JP3333230B2 - Hydrodesulfurization catalyst and method for producing the same - Google Patents
Hydrodesulfurization catalyst and method for producing the sameInfo
- Publication number
- JP3333230B2 JP3333230B2 JP12376692A JP12376692A JP3333230B2 JP 3333230 B2 JP3333230 B2 JP 3333230B2 JP 12376692 A JP12376692 A JP 12376692A JP 12376692 A JP12376692 A JP 12376692A JP 3333230 B2 JP3333230 B2 JP 3333230B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- weight
- compound
- erbium
- extruded
- 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 147
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052750 molybdenum Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 239000010941 cobalt Substances 0.000 claims description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 150000002123 erbium compounds Chemical class 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052691 Erbium Inorganic materials 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- -1 phosphorus compound Chemical class 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 235000012438 extruded product Nutrition 0.000 claims description 9
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002816 nickel compounds Chemical class 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000005078 molybdenum compound Substances 0.000 claims description 7
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 60
- 239000003921 oil Substances 0.000 description 40
- 238000006477 desulfuration reaction Methods 0.000 description 31
- 230000023556 desulfurization Effects 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000007791 liquid phase Substances 0.000 description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 23
- 229910052717 sulfur Inorganic materials 0.000 description 23
- 239000011593 sulfur Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000012153 distilled water Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 11
- 229940010552 ammonium molybdate Drugs 0.000 description 11
- 235000018660 ammonium molybdate Nutrition 0.000 description 11
- 239000011609 ammonium molybdate Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 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 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 150000001869 cobalt compounds Chemical class 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- DBUHPIKTDUMWTR-UHFFFAOYSA-K erbium(3+);triacetate Chemical compound [Er+3].CC([O-])=O.CC([O-])=O.CC([O-])=O DBUHPIKTDUMWTR-UHFFFAOYSA-K 0.000 description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 2
- SXJVNCWLEGIRSJ-UHFFFAOYSA-N erbium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SXJVNCWLEGIRSJ-UHFFFAOYSA-N 0.000 description 2
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QGJSAGBHFTXOTM-UHFFFAOYSA-K trifluoroerbium Chemical compound F[Er](F)F QGJSAGBHFTXOTM-UHFFFAOYSA-K 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 150000000917 Erbium Chemical class 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- ICCXQXBGPCFVDG-UHFFFAOYSA-N cobalt(2+) erbium(3+) pentanitrate Chemical compound [Er+3].[N+](=O)([O-])[O-].[Co+2].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] ICCXQXBGPCFVDG-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XFULIUKARWFBDF-UHFFFAOYSA-K erbium(3+);phosphate Chemical compound [Er+3].[O-]P([O-])([O-])=O XFULIUKARWFBDF-UHFFFAOYSA-K 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004525 petroleum distillation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は硫黄化合物を含有してい
る炭化水素留分、特に軽油留分を水素化脱硫するための
改善された触媒ならびにその製造方法および使用に関す
る。The present invention relates to an improved catalyst for the hydrodesulfurization of hydrocarbon fractions containing sulfur compounds, in particular gas oil fractions, and to a process for their preparation and use.
【０００２】[0002]
【従来の技術】今日環境問題が大きく取り上げられてい
ることを背景に、脱硫技術においては軽油中の硫黄分の
軽減規制に関心が持たれている。我が国でも１９８９年
から軽油製品中の硫黄含有量規制の検討が開始され、第
一段階として１９９２年４月より軽油製品中の硫黄含有
量が０．２重量％以下に規制され、さらに第二段階とし
て１９９７年までには０．０５重量％以下にする規制が
検討されている。2. Description of the Related Art With environmental issues being widely taken up today, there is an interest in desulfurization technology in reducing sulfur content in light oil. In Japan, studies on the regulation of sulfur content in gas oil products have begun in 1989. As a first step, the sulfur content in gas oil products was regulated to 0.2% by weight or less in April 1992. By 1997, regulations for reducing the content to 0.05% by weight or less have been studied.
【０００３】現状の軽油脱硫装置と既存の触媒を用いる
脱硫技術では、反応条件の苛酷度を上げても硫黄含有量
を０．１〜０．１５重量％程度まで低減することが限界
であると言われている。現有設備においては、極端に液
空間速度を下げると処理能力が低下するため設備の規模
を拡大する必要が生じるのみならず、副反応を助長し製
品軽油中の色相（色相値および安定性）を損なう。また
活性を増加するため反応温度を上げると副反応が起こ
り、やはり製品軽油中の色相を低下させてしまう。そこ
で現状の軽油脱硫装置を使用して、苛酷度がより小さい
反応条件下で作用する触媒の出現ならびに水素化精製法
の開発が待望されている。[0003] In the current gas oil desulfurization apparatus and desulfurization technology using an existing catalyst, it is limited that the sulfur content can be reduced to about 0.1 to 0.15% by weight even if the severity of the reaction conditions is increased. It is said. In the existing equipment, if the liquid space velocity is extremely reduced, the processing capacity will be reduced, so not only will it be necessary to enlarge the equipment scale, but it will also promote side reactions and reduce the hue (hue value and stability) in the product light oil. Spoil. When the reaction temperature is raised to increase the activity, a side reaction occurs, and the hue in the product light oil also decreases. Therefore, there is a long-awaited demand for the appearance of a catalyst that operates under less severe reaction conditions and the development of a hydrorefining method using a current gas oil desulfurization unit.
【０００４】水素化精製すなわち水素化脱硫は、一般に
通常約１００〜６００℃、好ましくは２００〜４５０℃
の範囲内にある温度、通常約１０〜３００Ｋｇ／ｃ
ｍ2、好ましくは２０〜１００Ｋｇ／ｃｍ2の範囲内にあ
る圧力、通常約０．１〜１０ｈｒ-1、好ましくは０．５
〜６ｈｒ-1の範囲内にある液空間速度、および通常約３
０〜１５００Ｎｍ3／ＫＬ、好ましくは５０〜５００Ｎ
ｍ3／ＫＬの範囲内にある水素／原料油比の供給速度の
反応条件下で行われる。水素化脱硫触媒は、好ましくは
耐火性担体上に周期律表第ＶＩＢ族金属（通常モリブデ
ンもしくはタングステン）化合物、周期律表第ＶＩＩＩ
族金属（通常コバルトもしくはニッケル）化合物を担持
させたものが広く用いられている。[0004] Hydrorefining, ie, hydrodesulfurization, is generally usually about 100-600 ° C, preferably 200-450 ° C.
