JP3802939B2 - Catalyst for hydrotreating - Google Patents
Catalyst for hydrotreating Download PDFInfo
- Publication number
- JP3802939B2 JP3802939B2 JP25285694A JP25285694A JP3802939B2 JP 3802939 B2 JP3802939 B2 JP 3802939B2 JP 25285694 A JP25285694 A JP 25285694A JP 25285694 A JP25285694 A JP 25285694A JP 3802939 B2 JP3802939 B2 JP 3802939B2
- Authority
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- Prior art keywords
- catalyst
- range
- diameter
- pore volume
- silica
- 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 - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims description 69
- 229910052751 metal Inorganic materials 0.000 claims description 60
- 239000002184 metal Substances 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 50
- 239000011148 porous material Substances 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052753 mercury Inorganic materials 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000002459 porosimetry Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 34
- 239000003921 oil Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 20
- 238000005470 impregnation Methods 0.000 description 16
- -1 boria Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 10
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052911 sodium silicate Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 230000000737 periodic effect Effects 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 241000588731 Hafnia Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 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 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は炭化水素油の水素化処理用触媒に関するものである。
【０００２】
【従来の技術】
炭化水素油の水素化処理用触媒としては、従来各種のものが提案されているが、その中でも比較的すぐれた脱硫性能を有するものとして、比表面積２００〜４００ｍ2／ｇを有する特定の細孔容積分布を有するシリカ−アルミナ上に水素化活性金属成分を担持させたものがある（特公平５−３９６６２号公報、特公平３−３１４９６号公報等）。
これらの公知触媒は、細孔直径が３００Å以上のマクロポアーの含有割合を低く規定したもので、その脱硫活性が長時間にわたって保持されるという特徴を有する。
しかしながら、これらの触媒の場合、脱硫活性長時間にわたって保持し得るものの、その脱硫活性の点で未だ満足し得るものではなかった。
【０００３】
【発明が解決しようとする課題】
本発明は、その脱硫活性において改善された水素化処理用触媒を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。
即ち、本発明によれば、核としてのアルミナ表面上にシリカ層を形成した構造を有し、シリカを２〜４０重量％含有するシリカ−アルミナからなる担体に少なくとも１種の水素化活性金属成分を担持させた水素化処理触媒であって、２００〜４００ｍ2／ｇの比表面積を有するとともに、水銀圧入法により測定した全細孔容積が０．４０〜０．５５ｍｌ／ｇ、窒素吸着法により測定した０〜３００Åの範囲の直径を有する細孔容積が、水銀圧入法により測定した４０Å以上の範囲の直径を有する細孔容積の７５％以上を占め、窒素吸着法により測定した０〜３００Åの範囲の直径を有する細孔の平均細孔直径が４０〜９０Åであり、水銀圧入法により測定した３００Å以上１５０，０００以下の範囲の直径を有する細孔容積が０．０１〜０．２５ｍｌ／ｇであり、水銀圧入法により測定した３００〜６００Åの範囲の直径を有する細孔容積が、３００Å以上１５０，０００Å以下の範囲の直径を有する細孔容積の４０％以上を占めることを特徴とする水素化処理用触媒が提供される。
【０００５】
本発明の水素化処理用触媒においては、触媒担体の少なくとも一部として、核としてのアルミナの表面上にシリカ層を形成した構造を有するシリカ−アルミナを用いる。この触媒におけるシリカの含有率は、一般的には、２〜４０重量％であるが、水素化脱硫反応や水素化脱窒素反応における過度の分解反応に伴う水素消費量の増大又はコークの生成等を制御するために、そのシリカ含有量は５〜２０重量％、好ましくは７〜１５重量％の範囲に規定するのがよい。また、このシリカ−アルミナからなる担体は、シリカの他、他の耐火性無機酸化物、例えば、マグネシア、酸化カルシウム、ジルコニア、チタニア、ボリア、ハフニア及び結晶性ゼオライト等の一種又は二種以上を含有することができる。本発明で用いるシリカ−アルミナからなる担体おいて、シリカは、触媒に必要な固体酸性度を制御する作用を示し、その具体的添加量は、所望する触媒酸強度に応じて適宜決める。シリカは、触媒に強酸点を賦与し、触媒の炭化水素分解活性を増大させるが、一方、例えば、前記マグネシアは、アルミナ−シリカ等が有する強酸点を減少させ、同時に弱酸点を増加させて触媒の選択性を向上させる作用を有する。前記マグネシア、酸化カルシウム、ジルコニア、チタニア、ボリア、ハフニア及び結晶性ゼオライト等の耐火性無機酸化物の含有量は、アルミナ−シリカに対して約１〜１０重量％の範囲が適当である。アルミナとしては、γ−アルミナ、χ−アルミナ又はη−アルミナのいずれか又はそれらの混合体を形成するものが好適である。
