これを100℃の温度で、３時
間乾燥し、次いで800℃で、３時間焼成し、タングステ
ン添加触媒WA−１を調整した。(2) The zirconyl chloride (ZrOCl 2 · 8H 2 O) aqueous solution was added with ammonia water to obtain a zirconium hydroxide precipitate, and the moistened tungstic acid was 15% by weight as the amount of tungsten with respect to zirconium hydroxide. And added for 2 to 5 hours. This was dried at a temperature of 100 ° C. for 3 hours and then calcined at 800 ° C. for 3 hours to prepare a tungsten-added catalyst WA-1.
（３）塩化ジルコニル（ZrOCl2・8H2O）水溶液にアンモ
ニア水を加えて得られた水酸化ジルコニウムの沈殿物
を、100℃で20時間乾燥し、32〜60メッシュの大きさの
ものに粉砕、篩別した。これを、10％濃度のアンモニウ
ム水溶液に５〜20重量％のモリブデン酸を溶解した溶液
にいれ、加熱して水分を蒸発乾固させてモリブデンを担
持した。これを第２表の温度で３時間焼成し、モリブデ
ン担持触媒Ｍ−１〜４、M7〜11、Ｍ−13〜18及びＭ−20
〜22を調整した。(3) A precipitate of zirconium hydroxide obtained by adding aqueous ammonia to a zirconyl chloride (ZrOCl 2 · 8H 2 O) aqueous solution is dried at 100 ° C for 20 hours and crushed to a size of 32 to 60 mesh. , Sieved. This was put into a solution in which 5 to 20% by weight of molybdic acid was dissolved in a 10% aqueous solution of ammonium, and heated to evaporate water to dryness to support molybdenum. This was calcined at the temperature shown in Table 2 for 3 hours, and molybdenum-supported catalysts M-1 to M4, M7 to 11, M-13 to 18 and M-20.
Adjusted ~ 22.
酸強度の測定 上記方法で得られた触媒について、指示薬法により酸
強度を測定した。この結果を第１表及び第２表にて併せ
て記載した。尚、酸強度の測定に用いた指示薬を第３表
に示した。Measurement of Acid Strength With respect to the catalyst obtained by the above method, the acid strength was measured by an indicator method. The results are also shown in Tables 1 and 2. The indicators used for measuring the acid strength are shown in Table 3.
反 応 （アシル化） トルエン15mlと無水安息香酸0.185gとを入れた反応容
器に上記で調整した触媒を0.5g入れ、80℃で３時間、還
流条件下に反応させた。得られたメチルベンゾフェノン
をガスクロマトグラフィーでイソプロピルベンゼンを用
いた内部標準法により測定し、転化率を求めた。この結
果を第４表に示す。 Reaction (acylation) 0.5 g of the above-prepared catalyst was placed in a reaction vessel containing 15 ml of toluene and 0.185 g of benzoic anhydride, and reacted at 80 ° C. for 3 hours under reflux conditions. The obtained methylbenzophenone was measured by gas chromatography by an internal standard method using isopropylbenzene to determine the conversion rate. The results are shown in Table 4.
（異性化） （１）マイクロ触媒パルス反応器を用い、前述の触媒を
0.5g充填してペンタンの異性化反応を行った。反応温度
は280℃とし、キャリヤーガスとしてヘリウムを10ml/mi
nの流量で流し、サンプル量１μを注入し、直接ガス
クロマトグラフィーに導入して分析した。また、同様に
原料として、ヘキサンを用い、反応温度240℃で行っ
た。これらの結果を、第５表に示した。 (Isomerization) (1) Using a microcatalyst pulse reactor,
0.5 g was charged to carry out an isomerization reaction of pentane. The reaction temperature was 280 ° C, and helium was used as a carrier gas at 10 ml / mi.
Flowing at a flow rate of n, a sample amount of 1 μm was injected and directly introduced into gas chromatography for analysis. Similarly, hexane was used as a raw material, and the reaction temperature was 240 ° C. The results are shown in Table 5.
（２）閉鎖循環系反応装置を用いてブタン及びペンタン
を原料に異性化反応を行った。触媒量は1gとし、反応生
成物は、ガスクロマトグラフィーで分析し、これらの結
果と反応条件を第６表に示した。 (2) An isomerization reaction was performed using butane and pentane as raw materials using a closed circulation system reactor. The catalyst amount was 1 g, and the reaction product was analyzed by gas chromatography. The results and reaction conditions are shown in Table 6.