, Usually about 10 to 300 Kg / c
m 2 , preferably in the range of 20-100 kg / cm 2 , usually about 0.1-10 hr -1 , preferably 0.5
Liquid hourly space velocity in the range of 範 囲 6 hr −1 and usually about 3
0 to 1500 Nm 3 / KL, preferably 50 to 500 N
It is carried out under reaction conditions with a feed rate of hydrogen / feedstock ratio in the range of m 3 / KL. The hydrodesulfurization catalyst is preferably a compound of Group VIB metal (usually molybdenum or tungsten) on a refractory support, a compound of Group VIII of the Periodic Table.
Those carrying a group metal (usually cobalt or nickel) compound are widely used.
【０００５】この種の水素化脱硫触媒、触媒担体、それ
らの製造方法および使用方法としてこれまでに様々な提
案がなされている。特開昭５０−６４１９０号公報に
は、耐火性担体上に担持された鉄族金属、第ＶＩＢ族金
属よりなり異なる大きさの微細孔を有する触媒へ更に希
土類（セリウムまたはランタン）を添加することによっ
て、脱硫の程度が増加するだけでなく脱硫活性の低下率
が低くなることが開示されている。[0005] Various proposals have been made so far as hydrodesulfurization catalysts of this kind, catalyst carriers, and methods for their production and use. JP-A-50-64190 discloses that a rare earth element (cerium or lanthanum) is further added to a catalyst having fine pores of different sizes composed of an iron group metal and a group VIB metal supported on a refractory carrier. It discloses that not only does the degree of desulfurization increase, but also the rate of decrease in desulfurization activity decreases.
【０００６】特開昭５２−５６９１号公報においては、
耐火性担体上の鉄族金属または第ＶＩ族金属よりなる触
媒を、アルカリまたはアルカリ土類金属、希土類金属ま
たは遷移金属の水溶液で還流することよりなる触媒の製
造方法が提案されているが、希土類金属または遷移金属
として具体的にどのような元素を使用するかについては
全く教示されていない。In Japanese Patent Application Laid-Open No. 52-5691,
There has been proposed a method for producing a catalyst comprising refluxing a catalyst comprising an iron group metal or a group VI metal on a refractory carrier with an aqueous solution of an alkali or alkaline earth metal, a rare earth metal or a transition metal. There is no teaching as to what elements to use specifically as metals or transition metals.
【０００７】特公昭５３−６１１３号公報には、第ＶＩ
Ｂ族金属化合物、第ＶＩＩＩ族金属化合物および耐火性
無機酸化物を用いて混合および解コウして押し出し可能
な軟塊を形成し、この軟塊を押し出し、押し出された軟
塊を乾燥およびカ焼し、カ焼した押出成形体を第ＶＩＢ
族金属化合物と第ＶＩＩＩ族金属化合物で含浸処理した
後、酸化雰囲気中で乾燥およびカ焼することからなる水
素脱硫触媒の製造方法が記載されている。Japanese Patent Publication No. 53-6113 discloses a VI
Using a Group B metal compound, a Group VIII metal compound and a refractory inorganic oxide, the mixture is mixed and crushed to form an extrudable soft lump, and the extruded soft lump is dried, and the extruded soft lump is dried and calcined. Then, the calcined extruded product is converted to VIB
A method for producing a hydrogen desulfurization catalyst is described which comprises impregnating with a group III metal compound and a group VIII metal compound, followed by drying and calcining in an oxidizing atmosphere.
【０００８】特開昭５４−１２７４０６号公報には、炭
化水素油、特に残渣油のような石油蒸留区分を水素化脱
金属および水素化脱硫するための改善された触媒、特に
水素化脱金属するのに適した触媒が開示されており、約
０．５〜約７．０重量％、好適には約１．０〜約６．０
重量％の希土類元素酸化物（ＲＥ2Ｏ3）をアルミナに含
浸させた後、約７０４℃〜約９２７℃の温度で予備焼成
してアルミナと希土類元素酸化物とを複合させ、次いで
含浸処理することにより鉄族金属および第ＶＩＢ族金属
を含有する水素化脱金属触媒が開示されている。JP 54-127406 discloses an improved catalyst for hydrodemetallization and hydrodesulfurization of petroleum distillation sections, such as hydrocarbon oils, especially residual oils, in particular hydrodemetallization. Disclosed are catalysts suitable for about 0.5 to about 7.0% by weight, preferably about 1.0 to about 6.0% by weight.
After impregnating alumina with a rare earth element oxide (RE 2 O 3 ) by weight, alumina is preliminarily calcined at a temperature of about 704 ° C. to about 927 ° C. to combine the alumina with the rare earth element oxide, followed by impregnation. Thus, hydrodemetallization catalysts containing iron group metals and group VIB metals have been disclosed.
【０００９】特開昭６０−２５５１４３号公報には、少
なくともモリブデンまたはタングステンの化合物を１種
およびコバルト化合物１種および／またはニッケルの化
合物１種と、Ｍｏ又はＷ１モル当たり０．２〜１．０モ
ルの安定化量の燐と、支持体に対して２〜６重量％の適
当な可溶性アミン化合物とを混合することによって得ら
れるｐＨ範囲０．７〜２．７の水性含浸用溶液を製造
し、適当な触媒支持体をこの溶液で含浸し、この複合材
料を乾燥してから焼成することからなる支持された水素
化変換触媒の製造方法が開示されている。JP-A-60-255143 discloses that at least one compound of molybdenum or tungsten and one compound of cobalt and / or one compound of nickel are combined with 0.2 to 1.0 mol / mol of Mo or W. An aqueous impregnating solution having a pH range of 0.7 to 2.7 is obtained by mixing a molar stabilizing amount of phosphorus with 2 to 6% by weight of a suitable soluble amine compound, based on the support. A process for producing a supported hydroconversion catalyst is disclosed which comprises impregnating a suitable catalyst support with the solution, drying the composite and calcining.
【００１０】特開昭６１−１３８５３７号公報には、ｐ
Ｈ７．５〜１０．５に調整した非晶質アルミナ水和物の
フィルターケーキをフィルタープレスで脱水してそのＡ
ｌ2Ｏ3濃度を２８〜３５ｗｔ％に上昇させた後、これを
セルフクリーニング型混練機に供給して滞留時間１０秒
以上混練し、得られるドウを混練機の入り口直前で第Ｖ
ＩＢ族および第ＶＩＩＩ族金属を、その全使用量に対し
それぞれ２０〜６０ｗｔ％（金属として）を水溶性塩の
水溶液として同時に添加して混練し、次いで押出し機で
押し出し成形し、成形物を乾燥カ焼し、カ焼物を残部触
媒金属のアンモニア性水溶液を含浸させた後乾燥カ焼す
ることからなる水素脱硫触媒の製造方法が記載されてい
る。Japanese Unexamined Patent Publication (Kokai) No. 61-138538 discloses p
The filter cake of amorphous alumina hydrate adjusted to H 7.5 to 10.5 was dehydrated with a filter press and the
After the l 2 O 3 concentration was increased to 28 to 35 wt%, it was supplied to a self-cleaning kneader and kneaded for a residence time of 10 seconds or more.