【０００６】
本発明の触媒担体として好適なシリカ−アルミナを製造するには、先ずｐＨ７〜１３、好ましくは１１〜１２．５に調整したアルカリ水溶液を調製する。アルカリとしては、水酸化ナトリウム、水酸化カリウム、水酸化アンモニウム等が用いられる。
次に、このアルカリ水溶液中に、酸性アルミニウム化合物水溶液を添加混合する。酸性アルミニウム化合物としては、アルミニウムの硫酸塩、塩化物、硝酸塩等が用いられる。水溶液中の酸性アルミニウム化合物の濃度は、通常、３６〜４２重量％、好ましくは３８〜４０重量％である。この場合、混合水溶液中のｐＨは７〜１１、好ましくは８〜１０である。
【０００７】
前記のようにして得られる混合水溶液は、これを温度５０〜８０℃、好ましくは６０〜７５℃に保持する。この場合の保持時間は、長くとも２時間、好ましくは０．２〜１．５時間である。このことにより、混合水溶液中には、アルミナ水和物の沈殿（ゲル）が生じる。
【０００８】
次に、このようなアルミナ水和物の沈殿を含む混合水溶液に対し、水溶性ケイ素化合物の水溶液を添加混合する。水溶性ケイ素化合物としては、アルカリ金属ケイ酸塩や、テトラアルコキシシラン、オルソケイ酸エステル等が用いられる。アルカリ金属ケイ酸塩としては、Ｎａ2Ｏ：ＳｉＯ2のモル比が１：２〜１：４の範囲にあるケイ酸ナトリウムの使用が好ましい。水溶液中のケイ素化合物の濃度は、５〜１０重量％、好ましくは６〜８重量％である。前記アルミナ水和物の沈殿を含む水溶液に対するケイ素化合物の添加量は、最終製品であるシリカ含有アルミナの組成に対応する量であり、シリカ含有量が２〜４０重量％になるような量である。アルミナ水和物の沈殿を含む水溶液とケイ素化合物の水溶液との混合溶液は、ｐＨ７〜１１、好ましくは８〜１０の条件に保持する。この場合、必要に応じて、鉱酸水溶液等のｐＨ調節剤を添加し、混合水溶液のｐＨを前記範囲に保持する。この混合水溶液は、温度５０〜８０℃、好ましくは６０〜７５℃に保持する。その保持時間は長くとも２時間であり、好ましくは０．２〜１．５時間である。この操作により、アルミナ水和物上にシリカ水和物が沈着した沈殿粒子が得られる。この沈殿粒子は、液中から分離した後、常法の洗浄処理、例えば、炭酸アンモニウム水溶液及び水を用いて洗浄処理を施して不純物イオンを除去し、混練後成形機により所望の形状に成形される。次いでこの成形物を乾燥及び焼成処理を施す。乾燥は、酸素の存在下又は非存在下で常温〜２００℃の温度で行う。また、焼成は、酸素の存在下で、２００〜８００℃、好ましくは６００〜７００℃で行う。このようにして、核としてのアルミナ表面上にシリカ層が形成した構造を有し、前記した触媒に関して示した細孔特性とほぼ一致する細孔特性を有するシリカ−アルミナを得ることができる。
また、沈着法により得られた沈殿粒子を含むスラリー液をろ過したケーキを、混練機により混練し、押出し成形機により成形する際、混練に必要な水分量及び酸量を変化させることにより細孔分布の微調整を行なうことができる。
【０００９】
シリカ−アルミナには、前記したように、必要に応じ、他の金属成分、例えば、マグネシア、酸化カルシウム、ジルコニア、ボリア、ハフニア、結晶性ゼオライト等を添加することができる。これらの金属成分は、混合法により添加することができる他、従来公知の含浸法や共沈法により添加することができるが、含浸法により添加するのが好ましい。含浸法により添加する場合には、シリカ−アルミナを、所定の可溶性金属成分を含む含浸溶液中に浸漬して、その金属成分をシリカ−アルミナ中に所望量含浸させた後、乾燥し、焼成する。
本発明の水素化処理用触媒は、前記シリカ−アルミナを含有する担体に対して、水素化活性金属を担持させることによって得ることができる。この水素化活性金属の担持方法としては、従来公知の含浸法や、共沈法により行うことがきるが、含浸法により行うのが好ましい。
本発明の水素化処理用触媒の細孔特性は、その担体として用いるシリカ−アルミナに対応するもので、本発明の触媒は、担体として用いるシリカ−アルミナとほぼ同等の細孔特性を有する。
【００１０】
シリカ−アルミナ担体上に担持させる水素化活性金属成分としては、元素周期律表第VIB族金属及び第VIII族金属の群から選択される一種又は二種以上の金属を選択する。すなわち、第VIB族のクロム、モリブデン及びタングステン、第VIII族の鉄、コバルト、ニッケル、パラジウム、白金、オスミウム、イリジウム、ルテニウム及びロジウム等から一種又は二種以上を選択して使用する。炭化水素油の水素化脱硫のためには、特に、第VIB族金属と第VIII族金属との組合せ、例えば、モリブデン−コバルト、モリブデン−ニッケル、タングステン−ニッケル、モリブデン−コバルト−ニッケル又はタングステン−コバルト−ニッケル等の組合せを好ましく使用することができる。これらの活性金属成分に元素周期律表第ＶII族金属、例えばマンガン、及び第IV族金属、例えば、錫、ゲルマニウム等を添加して使用することもできる。これら水素化活性金属成分は、酸化物及び／又は硫化物として担持させることが好適である。また、担体には、触媒強度を高めるために、チタニア等を同時に担持させることもできる。
金属成分の担持量としては、酸化物として、前記第VIII族金属については、触媒中約０．５〜２０重量％の範囲、第VIB族金属は、約５〜３０重量％の範囲でよい。また、触媒強度の向上のために添加する金属成分は、触媒中、０．５〜２重量％、好ましくは０．９〜１．５重量％の範囲にするのがよい。
【００１１】
担持金属を含浸法によりシリカ−アルミナ担体に担持させる場合、担持させる金属の種類により一液含浸法又は二液含浸法等のいずれの方法を採用してもよい。すなわち、二種以上の金属成分を担持するには、二種以上の金属成分を混合し、その混合溶液から同時に含浸（一液含浸法）させるか又は二種以上の金属成分の溶液を別々に調製し、逐次含浸させていく（二液含浸法）こともでき、本発明においてはこの金属担持法は特に制約されない。
【００１２】
本発明の触媒を好ましく製造するには、前記したシリカ−アルミナをを少なくともその一部として含む担体に対し、先ず元素周期律表第VIII族金属の群から選択される一種又は二種以上の金属を担持させ(第1ステップ)、次いで元素周期律表第VIB族金属の群から選択される一種又は二種以上の金属を担持させる(第２ステップ）。更に詳しく説明すると、この２段階方法によると、担体上に第１ステップにて担持させる水素化活性金属成分は、元素周期律表第VIII族金属の中から選択される一種又は二種以上の金属である。即ち、第VIII族の鉄、コバルト、ニッケル、パラジウム、白金、オスミウム、イリジウム、ルテニウム及びロジウム等から一種又は二種以上が選択して使用される。好ましくは、コバルト及びニッケルが単独又は両者を組合せて使用される。この場合、さらに好ましくは、コバルト／ニッケルの原子比が２．５〜８．５である。