（脱水素化） マイクロ触媒パルス反応器を用い、前述の触媒を0.1g
充填してメタノールのホルムアルデヒドへの脱水素反応
を行った。反応温度は170℃とし、キャリヤーガスとし
てヘリウムを20ml/minの流量で流し、サンプル量１μ
を注入し、直接ガスクロマトグラフィーに導入して分析
した。反応では、メタノールと空気（2cc）を交互に注
入した。結果を、第７表に示した。また、前述のＭ−15
の触媒を用い、反応温度をそれぞれ変えて同様の操作を
行った。この結果を、第８表に記載した。 (Dehydrogenation) Using a microcatalyst pulse reactor, 0.1 g of the above catalyst was used.
After filling, a dehydrogenation reaction of methanol to formaldehyde was performed. The reaction temperature was 170 ° C, helium was used as a carrier gas at a flow rate of 20 ml / min, and the sample amount was 1 μm.
Was injected and directly introduced into gas chromatography for analysis. In the reaction, methanol and air (2 cc) were alternately injected. The results are shown in Table 7. In addition, the above-mentioned M-15
The same operation was performed by using the catalyst of No. 1 and changing the reaction temperature. The results are shown in Table 8.
（分 解） マイクロ触媒パルス反応器を用い、前述のWT−３の触
媒を0.1g充填してキュメンのベンゼンとプロピレンへの
分解反応を行った。反応温度は160℃とし、キャリヤー
ガスとしてヘリウムを10ml/minの流量で流し、サンプル
量１μを注入し、直接ガスクロマトグラフィーに導入
して分析した。この結果、転化率は、11.8％であった。 (Degradation) Using a microcatalyst pulse reactor, 0.1 g of the above-mentioned WT-3 catalyst was charged and the decomposition reaction of cumene into benzene and propylene was performed. The reaction temperature was 160 ° C., helium was passed as a carrier gas at a flow rate of 10 ml / min, a sample amount of 1 μm was injected, and the sample was directly introduced into gas chromatography for analysis. As a result, the conversion rate was 11.8%.
一方、市販のシリカ−アルミナを空気中、500℃で、
３時間焼成し、酸強度が−12.70＜H0≦−11.35の触媒を
得た。これを用いて、反応温度を260℃とした以外は上
記と同じ方法で、キュメンの分解を行った。この結果、
転化率は、10.8％であった。このようにシリカ−アルミ
ナを用いた場合は、本発明の触媒に比べて、反応温度を
100℃も高くしなければ、同じ転化率は得られず、本発
明の触媒は、分解活性が極めて高いことが分かる。On the other hand, commercially available silica-alumina in air at 500 ° C.
It was calcined for 3 hours to obtain a catalyst having an acid strength of -12.70 <H 0 ≤-11.35. Using this, cumene was decomposed by the same method as above except that the reaction temperature was 260 ° C. As a result,
The conversion rate was 10.8%. When silica-alumina is used as described above, the reaction temperature is higher than that of the catalyst of the present invention.
The same conversion cannot be obtained unless the temperature is raised to 100 ° C., indicating that the catalyst of the present invention has extremely high decomposition activity.
（アルキル化） 50ccのオートクレーブに、イソブタン10.4g、イソブ
テン0.2g及び前述のWT−１の触媒を4.4gを入れ、100
℃、18kg/cm2で、30分間反応させた。この結果、イソブ
テンのイソオクタンへの転化率は、88.2％であった。(Alkylation) Into a 50 cc autoclave, 10.4 g of isobutane, 0.2 g of isobutene and 4.4 g of the above-mentioned WT-1 catalyst were placed, and 100
The reaction was carried out at 18 ° C. and 18 kg / cm 2 for 30 minutes. As a result, the conversion rate of isobutene to isooctane was 88.2%.
［比較例］ 実施例の触媒調整法と同様にし、焼成温度を高めて酸
強度（H0）を−11.99よりも弱めたモリブデン担持触媒
Ｍ−５、Ｍ−６、Ｍ−12及びＭ−19を調製した。これら
の触媒は、第４表及び第７表から明らかなように触媒活
性が低かった。[Comparative Example] The molybdenum-supported catalysts M-5, M-6, M-12 and M-19 obtained by increasing the calcination temperature and making the acid strength (H 0 ) weaker than -11.99 in the same manner as in the catalyst preparation method of Example Was prepared. These catalysts had low catalytic activity, as is apparent from Tables 4 and 7.
また、シリカ、アルミナ、二三酸化鉄、マグネシア、
チタニア等を用い、実施例の触媒調製法に記載したのと
同様の方法で、これらに対し金属量として５〜15重量％
の酸化モリブデン、又は酸化タングステンを担持した。
これらについて、実施例と同様にアシル化、異性化、脱
水素化反応を行なったが、反応はほとんど進まなかっ
た。Also, silica, alumina, ferric oxide, magnesia,
Using titania or the like, in the same manner as described in the catalyst preparation method of the example, 5 to 15% by weight as a metal amount relative to these
Supported molybdenum oxide or tungsten oxide.