Group IB and Group VIII metals are simultaneously added and kneaded in an amount of 20 to 60 wt% (as a metal) as an aqueous solution of a water-soluble salt with respect to the total amount thereof, and then extruded by an extruder, and the molded product is dried. A method for producing a hydrogen desulfurization catalyst is described which comprises calcining, impregnating the calcined product with an aqueous ammoniacal solution of a catalyst metal, and then drying and calcining the calcined product.
【００１１】特公平２−５４１４２号公報には、硫酸ア
ルミニウムとアルミン酸ナトリウムとをｐＨ６．０〜
８．５，温度５０〜６５℃の条件下で反応させて非晶質
アルミナ水和物を含有する第１の水性スラリーを調製
し、この水性スラリーにアルミン酸ナトリウムを加えて
Ａｌ2Ｏ3濃度が７ｗｔ％以上である第２の水性スラリー
を調製し、第２の水性スラリーに含まれる非晶質アルミ
ナ水和物を濾別し、得られたフィルターケーキをまず稀
アンモニア水で、次に稀硝酸溶液で洗浄後、再び稀アン
モニア水で洗浄してフィルターケーキのｐＨを７．５〜
１０．５に調整し、このフィルターケーキをフィルター
プレスで脱水してそのＡｌ2Ｏ3濃度を２８〜３５ｗｔ％
に上昇させた後、これをセルフクリーニング型混練機に
供給して滞留時間１０秒以上混練し、得られるドウを押
出し成形し、押出し成形物を乾燥し、さらに焼成するこ
とからなるアルミナ触媒担体の製造法が記載されてい
る。Japanese Patent Publication No. 54142/1990 discloses that aluminum sulfate and sodium aluminate are mixed at pH 6.0 to 6.0.
8.5, a reaction was carried out under the conditions of a temperature of 50 to 65 ° C. to prepare a first aqueous slurry containing amorphous alumina hydrate, and sodium aluminate was added to the aqueous slurry to obtain an Al 2 O 3 concentration. Is prepared by filtration, the amorphous alumina hydrate contained in the second aqueous slurry is filtered off, and the obtained filter cake is first diluted with dilute aqueous ammonia and then diluted with diluted aqueous ammonia. After washing with a nitric acid solution, the filter cake was washed again with diluted ammonia water to adjust the pH of the filter cake to 7.5 to 7.5.
10.5, the filter cake was dehydrated with a filter press, and the Al 2 O 3 concentration was 28 to 35 wt%.
After that, the mixture is supplied to a self-cleaning type kneader and kneaded for a residence time of 10 seconds or more. The resulting dough is extruded, the extruded product is dried, and the calcined alumina catalyst carrier is further calcined. A production method is described.
【００１２】[0012]
【発明が解決しようとする課題】我が国の第二段階規制
に適合するためには、軽油製品中の硫黄含有量を０．１
重量％以下に低減する必要があるため、従来の脱硫領域
では対象外であった深度脱硫領域の難反応性硫黄化合物
（多環芳香族の硫黄化合物）をも水素化脱硫する必要が
ある。In order to comply with Japan's second-stage regulations, the sulfur content of gas oil products must be 0.1%.
Since it is necessary to reduce the amount to less than 10% by weight, it is also necessary to hydrodesulfurize hard-to-react sulfur compounds (polycyclic aromatic sulfur compounds) in the deep desulfurization region, which were not applicable in the conventional desulfurization region.
【００１３】既存の軽油脱硫装置と水素化脱硫触媒を用
いてこれを達成しようとすれば、反応温度を上げるか、
あるいは液空間速度を落とすかいずれかが一応考えられ
る。しかし、前者の方法では触媒の活性が低下するとと
もに触媒寿命が短くなり、しかも製品軽油中の色相（色
相値および安定性）が低下して商品価値を著しく低下さ
せることになる。一方、後者の方法を採用しようとすれ
ば設備の能力不足を招来するため設備拡大が必要になる
が、これは現状ではほとんど不可能である。このように
従来の水素化脱硫触媒ではこの高深度脱硫に対応できな
いため、更に活性が高く触媒寿命が長い脱硫触媒を開発
することが望まれていた。If this is to be achieved using existing gas oil desulfurization units and hydrodesulfurization catalysts, the reaction temperature must be increased,
Alternatively, it is conceivable to reduce the liquid space velocity. However, in the former method, the activity of the catalyst is reduced and the life of the catalyst is shortened, and the hue (hue value and stability) in the product light oil is reduced, so that the commercial value is significantly reduced. On the other hand, if the latter method is adopted, the capacity of the equipment will be insufficient and the equipment needs to be expanded. However, this is almost impossible at present. As described above, since the conventional hydrodesulfurization catalyst cannot cope with the deep desulfurization, it has been desired to develop a desulfurization catalyst having higher activity and a longer catalyst life.
【００１４】また、従来の触媒を用いた場合、軽油の臭
いをより少なくしようとすれば着色の度合いが増し、逆
に、着色の度合いを低下させようとすれば臭いが強くな
るという問題点もあった。Further, when the conventional catalyst is used, there is also a problem that if the odor of light oil is reduced, the degree of coloring increases, and if the degree of coloring is reduced, the odor increases. there were.
【００１５】[0015]
【課題を解決するための手段】本発明者はこのような問
題点を解決して、現有の設備でこの高深度脱硫に対応で
きるような、更に活性が高く触媒寿命が長い優れた水素
化脱硫触媒を開発すべく鋭意研究を重ねた結果、従来の
水素化脱硫触媒にエルビウムの化合物を添加することに
より、難反応性硫黄化合物をも脱硫することができる高
活性な触媒となり、しかも臭いと色の双方が改善される
ことを見い出した。本発明はかかる知見に基づいて完成
したものである。SUMMARY OF THE INVENTION The present inventor has solved the above-mentioned problems, and has an excellent hydrodesulfurization having a higher activity and a longer catalyst life so that existing equipment can cope with this deep-depth desulfurization. As a result of intensive research to develop a catalyst, the addition of an erbium compound to a conventional hydrodesulfurization catalyst results in a highly active catalyst that can desulfurize even difficult-to-react sulfur compounds. Found that both were improved. The present invention has been completed based on such findings.