第２ステップで担体に担持させる水素化活性金属成分は、元素周期律表第VIB族金属の群から選択される一種又は二種以上の金属である。即ち、第VIB族のクロム、モリブデン及びタングステンの中から一種又は二種以上が選択して使用される。好ましくはモリブデン及びタングステンが単独で又は両者を組合せて使用される。
【００１３】
上記第VIII族及び第VIB族の水素化活性金属成分は、酸化物及び／又は硫化物として担持させることが好適であり、前記第１及び第２ステップによる２段階担持方法では、活性金属成分の担持量は、酸化物基準で、触媒中、第VIII族金属では０．１〜２０重量％、好ましくは１〜８重量％、より好ましくは２〜５重量％である。第VIB族金属では３〜３０重量％、好ましくは８〜２５重量％、より好ましくは５〜２０重量％である。第VIII族金属を０．１重量％未満担持させたのでは十分な活性を有する触媒が得られず、又２０重量％を超えると、担体と結合しない遊離の金属成分が増加する。第VIII族金属の遊離成分が増加すると、その後に第VIB族金属を担持させる場合に不活性の複合酸化物が生成し、第VIB族金属の分散性を低下せしめ、触媒活性を低下させる。一方、第VIB族金属が３重量％未満では活性が得られず、３０重量％を超えると分散性が低下すると同時に第VIII族金属の助触媒効果が発揮されない。
【００１４】
上記触媒金属の担持方法において、第１及び第２ステップにおける活性金属成分の担体への担持方法としては、担体を前記金属の可溶性塩の水溶液に浸漬し、金属成分を担体に導入する含浸法を採用することができる。含浸操作としては、担体を常温又は常温以上で含浸溶液に浸漬して所望成分が十分担体に含浸する条件に保持する。含浸溶液の量及び温度は、所望量の金属が担持されるように適宜調整することができる。担持量に応じて、含浸溶液に浸漬する担体の量が決定される。
【００１５】
本発明の触媒の形状は、円筒状、粒状又は錠剤状その他如何なるものでもよく、このような形状は、押出成形、造粒成形等の成形法に応じて決められる。成形物の直径は０．５〜３．０ｍｍの範囲が好ましい。
水素化活性金属成分を含浸した担体は、含浸溶液を分離した後、水洗、乾燥及び焼成を行う。乾燥及び焼成の条件は、前記担体の場合の条件と同一でもよいが、焼成条件は４００〜５５０℃が好ましい。重質炭化水素油の水素化脱硫において、触媒は、使用に先立ち、予備硫化を行うことが好ましい。その方法については、後に記載する。
【００１６】
前記のようにして製造される触媒は、シリカ−アルミナ担体上に少なくとも一種の水素化活性金属成分を担持させた触媒であるが、以下に示す触媒性状を有することを特徴とする。
（１）２００〜４００ｍ2／ｇ、好ましくは２２０〜３５０ｍ2／ｇの比表面積を有する。
（２）水銀圧入法により測定した全細孔容積が０．４０〜０．５５ｍｌ／ｇの範囲にある。
（３）窒素吸着法により測定した０〜３００Åの範囲の直径を有する細孔容積Ａが、水銀圧入法により測定した４０Å以上の範囲の直径を有する細孔容積Ｂの７５％以上、殊に、８０〜９０％の範囲にある（Ａ／Ｂ×１００≧７５）。
（４）窒素吸着法により測定した０〜３００Åの範囲内における平均細孔直径が４０〜９０Å、殊に、６０〜９０Åの範囲にある。
（５）水銀圧入法により測定した３００Å以上１５０，０００Å以下の範囲の直径を有する細孔容積が０．０１〜０．２５ｍｌ／ｇ、殊に、０．０３〜０．２０ｍｌ／ｇの範囲にある。
（６）水銀圧入法により測定した３００〜６００Åの範囲の直径を有する細孔容積Ｃが、水銀圧入法により測定した３００Å以上１５０，０００Å以下の範囲の直径を有する細孔容積Ｄの４０％以上、殊に、６０〜９０％の範囲にある（Ｃ／Ｄ×１００≧４０）。
【００１７】
シリカ含有アルミナ及び触媒の細孔容積の測定法として使用した窒素吸着法及び水銀圧入法は、Ｐ．Ｈ．エメット他著「キヤタリシス」第１巻、第１２３頁（ラインホールド・パブリシング・カンパニー発行」(1959年)P.H. Emmett, et al.“Catalysis”,1,123(1959)(Reinhold Publishing Co.)、及び触媒工学講座、第４巻、第６９頁〜第７８頁（地人書館発行）（昭和３９年）に記載の方法による。
水銀圧入法においては、触媒に対する水銀の接触角を１３０°、表面張力を４８５ダイン／ｃｍとし、すべての細孔は円筒形であると仮定した。
窒素吸着法に対しては多分子層吸着に基づく補正の方法が種々提案されており、その中でもＢＪＨ法〔E.P. Barreff. L.G. Joyner and P.P.Halnda, J._Amer., Chem, Sco., 73, 373(1951)〕及びＣＩ法〔R.W. Cranston and F.A. Inkley, “Advances in Catalysis," 1X, 143(1957)(New York Academic Press)〕が一般に用いられている。
本発明における細孔容積に係るデータは吸着等温線の吸着側を使用し、ＤＪＨ法によって計算したものである。
【００１８】
次に、本発明の触媒の使用による炭化水素油の水素化処理について述べる。炭化水素油としては、直留軽油、分解軽油、減圧蒸留軽油、重質分解油等を使用することができる。減圧蒸留軽油は、常圧蒸留残渣油を減圧蒸留して得られる約３７０℃〜６１０℃の範囲の沸点を有する留分を含有する留出油であり、硫黄分、窒素分及び金属分を相当量含有するものである。例えば、中東原油減圧蒸留軽油の一例を挙げるならば、約２〜４重量％の硫黄分、約０．０３〜０．２重量％の窒素分を含有する。重質分解油は、残渣油を熱分解して得られる約２００℃以上の沸点を有する分解油であり、例えば、接触分解装置からのライトサイクル油、残渣油のコーキング及びビスブレーキング等から得られる軽油を使用することができる。
また、炭化水素油としては、硫黄分、窒素分、アスファルト分及び金属含有化合物を含有し、実質的に約４８０℃以上に沸点を有するものを用いることができる。このような炭化水素油は、原油の常圧又は減圧蒸留残渣油を含有する。例えば、常圧において約４８０℃以上の沸点を有する炭化水素成分が約３０〜１００重量％の範囲の残渣油は、通常、約１〜１０重量％の硫黄分、約０．１〜１重量％の窒素分、約１０〜１０００ｐｐｍの金属及び約１重量％の残留炭素分（コンラドソン）を含有する。
以上のように、原料油としては、前記の如き常圧蒸留残渣油、減圧蒸留残渣油、減圧蒸留軽油、重質分解油、常圧蒸留軽油、分解軽油又はこれらの混合油を使用することができる。
【００１９】
反応条件は、原料油の種類、所望する脱硫率又は脱窒素率に応じて適宜選択することができる。すなわち、反応温度；約２８０〜４２０℃、反応圧力；約２０〜２００ｋｇ／ｃｍ2、水素含有ガスの対原料油割合；約１００〜２７０リットル／リットル、及び液空間速度；約０．５〜４．０Ｖ／Ｈ／Ｖを採用する。水素含有ガス中の水素濃度は、約６０〜１００％の範囲でよい。