These were subjected to acylation, isomerization and dehydrogenation reactions in the same manner as in Example, but the reaction hardly proceeded.
［発明の効果］ 以上のように本発明は、酸化ジルコニウムにタングス
テン又はモリブデン化合物を添加又は担持して酸強度
（H0）を−11.99より強くし、かつ実質的に硫酸分を含
有しない超強酸触媒であるため、触媒の失活が少なく、
よりマイルドな反応条件により各種の炭化水素転化反応
を行うことができるという効果を有する。[Effects of the Invention] As described above, the present invention is to add or support a tungsten or molybdenum compound to zirconium oxide to increase the acid strength (H 0 ) to more than -11.99, and to use a super strong acid containing substantially no sulfuric acid. Since it is a catalyst, the catalyst is less deactivated,
It has the effect that various hydrocarbon conversion reactions can be carried out under milder reaction conditions.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 9/00 9546−4Ｈ Ｃ０７Ｃ 9/00 9/16 9546−4Ｈ 9/16 11/06 9546−4Ｈ 11/06 15/04 9546−4Ｈ 15/04 45/46 9049−4Ｈ 45/46 47/052 9049−4Ｈ 47/052 49/784 9049−4Ｈ 49/784 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07C 9/00 9546-4H C07C 9/00 9/16 9546-4H 9/16 11/06 9546- 4H 11/06 15/04 9546-4H 15/04 45/46 9049-4H 45/46 47/052 9049-4H 47/052 49/784 9049-4H 49/784
Claims (2)
ブデン化合物の１種以上を当該金属量として１〜40重量
％添加又は担持し、実質的に硫酸分を含有せず、かつ−
11.99より強い酸強度（Ho）を有する炭化水素転化用固
体酸触媒。1. A zirconium oxide containing or supporting at least one tungsten or molybdenum compound in an amount of 1 to 40% by weight as the amount of the metal, containing substantially no sulfuric acid, and-
Solid acid catalyst for hydrocarbon conversion with acid strength (Ho) higher than 11.99.
コニウムに、タングステン化合物又はタングステン化合
物とモリブデン化合物の混合物を当該金属量として１〜
40重量％添加又は担持した場合は500〜1000℃の温度で
焼成し、モリブデン化合物のみをモリブデン金属量とし
て１〜２重量％添加又は担持した場合は500〜900℃の温
度で焼成し、モリブデン化合物のみをモリブデン金属量
として２重量％を超えて40重量％まで添加又は担持した
場合は500〜850℃の温度で焼成したものであり、かつ実
質的に硫酸分を含有しないことを特徴とする炭化水素転
化用固体触媒の製造方法。2. A zirconium hydroxide or an amorphous zirconium oxide containing a tungsten compound or a mixture of a tungsten compound and a molybdenum compound as the amount of the metal.
When 40% by weight is added or supported, it is calcined at a temperature of 500 to 1000 ° C, and when only 1 to 2% by weight of molybdenum metal is added or supported, it is baked at a temperature of 500 to 900 ° C. When only 2% by weight or 40% by weight of molybdenum metal is added or supported, it is calcined at a temperature of 500 to 850 ° C. and is substantially free of sulfuric acid content. A method for producing a solid catalyst for hydrogen conversion.
Priority Applications (1)
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|---|---|---|---|
| JP63114790A JP2566814B2 (en) | 1988-05-13 | 1988-05-13 | Solid acid catalyst for hydrocarbon conversion and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63114790A JP2566814B2 (en) | 1988-05-13 | 1988-05-13 | Solid acid catalyst for hydrocarbon conversion and method for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190004279A (en) * | 2016-05-06 | 2019-01-11 | 주식회사 쿠라레 | Method for producing conjugated diene |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5214017A (en) * | 1991-11-27 | 1993-05-25 | Sun Company, Inc. (R&M) | Solid-acid alkylation catalyst compositions for alkylation processes |
| US5212136A (en) * | 1991-11-27 | 1993-05-18 | Sun Company, Inc (R&M) | Solid-acid alkylation catalyst compositions for alkylation processes |
| US5396011A (en) * | 1992-12-28 | 1995-03-07 | Mallinckrodt Chemical, Inc. | Catalytic alkylation of aromatic compounds with alkenes |
| AU688351B2 (en) * | 1993-07-22 | 1998-03-12 | Mobil Oil Corporation | Modified solid oxide catalyst and process for producing same |
| US6224748B1 (en) | 1993-07-22 | 2001-05-01 | Mobil Oil Corporation | Process for hydrocracking cycle oil |
| US5543036A (en) * | 1993-07-22 | 1996-08-06 | Mobil Oil Corporation | Process for hydrotreating |
| US5719097A (en) * | 1993-07-22 | 1998-02-17 | Chang; Clarence D. | Catalyst comprising a modified solid oxide |
| US5345026A (en) * | 1993-07-22 | 1994-09-06 | Mobil Oil Corp. | Ring opening process |