【００１６】すなわち、本発明の一つの態様は、担持さ
れた全触媒の重量を基準にして元素換算で４〜３０重量
％のモリブデンと、１〜１０重量％のコバルトおよび／
またはニッケルと、１〜１０重量％のリンと、０．０５
〜５重量％のエルビウムとを耐火性担体上に担持させた
ことを特徴とする炭化水素の水素化脱硫触媒を提供する
ことである。 That is, one embodiment of the present invention relates to
4 to 30 weights in elemental conversion based on the weight of all catalysts obtained
% Molybdenum and 1-10% by weight of cobalt and / or
Or nickel, 1 to 10% by weight phosphorus, 0.05
~ 5% by weight of erbium on a refractory carrier
To provide a hydrocarbon hydrodesulfurization catalyst characterized by the following:
That is.
【００１７】本発明の別の態様は、担持された全触媒の
重量を基準にして元素換算で４〜３０重量％のモリブデ
ンと、１〜１０重量％のコバルトおよび／またはニッケ
ルと、１〜１０重量％のリンと、０．０５〜５重量％の
エルビウムとを耐火性担体上 に担持する水素化脱硫触媒
を製造するにあたり、（ａ）まず耐火性無機酸化物と最
終担持量の各々１０〜１００重量％となる量のモリブデ
ン化合物、コバルトおよび／またはニッケル化合物、リ
ン化合物およびエルビウム化合物とを混練して押し出し
可能な軟塊を形成し、（ｂ）この軟塊を押し出し、押し
出された軟塊を酸化雰囲気において乾燥、焼成した後、
（ｃ）焼成した押し出し成形体にモリブデン化合物、コ
バルトおよび／またはニッケル化合物、リン化合物およ
びエルビウム化合物の残量を含浸担持させた後、含浸担
持させた押し出し成形体を酸化雰囲気において乾燥、焼
成することを特徴とする炭化水素の水素化脱硫触媒の製
造方法を提供することである。 Another aspect of the present invention is a method for controlling the total supported catalyst.
Molybdenum of 4 to 30% by weight in elemental conversion based on weight
And 1 to 10% by weight of cobalt and / or nickel
And 1 to 10% by weight of phosphorus and 0.05 to 5% by weight of
Hydrodesulfurization catalyst supporting erbium on refractory support
(A) First, the refractory inorganic oxide and the
Molybdenum in an amount of 10 to 100% by weight of the final loading
Compounds, cobalt and / or nickel compounds,
Compound and erbium compound
Forming a possible lump, and (b) extruding and pressing the lump
After drying and firing the discharged soft lump in an oxidizing atmosphere,
(C) A molybdenum compound,
Baltic and / or nickel compounds, phosphorus compounds and
After impregnating and supporting the remaining amount of erbium and erbium compounds,
The extruded product is dried and fired in an oxidizing atmosphere.
Of a hydrodesulfurization catalyst for hydrocarbons, characterized in that
Is to provide a fabrication method.
【００１８】本発明の水素化脱硫触媒は、モリブデン化
合物、コバルトおよび／またはニッケル化合物、エルビ
ウム化合物およびリン化合物を耐火性担体上に担持させ
ることにより製造される。触媒成分の担持方法として、
従来用いられてきた含浸担持方法をそのまま適用するこ
とができる。慣用触媒にエルビウム化合物を更に含浸担
持させても同様な効果を示す。エルビウム化合物の添加
は、従来の担体もしくは触媒を調製するいずれの工程で
行っても良い。The hydrodesulfurization catalyst of the present invention is produced by supporting a molybdenum compound, a cobalt and / or nickel compound, an erbium compound and a phosphorus compound on a refractory carrier. As a method for supporting the catalyst component,
The conventionally used impregnation-supporting method can be applied as it is. Similar effects can be obtained by further impregnating and supporting an erbium compound on a conventional catalyst. The erbium compound may be added in any step of preparing a conventional carrier or catalyst.
【００１９】この場合、触媒成分を担体に添加する方法
としては、押し出し法においてアルミナの軟塊（ドウ）
を湿式・乾式の何れかの方法で混合した後、押し出し成
形することによって触媒を調製することができる。In this case, as a method for adding the catalyst component to the carrier, a soft lump of alumina (dough) is used in the extrusion method.
Can be mixed by any of wet or dry methods, and then extruded to prepare a catalyst.
【００２０】本発明で使用する耐火性担体の種類は特に
限定されず、耐火性を有する担体であればいかなるもの
でも使用可能である。例えば、特公平２−５４１４２号
公報に開示されているように、（ａ）イオン交換水を入
れた容器に硫酸アルミニウム溶液とアルミン酸ナトリウ
ム溶液を同時に注加し、硫酸アルミニウムとアルミン酸
ナトリウムとをｐＨ６．０〜８．５，温度５０〜６５℃
の条件下に反応させて非晶質アルミナ水和物を含有する
第１の水性スラリーを調製し、（ｂ）この水性スラリー
に、工程（ａ）で使用したアルミン酸ナトリウムとの合
計量で、工程（ａ）で使用した硫酸アルミニウムの０．
９５〜１．０５当量に相当するアルミン酸ナトリウム水
溶液を加えてＡｌ2Ｏ3濃度が７重量％以上である第２の
水性スラリーを調製し、（ｃ）第２の水性スラリーに含
まれる非晶質アルミナ水和物を濾別し、得られたフィル
ターケーキをまず稀アンモニア水で、次に稀硝酸溶液で
洗浄後、再び稀アンモニア水で洗浄してフィルターケー
キのｐＨを７．５〜１０．５に調整し、（ｄ）このフィ
ルターケーキをフィルタープレスで脱水してそのＡｌ2
Ｏ3濃度を２８〜３５重量％に上昇させた後、これをセ
ルフクリーニング型混練機に供給して滞留時間１０秒以
上混練し、（ｅ）工程（ｄ）から得られるドウを押出し
成形し、しかる後押出し成形物を乾燥し、さらに焼成す
ることにより所望通りの細孔特性特性と比表面積を有す
るアルミナ担体を調製できる。The type of the refractory carrier used in the present invention is not particularly limited, and any carrier having fire resistance can be used. For example, as disclosed in Japanese Patent Publication No. 2-54142, (a) an aluminum sulfate solution and a sodium aluminate solution are simultaneously poured into a container containing ion-exchanged water, and aluminum sulfate and sodium aluminate are added. pH 6.0-8.5, temperature 50-65 ° C
To prepare a first aqueous slurry containing amorphous alumina hydrate, and (b) adding the aqueous slurry to the aqueous slurry in total amount with the sodium aluminate used in step (a), 0.1% of the aluminum sulfate used in step (a).