水素化脱硫を行うにあたり、触媒は、固定床、流動床又は移動床のいずれの形式でも使用することができるが、装置面又は操作上からは固定床を採用することが好ましい。また、二基以上の複数基の反応塔を結合して水素化脱硫を行い、高度の脱硫率を達成することもできる。
【００２０】
本発明の触媒は、使用に先立ち予備硫化を行うことが好ましい。予備硫化は、反応塔のその場において行うことができる。すなわち、焼成した触媒を含硫黄留出油と、温度；約１５０〜４００℃、圧力（全圧）；約２０〜１００ｋｇ／ｃｍ2、液空間速度；約０．３〜２．０Ｖ／Ｈ／Ｖ及び約５０〜１５００リットル／リットルの水素含有ガスの存在下において接触させ、硫化処理の終了後含硫黄留出油を原料油に切替え原料油の脱硫に適当な運転条件に設定し運転を開始する。硫化処理の方法としては、以上の如き方法の他に、硫化水素その他の硫黄化合物を直接触媒と接触させるか又は適当な留出油に添加してこれを触媒と接触させることもできる。
【００２１】
【発明の効果】
本発明の触媒は、その触媒性状として、前記細孔特性を有することを特徴とするが、本発明の触媒の最も大きな特徴は、水銀圧入法により測定した３００〜６００Åの範囲の直径を有する細孔容積Ｃが、水銀圧入法により測定した３００Å以上１５０，０００Å以下の範囲の直径を有する細孔容積Ｄの４０％以上を占めること、すなわち、Ｃ／Ｄの比が４０％以上であることである。本発明の触媒と、前記した公知触媒と比較した場合、このＣ／Ｄの比に大きな相違があり、前記公知触媒のＣ／Ｄは、通常、３０％以下である。そして、本発明の触媒は、このような性状の相違により、前記公知触媒と比較し、高められた脱硫活性を有する。
【００２２】
【実施例】
次に、本発明を実施例について説明する。
実施例１
純水２．０リットルを約７０℃に加熱し、これに水酸化ナトリウム水溶液を添加し、ｐＨ約１２のアルカリ水を作った。次にこのアルカリ水に硫酸アルミニウム水溶液（硫酸アルミニウム５１８ｇ、純水７１０ｇ）を加えた後、水酸化ナトリウム溶液又は硝酸溶液でｐＨを８．４〜８．８に調整し、約７０℃で約０．５時間熟成した。これにより、アルミナ水和物の沈殿（ゲル）を含む水溶液が得られた。
この水溶液に、ケイ酸ナトリウム水溶液（３号水ガラス３８ｇ、純水２１０ｇ）を加え必要に応じて硝酸溶液を加えｐＨを約９とし、温度約７０℃で０．５時間熟成した。これにより、アルミナ水和物の表面にシリカ水和物が沈着した沈殿粒子を含むスラリー液が得られた。
このスラリー液を濾過し、濾別したケーキは、濾過した後の濾液のナトリウム濃度が５ｐｐｍ以下になるまで炭酸アンモニウム水溶液で洗浄した。
このケーキを、８０℃の混練機中で成形可能な含水量になるまで乾燥しながら混練し、押出し型成形機により、１．５ｍｍφの円柱状ペレットに成形した。
成形されたペレットは、１２０℃で１６時間乾燥し、さらに７００℃で３時間焼成して担体とした。
次いで、この担体に、パラモリブデン酸アンモニウムの水溶液（モリブデン液）を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次に、硝酸コバルト水溶液（コバルト液）を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ａとした。
【００２３】
実施例２
実施例１において、ケイ酸ナトリウム水溶液滴下後のｐＨを８．８〜９．２とした以外は同様にして触媒担体を作った。
次に、この触媒担体に、パラモリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次いで、硝酸コバルトと硝酸ニッケルを含有する水溶液を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ｂとした。
【００２４】
実施例３
実施例２と同様にして触媒担体を作った。
次に、この触媒担体に、パラモリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次いで、硝酸コバルトの水溶液を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ｃとした。
【００２５】
実施例４
実施例１において、ケイ酸ナトリウム水溶液の全添加量を５０ｇとし、また、ケイ酸ナトリウム水溶液滴下後のｐＨを８．６〜８．８とした以外は同様にして触媒担体を作った。
次に、この触媒担体に、パラモリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次いで、硝酸コバルトと硝酸ニッケルを含有する水溶液を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ｄとした。
【００２６】
実施例５
実施例１において、ケイ酸ナトリウム水溶液の全添加量を９２ｇとし、また、ケイ酸ナトリウム水溶液滴下後のｐＨを８．６〜８．８とした以外は同様にして触媒担体を作った。
次に、この触媒担体に、パラモリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次いで、硝酸コバルト水溶液を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ｅとした。
【００２７】
比較例１
市販の脱硫触媒を用いた（触媒Ｆ）。
【００２８】
比較例２
実施例１において、ケイ酸ナトリウム水溶液の全添加量を１４ｇとし、また、ケイ酸ナトリウム水溶液滴下後のｐＨを９．２〜９．４とした以外は実施例１〜５と同様にして触媒担体を作った。
次に、この触媒担体に、パラモリブデン酸アンモニウムの水溶液を含浸させ、１２０℃で乾燥し、４５０℃で焼成した。次いで、硝酸コバルト水溶液を含浸させ、１２０℃で乾燥し、５００℃で焼成して触媒Ｇとした。
【００２９】
前記のようにして得た各触媒の性状を比較触媒とともに、表１に示す。
なお、表１において示した符号は次の内容を示す。
ａ：窒素吸着法により測定された細孔直径が０〜３００Åの範囲にある細孔容積
ｂ：水銀圧入法により測定された細孔直径が４０Å以上の範囲にある細孔容積
ｃ：水銀圧入法により測定された細孔直径が３００〜６００Åの範囲にある細孔容積
ｄ：水銀圧入法により測定された細孔直径が３００Å以上（３００〜１５００００Å）の範囲にある細孔容積
【００３０】
【表１】
応用例１
実施例の触媒Ａ〜Ｄ及び比較触媒Ｆ、Ｇを用いて、中東原油減圧蒸留軽油の水素化脱硫処理を行った。
表２にその水素化脱硫条件を示す。
【００３２】
【表２】
【００３３】
【表３】
[Industrial application fields]
The present invention relates to a catalyst for hydroprocessing hydrocarbon oils.
