JP2014147931A - 水素化、水素化異性化、水素化分解および/または水素化脱硫のための触媒、触媒担体および方法 - Google Patents
水素化、水素化異性化、水素化分解および/または水素化脱硫のための触媒、触媒担体および方法 Download PDFInfo
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- JP2014147931A JP2014147931A JP2014075320A JP2014075320A JP2014147931A JP 2014147931 A JP2014147931 A JP 2014147931A JP 2014075320 A JP2014075320 A JP 2014075320A JP 2014075320 A JP2014075320 A JP 2014075320A JP 2014147931 A JP2014147931 A JP 2014147931A
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- catalyst
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- alumina
- silica
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010457 zeolite Substances 0.000 claims abstract description 29
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 20
- 239000000356 contaminant Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 16
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000003980 solgel method Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
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- 231100000719 pollutant Toxicity 0.000 claims description 5
- 229910052710 silicon Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- 239000010703 silicon Chemical class 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
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- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- 230000036961 partial effect Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
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- 239000010455 vermiculite Substances 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229920003350 Spectratech® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- CZPWVGJYEJSRLH-UHFFFAOYSA-O hydron;pyrimidine Chemical compound C1=CN=C[NH+]=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-O 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- -1 pyridine Lewis acid Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0246—Coatings comprising a zeolite
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
【解決手段】ゾル−ゲル法によって得られ、実質的にバインダーを含まないビーズ型担体物質、及び貴金属から選択される触媒的に活性な成分から成り、担体は、5〜50重量%の少なくとも1の分子ふるい物質及び50〜95重量%のシリカ−アルミナを含む。前記分子ふるい物質がゼオライト及び変性ゼオライトからなる触媒。前記触媒的に活性な成分は、Pt、Pd、Ru、Ir、及びRhから選択される少なくとも一成分を含む貴金属である触媒。
【選択図】なし
Description
実施例において示したデータを得るために、以下の方法を使用した。
ピリジン吸着実験を、KBr窓を備えた拡散反射率高温室(Spectra-Tech)で行った。気体がその部屋を通って流動し、かつその部屋が排気され得るように、その部屋を気体系と連結した。
分散度は、以下のように25℃および1バールの圧力で、触媒の還元された形態でサンプル上に吸着されたCOの量を測定することにより決定され得る。触媒の既知量のサンプルを反応器に入れ、200℃で水素を用いて還元した。水素中で25℃に冷却した後、ヘリウムを用いて少なくとも30分間反応器をフラッシングする。次いで、ヘリウム流を、既知量のCOの6パルスと交換し、COの濃度を、反応器の出口で、熱伝導率検出器を用いて測定する。触媒およびCOの量は、触媒が第1パルスの後にCOで飽和されるように選択され、第2〜6パルスは、これを立証するために使用される。
触媒製造
30重量%のゼオライトYを含有する担体を、ゼオライトHY粉末およびシリカおよびアルミニウム硫酸塩の溶液から、水性ゾル−ゲル法によって製造した。こうして得られた球をMVS052と命名する。MVS052のブレンステッド酸性度は、RTでのピリジン吸着および180℃での脱着によって決定されるとき、312μモル/gであった。MVS052に、PdおよびPtを含有する水性溶液を含浸させた。乾燥および還元の後、MVC069と命名された触媒が得られた。Pd含量は0.89重量%であった。Pt含量は0.30重量%であった。分散度は0.23であった。