A second aqueous slurry having an Al 2 O 3 concentration of 7% by weight or more is prepared by adding an aqueous solution of sodium aluminate corresponding to 95 to 1.05 equivalents, and (c) an amorphous slurry contained in the second aqueous slurry is prepared. The porous alumina hydrate is separated by filtration, and the obtained filter cake is washed with diluted ammonia water, then with a diluted nitric acid solution, and then again with diluted ammonia water to adjust the pH of the filter cake to 7.5 to 10. 5 and (d) the filter cake was dewatered with a filter press to remove the Al 2
After increasing the O 3 concentration to 28 to 35% by weight, this is supplied to a self-cleaning type kneader, and kneaded for a residence time of 10 seconds or more. (E) The dough obtained from the step (d) is extruded, Thereafter, the extruded product is dried and further calcined to prepare an alumina support having desired pore characteristics and specific surface area.
【００２１】上述したアルミナ担体もしくは慣用の耐火
性担体（アルミナ単独もしくはシリカ・アルミナおよび
／またはゼオライトを含有するアルミナ酸化物）に慣用
の含浸法を使用して、以下に述べる様な可溶性化合物の
水溶液を含浸させる。The above-mentioned alumina carrier or a conventional refractory carrier (alumina alone or alumina oxide containing silica-alumina and / or zeolite) is subjected to a conventional impregnation method to obtain an aqueous solution of a soluble compound as described below. Impregnated.
【００２２】触媒成分の含浸処理は、担体に一様に分散
させるのに適した最小容積の含浸溶液で行うのが好まし
い。例えばその使用量は、含浸溶液１容積につき担体
０．５〜１．０容積の割合が良い。The impregnation of the catalyst component is preferably carried out with a minimum volume of the impregnation solution suitable for uniformly dispersing the carrier. For example, the amount of the carrier is preferably 0.5 to 1.0 volume per 1 volume of the impregnating solution.
【００２３】一つの好ましい方法はスチーム・ジャケッ
ト付きエバポレイターの使用である。担体を含浸溶液中
に浸漬し、エバポレイターの回転運動によってその中で
撹拌させる。One preferred method is to use a steam jacketed evaporator. The carrier is immersed in the impregnation solution and is stirred therein by the rotary movement of the evaporator.
【００２４】エバポレイターのジャケットに水蒸気を使
用し、またエバポレイターを乾燥気体、好ましくは空気
または窒素ガスで連続的にパージすることによって、含
浸溶液の蒸発を促進することができる。こうして乾燥さ
れた含浸物を、更に酸素雰囲気下で２００〜６５０℃の
温度で１〜２４時間あるいはそれ以上焼成する。Evaporation of the impregnating solution can be facilitated by using steam in the evaporator jacket and continuously purging the evaporator with a dry gas, preferably air or nitrogen gas. The impregnated material thus dried is further calcined in an oxygen atmosphere at a temperature of 200 to 650 ° C. for 1 to 24 hours or more.
【００２５】特に適したモリブデン化合物はモリブデン
酸アンモニウムであり、特に適したコバルト化合物は硝
酸コバルトであり、特に適したリン化合物は燐酸であ
り、また特に適したエルビウム化合物は硝酸エルビウム
である。他の好適なモリブデン化合物には、無水モリブ
デン酸、モリブデン酸等の化合物がある。使用すること
のできるニッケル化合物には、硝酸ニッケル、硫酸ニッ
ケル、塩化ニッケル、酢酸ニッケル等があり、使用する
ことのできるコバルト化合物には、硫酸第一コバルト等
があり、リン化合物には、ピロ燐酸、メタ燐酸、五塩化
燐、十酸化四燐等がある。また他の好適なエルビウム化
合物には、塩化エルビウム、酸化エルビウム、フッ化エ
ルビウム、硫酸エルビウム、酢酸エルビウム等がある。A particularly suitable molybdenum compound is ammonium molybdate, a particularly suitable cobalt compound is cobalt nitrate, a particularly suitable phosphorus compound is phosphoric acid, and a particularly suitable erbium compound is erbium nitrate. Other suitable molybdenum compounds include compounds such as molybdic anhydride, molybdic acid, and the like. The nickel compounds which may be used, nickel nitrate, nickel sulfate, nickel chloride, there is nickel acetate and the like, used
Cobalt compounds that can be used include cobaltous sulfate and the like, and phosphorus compounds include pyrophosphoric acid, metaphosphoric acid, phosphorus pentachloride, and tetraphosphorous oxide. Other suitable erbium compounds include erbium chloride, erbium oxide, erbium fluoride, erbium sulfate, erbium acetate, and the like.
【００２６】特公昭５３−６１１３号公報に開示されて
いるような乾式押し出し法を利用して、担持された全触
媒の重量を基準にして元素換算で４〜３０重量％のモリ
ブデンと、１〜１０重量％のコバルトおよび／またはニ
ッケルと、１〜１０重量％のリンと、０．０５〜５重量
％のエルビウムとを耐火性担体上に担持する水素化脱硫
触媒を製造するにあたり、（ａ）まず耐火性無機酸化物
と最終担持量の各々１０〜１００重量％となる量のモリ
ブデン化合物、コバルトおよび／またはニッケル化合
物、リン化合物およびエルビウム化合物とを混合および
解膠して押し出し可能な軟塊（ドウ）を形成し、（ｂ）
この軟塊を押し出し、押し出された軟塊を酸化雰囲気に
おいて乾燥、焼成した後、（ｃ）焼成した押し出し成形
体にモリブデン化合物、コバルトおよび／またはニッケ
ル化合物、リン化合物およびエルビウム化合物の残量を
含浸担持させた後、（ｄ）含浸担持させた押し出し成形
体を酸化雰囲気において乾燥、焼成することによって請
求項１に記載した炭化水素の水素化脱硫触媒を調製でき
る。[0026] Using the dry extrusion method as disclosed in JP-B-53-6113, 4 to 30 wt% in terms of element based on the weight of the total catalyst supported Mori
Budene and 1-10% by weight of cobalt and / or
In producing a hydrodesulfurization catalyst supporting nickel , 1 to 10% by weight of phosphorus , and 0.05 to 5% by weight of erbium on a refractory carrier, (a) first, a refractory inorganic oxide and a final the amount of memory to be respectively 10 to 100 wt% of the supported amount
Buden compounds, cobalt and / or nickel compounds
(B) mixing and peptizing the substance, the phosphorus compound and the erbium compound to form an extrudable soft mass (dough);
This soft lump is extruded, and the extruded soft lump is dried and fired in an oxidizing atmosphere, and then (c) a molybdenum compound, cobalt and / or nickel is added to the fired extruded compact.