[0002]
[Prior art]
Various kinds of hydrocarbon oil hydrotreating catalysts have been proposed in the past. Among them, specific pores having a specific surface area of 200 to 400 m 2 / g are considered to have relatively excellent desulfurization performance. There are those in which a hydrogenation active metal component is supported on silica-alumina having a volume distribution (JP-B-5-39662, JP-B-3-31496, etc.).
These known catalysts are characterized in that the content of macropores having a pore diameter of 300 mm or more is specified low, and the desulfurization activity is maintained for a long time.
However, in the case of these catalysts, the desulfurization activity can be maintained for a long time, but the desulfurization activity is still not satisfactory.
[0003]
[Problems to be solved by the invention]
This invention makes it the subject to provide the catalyst for hydroprocessing improved in the desulfurization activity.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, according to the present invention, at least one hydrogenation-active metal component is formed on a support made of silica-alumina having a structure in which a silica layer is formed on an alumina surface as a nucleus and containing 2 to 40% by weight of silica. And having a specific surface area of 200 to 400 m 2 / g and a total pore volume of 0.40 to 0.55 ml / g measured by a mercury intrusion method, by a nitrogen adsorption method The measured pore volume having a diameter in the range of 0 to 300 cm accounted for 75% or more of the pore volume having a diameter in the range of 40 mm or more measured by mercury porosimetry, and was measured from 0 to 300 mm measured by the nitrogen adsorption method. The average pore diameter of pores having a diameter in the range is 40 to 90 mm, and the pore volume having a diameter in the range of 300 to 150,000 measured by mercury porosimetry is 0.01 to 0.00. It is 5 ml / g, and the pore volume having a diameter in the range of 300 to 600 mm measured by the mercury intrusion method occupies 40% or more of the pore volume having a diameter in the range of 300 to 150,000 mm. A hydrotreating catalyst is provided.
[0005]
In the hydrotreating catalyst of the present invention, silica-alumina having a structure in which a silica layer is formed on the surface of alumina as a nucleus is used as at least a part of the catalyst carrier. The content of silica in this catalyst is generally 2 to 40% by weight, but an increase in hydrogen consumption accompanying the excessive decomposition reaction in hydrodesulfurization reaction or hydrodenitrogenation reaction, production of coke, etc. In order to control the content, the silica content should be specified in the range of 5 to 20% by weight, preferably 7 to 15% by weight. In addition to silica, the carrier comprising silica-alumina contains one or more of other refractory inorganic oxides such as magnesia, calcium oxide, zirconia, titania, boria, hafnia and crystalline zeolite. can do. In the carrier composed of silica-alumina used in the present invention, silica exhibits an action of controlling the solid acidity necessary for the catalyst, and the specific amount of addition is appropriately determined according to the desired catalyst acid strength. Silica imparts a strong acid point to the catalyst and increases the hydrocarbon decomposition activity of the catalyst. On the other hand, for example, magnesia reduces the strong acid point of alumina-silica and the like, and increases the weak acid point at the same time. Has the effect of improving the selectivity. The content of refractory inorganic oxides such as magnesia, calcium oxide, zirconia, titania, boria, hafnia and crystalline zeolite is suitably in the range of about 1 to 10% by weight with respect to alumina-silica. As the alumina, those forming either γ-alumina, χ-alumina or η-alumina or a mixture thereof are suitable.
[0006]
In order to produce silica-alumina suitable as the catalyst carrier of the present invention, an aqueous alkali solution adjusted to pH 7 to 13, preferably 11 to 12.5 is first prepared. As the alkali, sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like is used.
Next, an acidic aluminum compound aqueous solution is added and mixed in the alkaline aqueous solution. As the acidic aluminum compound, aluminum sulfate, chloride, nitrate and the like are used. The concentration of the acidic aluminum compound in the aqueous solution is usually 36 to 42% by weight, preferably 38 to 40% by weight. In this case, the pH in the mixed aqueous solution is 7 to 11, preferably 8 to 10.
[0007]
The mixed aqueous solution obtained as described above is maintained at a temperature of 50 to 80 ° C, preferably 60 to 75 ° C. The holding time in this case is at most 2 hours, preferably 0.2 to 1.5 hours. This causes precipitation (gel) of alumina hydrate in the mixed aqueous solution.
[0008]
Next, an aqueous solution of a water-soluble silicon compound is added to and mixed with the mixed aqueous solution containing such precipitates of alumina hydrate. As the water-soluble silicon compound, alkali metal silicate, tetraalkoxysilane, orthosilicate ester and the like are used. As the alkali metal silicate, sodium silicate having a Na 2 O: SiO 2 molar ratio in the range of 1: 2 to 1: 4 is preferably used. The concentration of the silicon compound in the aqueous solution is 5 to 10% by weight, preferably 6 to 8% by weight. The amount of silicon compound added to the aqueous solution containing the alumina hydrate precipitate is an amount corresponding to the composition of the silica-containing alumina that is the final product, and is such an amount that the silica content is 2 to 40% by weight. . A mixed solution of an aqueous solution containing an alumina hydrate precipitate and an aqueous solution of a silicon compound is maintained at a pH of 7 to 11, preferably 8 to 10. In this case, if necessary, a pH adjusting agent such as a mineral acid aqueous solution is added to maintain the pH of the mixed aqueous solution in the above range. This mixed aqueous solution is maintained at a temperature of 50 to 80 ° C, preferably 60 to 75 ° C. The holding time is at most 2 hours, preferably 0.2 to 1.5 hours. By this operation, precipitated particles in which silica hydrate is deposited on alumina hydrate are obtained. The precipitated particles are separated from the liquid and then subjected to a conventional cleaning process, for example, an ammonium carbonate aqueous solution and water to remove impurity ions, and after kneading, the particles are molded into a desired shape. The Next, the molded product is dried and fired. Drying is performed at room temperature to 200 ° C. in the presence or absence of oxygen. Moreover, baking is performed at 200-800 degreeC in the presence of oxygen, Preferably it is 600-700 degreeC. In this manner, silica-alumina having a structure in which a silica layer is formed on the surface of alumina as a nucleus and having pore characteristics substantially coincident with the pore characteristics shown for the above-described catalyst can be obtained.
Further, when the cake obtained by filtering the slurry liquid containing the precipitated particles obtained by the deposition method is kneaded by a kneader and formed by an extrusion molding machine, the amount of water and acid required for kneading are changed to change the pores. Fine adjustment of the distribution can be performed.