| US6080904A (en) * | 1993-07-22 | 2000-06-27 | Mobil Oil Corporation | Isomerization process |
| US6217747B1 (en) | 1993-07-22 | 2001-04-17 | Mobil Oil Corporation | Process for selective wax hydrocracking |
| US5382731A (en) * | 1993-07-22 | 1995-01-17 | Mobil Oil Corp. | Combined paraffin isomerization/ring opening process |
| US5854170A (en) * | 1993-07-22 | 1998-12-29 | Mobil Oil Corporation | Method for preparing a modified solid oxide |
| US5401478A (en) * | 1993-08-03 | 1995-03-28 | Mobil Oil Corp. | Selective catalytic reduction of nitrogen oxides |
| US5552128A (en) * | 1993-08-03 | 1996-09-03 | Mobil Oil Corporation | Selective catalytic reduction of nitrogen oxides |
| WO1995007874A1 (en) * | 1993-09-14 | 1995-03-23 | Mobil Oil Corporation | Process for preparing alkyl aromatic compounds |
| US5563311A (en) * | 1993-09-14 | 1996-10-08 | Mobil Oil Corporation | Process for preparing short chain alkyl aromatic compounds |
| US5563310A (en) * | 1993-09-14 | 1996-10-08 | Mobil Oil Corporation | Toluene alkylation with methanol |
| US5516954A (en) * | 1993-09-16 | 1996-05-14 | Mobil Oil Corporation | Process for preparing long chain alkylaromatic compounds |
| US5449847A (en) * | 1994-04-18 | 1995-09-12 | Mobil Oil Corporation | Selective conversion of benzene to tercyclohexane |
| US5510309A (en) * | 1994-05-02 | 1996-04-23 | Mobil Oil Corporation | Method for preparing a modified solid oxide |
| US5780703A (en) * | 1994-05-02 | 1998-07-14 | Mobil Oil Corporation | Process for producing low aromatic diesel fuel with high cetane index |
| KR100247524B1 (en) | 1994-05-31 | 2000-03-15 | 겐지 아이다 | Catalyst for producing acrylic acid and method for production of acrylic acid by the use of the catalyst |
| TW349033B (en) * | 1994-05-31 | 1999-01-01 | Nippon Catalytic Chem Ind | Catalyst for production of methacrylic acid and method for production of methacrylic acid by the use of the catalysta catalyst for the production of methacrylic acid by the vapor-phase catalytic oxidation and/or oxidative dehydrogenation of at least one compound |
| KR100247525B1 (en) * | 1994-05-31 | 2000-03-15 | 겐지 아이다 | Catalyst for production of unsaturated aldehyde and unsaturated carboxylic acid and method for production of unsaturated aldehyde and unsaturated carboxylic acid by the use of the catalyst |
| DE4433606A1 (en) * | 1994-09-21 | 1996-03-28 | Basf Ag | Process for the preparation of polyetrahydrofuran |
| US5608133A (en) * | 1995-10-23 | 1997-03-04 | Mobil Oil Corporation | Catalytic oligomerization |
| US5804690A (en) * | 1995-12-14 | 1998-09-08 | Mobil Oil Corporation | Selective monomethylation of aromatics with dimethylcarbonate |
| US6162757A (en) * | 1999-07-20 | 2000-12-19 | Mobil Oil Corporation | Acid catalyst composition |
| DE10047642A1 (en) * | 2000-09-26 | 2002-04-11 | Basf Ag | Process for the dehydrogenation of hydrocarbons |
| KR101111129B1 (en) * | 2007-03-27 | 2012-03-13 | 디아이씨 가부시끼가이샤 | Solid acid catalyst for production of polyester, process for production of the catalyst, and process for production of polyester with the same |
| US20110301021A1 (en) * | 2009-03-02 | 2011-12-08 | Sud-Chemie Inc. | Promoted zirconium oxide catalyst support |
| JP5918272B2 (en) * | 2011-01-25 | 2016-05-18 | フイリツプス６６カンパニー | Condensation of alcohols for biofuel production |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6373409A (en) * | 1986-09-17 | 1988-04-04 | Toshiba Corp | Trouble detector for reactive power compensating device |
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1988
- 1988-05-13 JP JP63114790A patent/JP2566814B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190004279A (en) * | 2016-05-06 | 2019-01-11 | 주식회사 쿠라레 | Method for producing conjugated diene |
| KR102338451B1 (en) | 2016-05-06 | 2021-12-10 | 주식회사 쿠라레 | Method for preparing conjugated dienes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01288339A (en) | 1989-11-20 |
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