請 Le compounds, after the remaining amount of phosphorus compound and an erbium compound impregnated carrier, drying in an oxidizing atmosphere extrudates obtained by (d) impregnation, by calcining
A hydrocarbon hydrodesulfurization catalyst according to claim 1 can be prepared.
【００２７】また、湿式押し出し法として、担持された
全触媒の重量を基準にして元素換算で（ａ）モリブデン
の含有量が４〜３０重量％になるのに十分な量のモリブ
デンの塩の溶液と（ｂ）コバルトおよび／またはニッケ
ルの含有量が１〜１０重量％になるのに十分な量のコバ
ルトおよび／またはニッケルの塩の溶液と（ｃ）リンの
含有量が１〜１０重量％になるのに十分な量のリンの塩
の溶液および（ｄ）エルビウムの含有量が０．０１〜５
重量％になるのに十分な量のエルビウムの塩の溶液を、
任意の順序でアルミナドウに直接添加することによって
も調製できる。Further, as a wet extrusion process, in an amount sufficient content is 4 to 30% by weight of in terms of an element based on the weight of the total catalyst supported (a) molybdenum <br/> molybdenum
A solution of a salt of den and (b) cobalt and / or nickel
A sufficient amount of edge to content Le is 1 to 10 wt%
Belt and / or content of the solution and (d) erbium phosphate salt solution and (c) an amount sufficient to phosphorus content is 1 to 10 wt% of nickel salts 0.01-5
Erbium salt solution in an amount sufficient to make up
It can also be prepared by directly adding to the alumina dough in any order.
【００２８】前述の特公平２−５４１４２号公報に開示
されている技術によって調製されたアルミナドウを使用
すると、解膠剤の使用が避けられるため有効比表面積の
減少を防止できるため好適である。The use of alumina dough prepared by the technique disclosed in the above-mentioned Japanese Patent Publication No. 54142/1990 is preferred because the use of a deflocculant can be avoided and a decrease in the effective specific surface area can be prevented.
【００２９】アルミナドウに混合するのに特に適したモ
リブデン化合物はモリブデン酸アンモニウムであり、特
に適したコバルト化合物は硝酸コバルトであり、特に適
したリン化合物は燐酸であり、また特に適したエルビウ
ム化合物は硝酸エルビウムである。他の好適なモリブデ
ン化合物には、無水モリブデン酸、モリブデン酸等の化
合物がある。使用することのできる他のコバルト化合物
および／またはニッケル化合物には、硝酸ニッケル、硫
酸ニッケル、塩化ニッケル、酢酸ニッケル、硫酸第一コ
バルト等があり、リン化合物には、ピロ燐酸、メタ燐
酸、五塩化燐、十酸化四燐等がある。また他の好適なエ
ルビウム化合物には、塩化エルビウム、酸化エルビウ
ム、フッ化エルビウム、硫酸エルビウム、酢酸エルビウ
ム等がある。[0029] model particularly suitable for mixing in Aruminadou
The lithium compound is ammonium molybdate, a particularly suitable cobalt compound is cobalt nitrate, a particularly suitable phosphorus compound is phosphoric acid, and a particularly suitable erbium compound is erbium nitrate. Other suitable molybdenum
The compound includes molybdic anhydride, molybdic acid and the like. Other cobalt compounds that can be used
And / or nickel compounds include nickel nitrate, nickel sulfate, nickel chloride, nickel acetate, cobaltous sulfate, and the like, and phosphorus compounds include pyrophosphoric acid, metaphosphoric acid, phosphorus pentachloride, tetraphosphorous oxide and the like. . Other suitable erbium compounds include erbium chloride, erbium oxide, erbium fluoride, erbium sulfate, erbium acetate, and the like.
【００３０】[0030]
【実施例】以下に本発明の実施例を挙げて本発明を更に
詳しく説明するが、本発明はこれらの実施例によって何
ら限定されるものではない。 ［比較例１］ セルフクリーニング型混練機で３分間含水率６２．５重
量％の非晶質アルミナを約９０℃で混練して得られた擬
ベーマイトゲルからなる非晶質アルミナ水和物（Ａｌ2
Ｏ3：３７．５重量％、強熱損失：６２．５重量％）約
８８０ｇ（Ａｌ2Ｏ3として３３０ｇ）のアルミナドウと
モリブデン酸アンモニウム水溶液（４１ｇのモリブデン
酸アンモニウム塩含有）および硝酸コバルト水溶液（３
８ｇ硝酸コバルト・６水和物含有）を約１時間混練機で
よく湿式混練および混合した。この軟塊混合物をその後
１．１ｍｍの孔を多数有する有孔板を通して押し出し
た。この押し出し成形体を空気中で３５０℃に１時間、
次いで６００℃に更に２時間加熱して乾燥・焼成した。
平均長さが約３．５ｍｍに折れていた押し出し成形粒子
は２重量％Ｃｏと６．５重量％Ｍｏを含有していた。次
に、この焼成押し出し成形体を含浸処理した。２７ｇの
モリブデン酸アンモニウム塩と４５ｇの水酸化アンモニ
ウムからなる水溶液と、２０ｇの硝酸コバルト・６水和
物と１０ｇの蒸留水からなる水溶液とを混合し、得られ
た水溶液を蒸留水で１２０ｃｃまで希釈して調製したモ
リブデンとコバルトを含有するアンモニウム水溶液で１
４０ｇの焼成押し出し成形体を含浸処理した。押し出し
成形体は含浸溶液に浸漬した後蒸発乾固し、空気中にお
いて３５０℃に１時間、次いで５５０℃に更に２時間乾
燥・焼成した。焼成後、押し出し成形体は４重量％Ｃｏ
と１４．６重量％Ｍｏを含有していた。この押し出し成
形体を触媒Ｒとする。 ［参考例１］ セルフクリーニング型混練機で３分間含水率６２．５重
量％の非晶質アルミナを約９０℃で混練して得られた擬
ベーマイトゲルからなる非晶質アルミナ水和物（Ａｌ2
Ｏ3：３７．５重量％、強熱損失：６２．５重量％）約
８８０ｇ（Ａｌ2Ｏ3として３３０ｇ）のアルミナドウと
モリブデン酸アンモニウム水溶液（４１ｇのモリブデン
酸アンモニウム塩含有）および硝酸コバルト・エルビウ
ム混合水溶液（３８ｇ硝酸コバルト・６水和物および
６．５ｇ硝酸エルビウム・６水和物含有）を約１時間混
練機でよく湿式混練および混合した。この軟塊混合物を
その後１．１ｍｍの孔を多数有する有孔板を通して押し
出した。この押し出し成形体を空気中で３５０℃に１時
間、次いで６００℃に更に２時間加熱して乾燥・焼成し
た。平均長さが約３．５ｍｍに折れていた押し出し成形
粒子は０．６５重量％Ｅｒと２重量％Ｃｏと６．３重量
％Ｍｏを含有していた。次に、この押し出し成形体を含
浸処理した。２７ｇのモリブデン酸アンモニウム塩と４
５ｇの水酸化アンモニウムからなる水溶液と、２０ｇの
硝酸コバルト・６水和物と１０ｇの蒸留水からなる水溶
液とを混合し、得られた水溶液を蒸留水で１２０ｃｃま
で希釈して調製したモリブデンとコバルトを含有するア
ンモニウム水溶液で１４０ｇの焼成押し出し成形体を含
浸処理した。押し出し成形体は含浸溶液に浸漬した後蒸
発乾固し、空気中において３５０℃に１時間、次いで５
５０℃に更に２時間乾燥・焼成した。焼成後、押し出し
成形体は０．５重量％Ｅｒと３．９重量％Ｃｏと１４．
３重量％Ｍｏを含有していた。この押し出し成形体を触
媒Ａとする。 ［試験例１］ 上記参考例１で得られた触媒Ａおよび比較例１で得られ