[0009]
As described above, other metal components such as magnesia, calcium oxide, zirconia, boria, hafnia, crystalline zeolite and the like can be added to silica-alumina as necessary. These metal components can be added by a mixing method or can be added by a conventionally known impregnation method or coprecipitation method, but are preferably added by an impregnation method. When adding by an impregnation method, silica-alumina is immersed in an impregnation solution containing a predetermined soluble metal component, the metal component is impregnated in a desired amount in silica-alumina, dried, and fired. .
The hydrotreating catalyst of the present invention can be obtained by supporting a hydrogenation active metal on the support containing silica-alumina. As a method for supporting the hydrogenation active metal, a conventionally known impregnation method or a coprecipitation method can be used, but an impregnation method is preferable.
The pore characteristics of the hydrotreating catalyst of the present invention correspond to the silica-alumina used as the carrier, and the catalyst of the present invention has pore characteristics almost equivalent to the silica-alumina used as the carrier.
[0010]
As the hydrogenation active metal component to be supported on the silica-alumina support, one or more metals selected from the group of Group VIB metals and Group VIII metals of the Periodic Table of Elements are selected. That is, one or more selected from Group VIB chromium, molybdenum and tungsten, Group VIII iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium and rhodium are used. For hydrodesulfurization of hydrocarbon oils, in particular, combinations of Group VIB metals and Group VIII metals, such as molybdenum-cobalt, molybdenum-nickel, tungsten-nickel, molybdenum-cobalt-nickel or tungsten-cobalt. -A combination of nickel and the like can be preferably used. These active metal components can be used by adding Group VII metals such as manganese and Group IV metals such as tin and germanium to the periodic table of elements. These hydrogenation active metal components are preferably supported as oxides and / or sulfides. In addition, titania or the like can be simultaneously supported on the carrier in order to increase the catalyst strength.
The supported amount of the metal component may be in the range of about 0.5 to 20% by weight in the catalyst for the Group VIII metal and about 5 to 30% by weight for the Group VIB metal as oxides. The metal component added for improving the catalyst strength is 0.5 to 2% by weight in the catalyst, preferably 0.9 to 1.5% by weight.
[0011]
When the supported metal is supported on the silica-alumina support by the impregnation method, any method such as a one-component impregnation method or a two-component impregnation method may be employed depending on the type of metal to be supported. That is, in order to carry two or more metal components, two or more metal components are mixed and impregnated simultaneously from the mixed solution (one-component impregnation method) or two or more metal component solutions are separately provided. It can also be prepared and impregnated sequentially (two-component impregnation method), and the metal loading method is not particularly limited in the present invention.
[0012]
In order to preferably produce the catalyst of the present invention, one or two or more metals selected from the group VIII metal of the Periodic Table of Elements are first applied to the support containing silica-alumina as at least a part thereof. Is then supported (first step), and then one or more metals selected from the group VIB metals of the periodic table of elements are supported (second step). More specifically, according to this two-stage method, the hydrogenation active metal component supported on the support in the first step is one or more metals selected from Group VIII metals of the Periodic Table of Elements. It is. That is, one or more of Group VIII iron, cobalt, nickel, palladium, platinum, osmium, iridium, ruthenium and rhodium are selected and used. Preferably, cobalt and nickel are used alone or in combination. In this case, more preferably, the atomic ratio of cobalt / nickel is 2.5 to 8.5.
The hydrogenation active metal component supported on the support in the second step is one or more metals selected from the group VIB metals of the Periodic Table of Elements. That is, one or more of VIB group chromium, molybdenum and tungsten are selected and used. Preferably, molybdenum and tungsten are used alone or in combination.
[0013]
The Group VIII and Group VIB hydrogenation active metal components are preferably supported as oxides and / or sulfides. In the two-stage loading method according to the first and second steps, the active metal component The supported amount is 0.1 to 20% by weight, preferably 1 to 8% by weight, more preferably 2 to 5% by weight, based on oxides, of the Group VIII metal in the catalyst. For Group VIB metals, it is 3-30% by weight, preferably 8-25% by weight, more preferably 5-20% by weight. If the Group VIII metal is supported in an amount of less than 0.1% by weight, a catalyst having sufficient activity cannot be obtained, and if it exceeds 20% by weight, the amount of free metal components not bound to the support increases. When the free component of the Group VIII metal increases, an inactive composite oxide is formed when the Group VIB metal is subsequently supported, thereby reducing the dispersibility of the Group VIB metal and reducing the catalytic activity. On the other hand, if the Group VIB metal is less than 3% by weight, the activity cannot be obtained, and if it exceeds 30% by weight, the dispersibility is lowered and the cocatalyst effect of the Group VIII metal is not exhibited.
[0014]
In the catalyst metal loading method, the active metal component is supported on the carrier in the first and second steps by an impregnation method in which the carrier is immersed in an aqueous solution of a soluble salt of the metal and the metal component is introduced into the carrier. Can be adopted. In the impregnation operation, the support is immersed in an impregnation solution at room temperature or above, and the condition is maintained such that the desired component is sufficiently impregnated into the support. The amount and temperature of the impregnation solution can be appropriately adjusted so that a desired amount of metal is supported. Depending on the loading amount, the amount of carrier immersed in the impregnation solution is determined.
[0015]
The shape of the catalyst of the present invention may be any shape such as a cylindrical shape, a granular shape or a tablet shape, and such a shape is determined according to a molding method such as extrusion molding or granulation molding. The diameter of the molded product is preferably in the range of 0.5 to 3.0 mm.
The carrier impregnated with the hydrogenation active metal component is washed with water, dried and fired after separating the impregnating solution. The drying and firing conditions may be the same as those for the carrier, but the firing conditions are preferably 400 to 550 ° C. In the hydrodesulfurization of heavy hydrocarbon oil, the catalyst is preferably pre-sulfurized prior to use. The method will be described later.
[0016]
The catalyst produced as described above is a catalyst in which at least one hydrogenation active metal component is supported on a silica-alumina support, and has the following catalytic properties.
(1) It has a specific surface area of 200 to 400 m 2 / g, preferably 220 to 350 m 2 / g.
(2) The total pore volume measured by mercury porosimetry is in the range of 0.40 to 0.55 ml / g.
(3) The pore volume A having a diameter in the range of 0 to 300 mm measured by the nitrogen adsorption method is 75% or more of the pore volume B having a diameter in the range of 40 mm or more measured by the mercury intrusion method, in particular, It is in the range of 80 to 90% (A / B × 100 ≧ 75).