MVC069を固定床反応器に充填し、50バールの全圧、260℃の反応器入口温度、1.5リットル/hのLHSVおよび750リットル/hの水素GHSVで炭化水素流と接触させた。供給原料および生成物の特性を表に示す。
Claims (23)
- 炭化水素供給原料の水素化、水素化異性化、水素化分解および/または水素化脱硫のための触媒において、該触媒が、ゾル−ゲル法によって得られる実質的にバインダーを含まないビーズ型担体物質、および貴金属から選択される触媒的に活性な成分から成り、担体が5〜50重量%の少なくとも1の分子ふるい物質および50〜95重量%のシリカ−アルミナを含むところの触媒。
- 担体物質が10〜60重量%の少なくとも1の分子ふるい物質および40〜90重量%のシリカ−アルミナから成る、請求項1記載の触媒。
- 担体物質中のシリカ−アルミナがゾル−ゲル法によって得られる非結晶性の酸性シリカ−アルミナであり、かつSiとAlとの比が1:10〜200:1である、請求項1または2に記載の触媒。
- 分子ふるい物質が、所望により変性されている、ゼオライトY、ゼオライトβ、ZSM−5、MCM−41およびゼオライトX、ならびにその他のゼオライトおよび変性ゼオライトの群から選択される、請求項1〜3のいずれか1項記載の触媒。
- 触媒が、触媒的に活性な成分として、触媒の重量において計算して0.01〜5重量%の貴金属を含む、請求項1〜4のいずれか1項記載の触媒。
- 分子ふるい物質をその中に分散させて含む、アルミニウムおよび珪素の無機塩の水性ゾルを、油相を通ってアルカリ性水相に添加することにより得ることができる、請求項1〜5のいずれか1項記載の触媒。
- 少なくとも0.2の分散度を有する、請求項1〜6のいずれか1項記載の触媒。
- 少なくとも5μモル/gのブレンステッド酸性度を有する、請求項1〜7のいずれか1項記載の触媒。
- 触媒的に活性な成分が、白金、パラジウム、ルテニウム、イリジウムおよびロジウムの群から選択される少なくとも1の成分を含む、請求項1〜8のいずれか1項記載の触媒。
- 触媒的に活性な成分が、白金、パラジウムまたはそれらの組み合わせを含む群から選択される、請求項9記載の触媒。
- 触媒的に活性な成分が、白金およびパラジウムを10:1〜1:10の重量比で含む、請求項10記載の触媒。
- ゾル−ゲル法によって得られ、かつ5〜50重量%の少なくとも1の分子ふるい物質および50〜95重量%のシリカ−アルミナを含んで実質的にバインダーを含まない物質から成る、ビーズ型触媒担体または触媒。
- 該物質が、10〜40重量%の少なくとも1の分子ふるい物質および60〜90重量%のシリカ−アルミナから成る、請求項12記載の触媒担体または触媒。
- 担体物質中のシリカ−アルミナが非結晶性の酸性シリカ−アルミナであり、ここでSiとAlとの比が1:10〜200:1である、請求項12または13記載の触媒担体または触媒。
- 分子ふるい物質が、ゼオライトY、ゼオライトβ、ZSM−5、MCM−41およびゼオライトX、ならびにその他のゼオライトおよび粘土鉱物の群から選択される、請求項12〜14のいずれか1項記載の触媒担体または触媒。
- 硫黄汚染物質を含有する炭化水素供給原料の水素化、水素化異性化、水素化分解および/または水素化脱硫のための方法において、供給原料を、水素気体の存在下で、請求項1〜15のいずれか1項記載の触媒と接触させるところの方法。
- 供給原料の重量に基づいて、硫黄として計算して0.1〜500ppmの硫黄汚染物質含量を有する供給原料が処理される、請求項16記載の方法。
- 炭化水素供給原料がチオフェン様硫黄汚染物質を含む、請求項16〜17のいずれか1項記載の方法。
- 硫黄汚染物質を含有する炭化水素供給原料が、ホワイトオイル、溶媒、ディーゼル油または中間留分、ガソリン、樹脂およびケロシンから成る群から選択される、請求項16〜18のいずれか1項記載の方法。
- 供給原料が、上流の水素化脱硫装置からの生成物である、請求項16〜19のいずれか1項記載の方法。
- 供給原料を、50〜450℃の範囲の温度で触媒と接触させる、請求項16〜20のいずれか1項記載の方法。
- 供給原料を、5〜300バールの水素圧下で触媒と接触させる、請求項16〜21のいずれか1項記載の方法。
- 請求項1〜15のいずれか1項記載の触媒または触媒担体の製造法において、該方法が、分子ふるい物質をその中に分散させて含む、アルミニウムおよび珪素の無機塩の水性ゾルを、油相を通ってアルカリ性水相に滴下すること、アルカリ性水相から物質を回収し、所望により次いで更なる処理を行うこと、および触媒的に活性な成分を該物質上に施与することを含む方法。
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EP00201443A EP1147811A1 (en) | 2000-04-20 | 2000-04-20 | Catalyst, catalyst support and process for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurization. |
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KR100801783B1 (ko) | 2008-02-05 |
US8128805B2 (en) | 2012-03-06 |
US20120077666A1 (en) | 2012-03-29 |
CA2406662A1 (en) | 2001-11-01 |
JP2003531002A (ja) | 2003-10-21 |
EP1274506A1 (en) | 2003-01-15 |
EP1147811A1 (en) | 2001-10-24 |
CA2406662C (en) | 2013-12-31 |
AU5066801A (en) | 2001-11-07 |
BR0110159A (pt) | 2003-03-05 |
US20030173252A1 (en) | 2003-09-18 |
JP5933905B2 (ja) | 2016-06-22 |
KR20030009443A (ko) | 2003-01-29 |
WO2001080996A1 (en) | 2001-11-01 |
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