た触媒Ｒを用いて下記の２種類の活性試験を行った。The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. [Comparative Example 1] Amorphous alumina hydrate (Al) comprising pseudo-boehmite gel obtained by kneading amorphous alumina having a water content of 62.5% by weight with a self-cleaning kneader for 3 minutes at about 90 ° C Two
O 3 : 37.5% by weight, ignition loss: 62.5% by weight) About 880 g (330 g as Al 2 O 3 ) of alumina dough and an aqueous solution of ammonium molybdate (containing 41 g of ammonium molybdate) and an aqueous solution of cobalt nitrate ( 3
8 g of cobalt nitrate hexahydrate) was well kneaded and mixed with a kneader for about 1 hour. The lump mixture was then extruded through a perforated plate having a number of 1.1 mm holes. This extruded body is heated at 350 ° C. for 1 hour in air.
Then, it was dried and fired by further heating to 600 ° C. for 2 hours.
The extruded particles, which had an average length of about 3.5 mm, contained 2% by weight Co and 6.5% by weight Mo. Next, the fired extruded product was impregnated. An aqueous solution consisting of 27 g of ammonium molybdate and 45 g of ammonium hydroxide is mixed with an aqueous solution consisting of 20 g of cobalt nitrate hexahydrate and 10 g of distilled water, and the resulting aqueous solution is diluted to 120 cc with distilled water. With an aqueous ammonium solution containing molybdenum and cobalt
40 g of the fired extrudate was impregnated. The extruded body was immersed in the impregnating solution, evaporated to dryness, dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for 2 hours. After sintering, the extruded body is 4% by weight Co
And 14.6% by weight of Mo. This extruded product is referred to as catalyst R. [ Reference Example 1 ] Amorphous alumina hydrate (Al) consisting of pseudo-boehmite gel obtained by kneading amorphous alumina having a water content of 62.5% by weight at about 90 ° C. for 3 minutes with a self-cleaning kneader Two
O 3 : 37.5% by weight, loss on ignition: 62.5% by weight) About 880 g (330 g as Al 2 O 3 ) of alumina dough and an aqueous solution of ammonium molybdate (containing 41 g of ammonium molybdate) and erbium cobalt nitrate The mixed aqueous solution (containing 38 g of cobalt nitrate hexahydrate and 6.5 g of erbium nitrate hexahydrate) was well kneaded and mixed with a kneader for about 1 hour. The lump mixture was then extruded through a perforated plate having a number of 1.1 mm holes. The extruded body was dried and fired in air at 350 ° C. for 1 hour and then at 600 ° C. for 2 hours. The extruded particles, which had an average length of about 3.5 mm, contained 0.65 wt% Er, 2 wt% Co and 6.3 wt% Mo. Next, the extruded product was impregnated. 27 g of ammonium molybdate and 4
Molybdenum and cobalt prepared by mixing an aqueous solution consisting of 5 g of ammonium hydroxide, an aqueous solution consisting of 20 g of cobalt nitrate hexahydrate and 10 g of distilled water, and diluting the resulting aqueous solution to 120 cc with distilled water. 140 g of the calcined extruded body was impregnated with an aqueous ammonium solution containing The extruded body was immersed in the impregnating solution, evaporated to dryness, and then in air at 350 ° C. for 1 hour,
It was dried and baked at 50 ° C. for another 2 hours. After firing, the extrudate was 0.5 wt% Er, 3.9 wt% Co and 14.
It contained 3% by weight of Mo. This extruded product is referred to as Catalyst A. Test Example 1 The following two types of activity tests were performed using the catalyst A obtained in Reference Example 1 and the catalyst R obtained in Comparative Example 1.
【００３１】活性試験−１： ４１気圧（絶対圧）、３
７０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＶＧＯを液空間速度３．０ｈｒ
-1および水素／原料油の比の供給速度が３２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 70 ° C., and the feed oil VGO was supplied at a liquid hourly space velocity of 3.0 hr.
-1 and the feed rate of hydrogen / feedstock ratio is 320 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３２】活性試験−２： ２０気圧（絶対圧）、３
４０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＬＧＯを液空間速度２．０ｈｒ
-1および水素／原料油の比の供給速度が１２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 40 ° C., and the feed oil LGO was supplied at a liquid hourly space velocity of 2.0 hr.