(4) The average pore diameter in the range of 0 to 300 mm measured by the nitrogen adsorption method is in the range of 40 to 90 mm, particularly 60 to 90 mm.
(5) The pore volume having a diameter in the range of 300 to 150,000 し た measured by the mercury intrusion method is in the range of 0.01 to 0.25 ml / g, particularly 0.03 to 0.20 ml / g. is there.
(6) 40% or more of the pore volume D having a diameter in the range of 300 to 600 mm measured by the mercury intrusion method and having a diameter in the range of 300 to 150,000 kg measured by the mercury intrusion method In particular, it is in the range from 60 to 90% (C / D × 100 ≧ 40).
[0017]
The nitrogen adsorption method and the mercury intrusion method used as methods for measuring the pore volume of silica-containing alumina and catalyst are described in P.A. H. Emmet et al., “Catalysis”, Volume 1, page 123 (published by Linehold Publishing Company) (1959) PH Emmett, et al. “Catalysis”, 1,123 (1959) (Reinhold Publishing Co.), and catalytic engineering Lecture, Volume 4, pages 69-78 (published by Jinjinshokan) (Showa 39).
In the mercury intrusion method, the contact angle of mercury with the catalyst was 130 °, the surface tension was 485 dynes / cm, and all pores were assumed to be cylindrical.
For the nitrogen adsorption method, various correction methods based on multi-layer adsorption have been proposed. Among them, the BJH method [EP Barreff. LG Joyner and PPHalnda, J._Amer., Chem, Sco., 73 , 373 ( 1951)] and the CI method [RW Cranston and FA Inkley, “Advances in Catalysis,” 1X , 143 (1957) (New York Academic Press)].
The data relating to the pore volume in the present invention is calculated by the DJH method using the adsorption side of the adsorption isotherm.
[0018]
Next, the hydrotreating of hydrocarbon oil by using the catalyst of the present invention will be described. As the hydrocarbon oil, straight-run gas oil, cracked gas oil, vacuum distilled gas oil, heavy cracked oil and the like can be used. Vacuum distillation gas oil is a distillate containing a fraction having a boiling point in the range of about 370 ° C. to 610 ° C. obtained by distillation under reduced pressure of atmospheric distillation residue oil, corresponding to sulfur, nitrogen and metal. It is contained in an amount. For example, if an example of the Middle Eastern crude oil vacuum distillation light oil is given, it contains about 2 to 4% by weight of sulfur and about 0.03 to 0.2% by weight of nitrogen. Heavy cracked oil is a cracked oil having a boiling point of about 200 ° C. or higher obtained by pyrolyzing residual oil. For example, it is obtained from light cycle oil from catalytic cracking equipment, coking and visbreaking of residual oil, etc. Can be used.
Moreover, as hydrocarbon oil, what contains a sulfur content, nitrogen content, asphalt content, and a metal containing compound, and has a boiling point substantially about 480 degreeC or more can be used. Such hydrocarbon oils contain crude oil normal pressure or vacuum distillation residue oil. For example, a residual oil having a hydrocarbon component having a boiling point of about 480 ° C. or higher at normal pressure in a range of about 30 to 100% by weight usually has a sulfur content of about 1 to 10% by weight and about 0.1 to 1% by weight. Nitrogen content, about 10 to 1000 ppm metal and about 1 wt% residual carbon (Conradson).
As described above, as the raw oil, it is possible to use the atmospheric distillation residue oil, the vacuum distillation residue oil, the vacuum distillation gas oil, the heavy cracked oil, the atmospheric distillation gas oil, the cracked gas oil or a mixed oil thereof as described above. it can.
[0019]
The reaction conditions can be appropriately selected according to the type of raw material oil, the desired desulfurization rate or denitrification rate. That is, reaction temperature: about 280-420 ° C., reaction pressure: about 20-200 kg / cm 2 , hydrogen-containing gas to feedstock ratio: about 100-270 liter / liter, and liquid space velocity: about 0.5-4 Adopt 0.0V / H / V. The hydrogen concentration in the hydrogen-containing gas may range from about 60 to 100%.
In carrying out hydrodesulfurization, the catalyst can be used in any form of a fixed bed, a fluidized bed or a moving bed, but it is preferable to adopt a fixed bed from the viewpoint of the apparatus or operation. It is also possible to achieve a high degree of desulfurization by performing hydrodesulfurization by combining two or more reaction towers.
[0020]
The catalyst of the present invention is preferably presulfided prior to use. Presulfiding can be performed in situ in the reaction tower. That is, the calcined catalyst is a sulfur-containing distillate, temperature: about 150 to 400 ° C., pressure (total pressure); about 20 to 100 kg / cm 2 , liquid space velocity: about 0.3 to 2.0 V / H / V and contact in the presence of a hydrogen-containing gas of about 50 to 1500 liters / liter. After the sulfidation treatment, the sulfur-containing distillate is switched to the feedstock, and the operation conditions are set to be suitable for desulfurization of the feedstock. To do. In addition to the method as described above, hydrogen sulfide or other sulfur compounds can be directly brought into contact with the catalyst, or added to an appropriate distillate and brought into contact with the catalyst.
[0021]
【The invention's effect】
The catalyst of the present invention is characterized by having the above-mentioned pore characteristics as its catalytic properties. The most significant feature of the catalyst of the present invention is that it has a diameter in the range of 300 to 600 mm measured by mercury porosimetry. The pore volume C occupies 40% or more of the pore volume D having a diameter in the range of 300 to 150,000 measured by the mercury intrusion method, that is, the C / D ratio is 40% or more. is there. When comparing the catalyst of the present invention with the above-mentioned known catalyst, there is a large difference in the C / D ratio, and the C / D of the known catalyst is usually 30% or less. And the catalyst of this invention has the desulfurization activity improved compared with the said well-known catalyst by the difference in such a property.
[0022]
【Example】
Next, examples of the present invention will be described.
Example 1
2.0 liters of pure water was heated to about 70 ° C., and an aqueous sodium hydroxide solution was added thereto to produce alkaline water having a pH of about 12. Next, an aqueous aluminum sulfate solution (aluminum sulfate 518 g, pure water 710 g) was added to the alkaline water, and then the pH was adjusted to 8.4 to 8.8 with a sodium hydroxide solution or a nitric acid solution. Aged for 5 hours. Thereby, the aqueous solution containing the precipitation (gel) of an alumina hydrate was obtained.
To this aqueous solution, an aqueous sodium silicate solution (38 g of No. 3 water glass, 210 g of pure water) was added, and if necessary, a nitric acid solution was added to adjust the pH to about 9, and the mixture was aged at a temperature of about 70 ° C. for 0.5 hours. Thereby, the slurry liquid containing the precipitation particle | grains which the silica hydrate deposited on the surface of the alumina hydrate was obtained.
This slurry was filtered, and the cake separated by filtration was washed with an aqueous ammonium carbonate solution until the sodium concentration of the filtrate after filtration was 5 ppm or less.
The cake was kneaded while being dried in a kneader at 80 ° C. until the water content was moldable, and formed into 1.5 mmφ cylindrical pellets by an extrusion molding machine.
The formed pellets were dried at 120 ° C. for 16 hours and further calcined at 700 ° C. for 3 hours to obtain a carrier.
Next, this carrier was impregnated with an aqueous solution of ammonium paramolybdate (molybdenum solution), dried at 120 ° C., and calcined at 450 ° C. Next, it was impregnated with an aqueous cobalt nitrate solution (cobalt solution), dried at 120 ° C., and calcined at 500 ° C. to obtain catalyst A.
[0023]
Example 2
A catalyst carrier was prepared in the same manner as in Example 1 except that the pH after dropping the aqueous sodium silicate solution was 8.8 to 9.2.
Next, this catalyst support was impregnated with an aqueous solution of ammonium paramolybdate, dried at 120 ° C., and calcined at 450 ° C. Next, the catalyst B was impregnated with an aqueous solution containing cobalt nitrate and nickel nitrate, dried at 120 ° C., and calcined at 500 ° C.
[0024]
Example 3
A catalyst carrier was prepared in the same manner as in Example 2.
Next, this catalyst support was impregnated with an aqueous solution of ammonium paramolybdate, dried at 120 ° C., and calcined at 450 ° C. Next, an aqueous solution of cobalt nitrate was impregnated, dried at 120 ° C., and calcined at 500 ° C. to obtain catalyst C.
[0025]
Example 4
In Example 1, a catalyst carrier was prepared in the same manner except that the total amount of the sodium silicate aqueous solution was 50 g and the pH after dropping the sodium silicate aqueous solution was 8.6 to 8.8.
Next, this catalyst support was impregnated with an aqueous solution of ammonium paramolybdate, dried at 120 ° C., and calcined at 450 ° C. Next, the catalyst D was impregnated with an aqueous solution containing cobalt nitrate and nickel nitrate, dried at 120 ° C., and calcined at 500 ° C.
[0026]
Example 5
In Example 1, a catalyst carrier was prepared in the same manner except that the total amount of the sodium silicate aqueous solution was 92 g and the pH after dropping the sodium silicate aqueous solution was 8.6 to 8.8.
Next, this catalyst support was impregnated with an aqueous solution of ammonium paramolybdate, dried at 120 ° C., and calcined at 450 ° C. Subsequently, it was impregnated with an aqueous cobalt nitrate solution, dried at 120 ° C., and calcined at 500 ° C. to obtain catalyst E.
[0027]
Comparative Example 1
A commercially available desulfurization catalyst was used (Catalyst F).
[0028]
Comparative Example 2
In Example 1, the total amount of the sodium silicate aqueous solution added was 14 g, and the catalyst carrier was the same as in Examples 1-5 except that the pH after dropping the sodium silicate aqueous solution was 9.2 to 9.4. made.
Next, this catalyst support was impregnated with an aqueous solution of ammonium paramolybdate, dried at 120 ° C., and calcined at 450 ° C. Next, it was impregnated with an aqueous cobalt nitrate solution, dried at 120 ° C., and calcined at 500 ° C. to obtain catalyst G.
[0029]
Properties of each catalyst obtained as described above are shown in Table 1 together with a comparative catalyst.
In addition, the code | symbol shown in Table 1 shows the following content.
a: Pore volume with a pore diameter measured by the nitrogen adsorption method in the range of 0 to 300 mm b: Pore volume with a pore diameter measured by the mercury intrusion method in the range of 40 cm or more c: Mercury intrusion method Pore volume with pore diameter measured in the range of 300 to 600 mm: pore volume with pore diameter measured by mercury intrusion method in the range of 300 mm or more (300 to 150,000 mm)
[Table 1]
Application example 1
Using the catalysts A to D and the comparative catalysts F and G of the examples, hydrodesulfurization treatment of Middle Eastern crude oil vacuum distillation gas oil was performed.
Table 2 shows the hydrodesulfurization conditions.
[0032]
[Table 2]
[0033]
[Table 3]
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25285694A JP3802939B2 (en) | 1994-09-21 | 1994-09-21 | Catalyst for hydrotreating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25285694A JP3802939B2 (en) | 1994-09-21 | 1994-09-21 | Catalyst for hydrotreating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0889816A JPH0889816A (en) | 1996-04-09 |
| JP3802939B2 true JP3802939B2 (en) | 2006-08-02 |
Family
ID=17243130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25285694A Expired - Lifetime JP3802939B2 (en) | 1994-09-21 | 1994-09-21 | Catalyst for hydrotreating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3802939B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2793706B1 (en) * | 1999-05-18 | 2001-08-03 | Total Raffinage Distribution | OXIDE-BASED CATALYTIC SUPPORT OF A METAL FROM GROUP IVB OF THE PERIODIC CLASSIFICATION OF ELEMENTS, ITS PREPARATION AND USES |
| JP4865940B2 (en) * | 1999-09-29 | 2012-02-01 | 一般財団法人石油エネルギー技術センター | Hydrotreating catalyst and method for hydrotreating heavy hydrocarbon oil using the catalyst |
| JP4773634B2 (en) * | 2001-06-08 | 2011-09-14 | 日本ケッチェン株式会社 | Two-stage hydroprocessing method for heavy hydrocarbon oil |
| JP4773633B2 (en) * | 2001-06-08 | 2011-09-14 | 日本ケッチェン株式会社 | Two-stage hydroprocessing method for heavy hydrocarbon oil |
| JP4838258B2 (en) | 2005-10-05 | 2011-12-14 | 株式会社キャタラー | Exhaust gas purification catalyst |
| KR102238548B1 (en) * | 2017-12-29 | 2021-04-08 | 한화솔루션 주식회사 | Noble metal-transition metal complex catalyst of carbon coated silica-alumina and preparation method of thereof |
-
1994
- 1994-09-21 JP JP25285694A patent/JP3802939B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0889816A (en) | 1996-04-09 |
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