-1 and a feed rate of hydrogen / feed oil ratio of 120 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３３】これらの活性試験の結果を下記表１に示
す。なお、活性効果を表す触媒Ａの数値は触媒Ｒの脱硫
率（製品の水素化脱硫前後の硫黄含有率から算出）を１
００とした場合の指数で表したものである。 表１ 各触媒の脱硫効果 触媒Ｒ 触媒Ａ 粒子密度（ｇ／ｃｃ） １．２５ １．２７ 粒径（円柱）（ｍｍ） ０．８５ ０．８５ Ｃｏ重量％ ４．０ ３．９ Ｍｏ重量％ １４．６ １４．３ Ｅｒ重量％ ０ ０．５ 活性試験−１ １００ １１８ 活性試験−２ １００ １１０ 表１から明らかなように、参考例１の触媒Ａは従来の触
媒Ｒに比べて、活性試験−１の脱硫活性では１８％、活
性試験−２の脱硫活性では１０％それぞれ優れているこ
とが裏付けられた。 ［比較例２］ １．５重量％Ｃｏと３．５重量％Ｍｏを含有するアルミ
ナ押し出し担体２００ｇに、３７ｇのモリブデン酸アン
モニウム塩と７０ｇの水酸化アンモニウムからなる水溶
液と、３０ｇの硝酸コバルト・６水和物と１５ｇ蒸留水
からなる水溶液とを混合し、得られた水溶液を蒸留水で
２００ｃｃまで希釈して調製したモリブデンとコバルト
を含有するアンモニウム水溶液で含浸処理した。押し出
し担体は含浸溶液に浸漬した後蒸発乾固し、空気中にお
いて３５０℃に１時間、次いで５５０℃に更に２時間乾
燥・焼成して触媒を調製した。３．７重量％Ｃｏと１２
重量％Ｍｏを含有していた。これを触媒Ｓとする。 ［参考例２］ 比較例２の触媒２００ｇに２．８ｇ硝酸エルビウム・６
水和物を蒸留水で１８０ｃｃまで希釈して調製した含浸
溶液に浸漬した後蒸発乾固し、空気中において３５０℃
に１時間、次いで５５０℃に更に２時間乾燥・焼成し
た。焼成後、押し出し触媒は０．１重量％Ｅｒと３．７
重量％Ｃｏと１１．９重量％Ｍｏを含有していた。これ
を触媒Ｂとする。 ［試験例２］ 上記参考例２で得られた触媒Ｂおよび比較例２で得られ
た触媒Ｓを用いて下記の２種類の活性試験を行った。The results of these activity tests are shown in Table 1 below. The value of the catalyst A showing the activity effect is calculated by calculating the desulfurization rate of the catalyst R (calculated from the sulfur content before and after hydrodesulfurization of the product) by 1
It is represented by an index when 00 is set. Table 1 Desulfurization effect of each catalyst Catalyst R Catalyst A Particle density (g / cc) 1.25 1.27 Particle size (cylindrical) (mm) 0.85 0.85 Co weight% 4.0 3.9 Mo weight% 14.6 14.3 Er wt% 0 0.5 Activity test-1 100 118 Activity test-2 100 110 As is clear from Table 1, the catalyst A of Reference Example 1 has an activity test in comparison with the conventional catalyst R. It was proved that the desulfurization activity of -1 was 18%, and the desulfurization activity of activity test 2 was 10%, respectively. Comparative Example 2 An aqueous solution composed of 37 g of ammonium molybdate and 70 g of ammonium hydroxide and 30 g of cobalt nitrate · 6 were added to 200 g of an alumina extruded support containing 1.5 wt% Co and 3.5 wt% Mo. The hydrate was mixed with an aqueous solution consisting of 15 g of distilled water, and the resulting aqueous solution was impregnated with an aqueous ammonium solution containing molybdenum and cobalt prepared by diluting the aqueous solution to 200 cc with distilled water. The extruded carrier was immersed in the impregnating solution, evaporated to dryness, dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for 2 hours to prepare a catalyst. 3.7 wt% Co and 12
% Mo by weight. This is designated as catalyst S. [ Reference Example 2 ] 2.8 g of erbium nitrate-6 was added to 200 g of the catalyst of Comparative Example 2.
The hydrate is immersed in an impregnation solution prepared by diluting the hydrate to 180 cc with distilled water, and then evaporated to dryness, and 350 ° C. in air.
For 1 hour and then at 550 ° C. for another 2 hours. After calcination, the extruded catalyst contained 0.1 wt% Er and 3.7
% Co and 11.9% Mo by weight. This is designated as catalyst B. [Test Example 2] The following two types of activity tests were performed using the catalyst B obtained in Reference Example 2 and the catalyst S obtained in Comparative Example 2.
【００３４】活性試験−１： ４１気圧（絶対圧）、３
７０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＶＧＯを液空間速度３．０ｈｒ
-1および水素／原料油の比の供給速度が３２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 70 ° C., and the feed oil VGO was supplied at a liquid hourly space velocity of 3.0 hr.
-1 and the feed rate of hydrogen / feedstock ratio is 320 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３５】活性試験−２： ２０気圧（絶対圧）、３
４０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＬＧＯを液空間速度２．０ｈｒ
-1および水素／原料油の比の供給速度が１２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 40 ° C., and the feed oil LGO was supplied at a liquid hourly space velocity of 2.0 hr.
-1 and a feed rate of hydrogen / feed oil ratio of 120 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３６】これらの活性試験の結果を下記表２に示
す。なお、活性効果を表す触媒Ｂの数値は触媒Ｓの脱硫
率（製品の水素化脱硫前後の硫黄含有率から算出）を１
００とした場合の指数で表したものである。 表２ 各触媒の脱硫効果 触媒Ｓ 触媒Ｂ 粒子密度（ｇ／ｃｃ） １．２０ １．２１ 粒径（円柱）（ｍｍ） １．４０ １．４０ Ｃｏ重量％ ３．７ ３．７ Ｍｏ重量％ １２．０ １１．９ Ｅｒ重量％ ０ ０．１ 活性試験−１ １００ １２０ 活性試験−２ １００ １１２ 表２から明らかなように、参考例２の触媒Ｂは従来の触
媒Ｓに比べて、活性試験−１の脱硫活性では２０％、活
性試験−２の脱硫活性では１２％それぞれ優れているこ
とが裏付けられた。 ［比較例３］ １．４５重量％Ｃｏと３．２重量％Ｍｏを含有するアル
ミナ押し出し担体２００ｇに、３６ｇのモリブデン酸ア
ンモニウム塩と２０ｇのモノエタノールアミンと１００
Ｇの蒸留水からなる水溶液と、２７ｇの８５％燐酸溶液
と２８ｇの硝酸コバルト・６水和物と１５ｇの蒸留水か
らなる水溶液とを混合し、得られた水溶液を蒸留水で２
００ｃｃまで希釈して調製したモリブデンとコバルトを
含有するアンモニウム水溶液で含浸処理した。押し出し
担体は含浸溶液に浸漬した後蒸発乾固し、空気中におい
て３５０℃に１時間、次いで５５０℃に更に２時間乾燥
・焼成して触媒を調製した。３．４重量％Ｃｏと１１．
２重量％Ｍｏと３．０重量％Ｐを含有していた。これを
触媒Ｔとする。 ［実施例１］ 本発明に従って、比較例３の触媒２００ｇに２．８ｇ硝
酸エルビウム・６水和物を蒸留水で１８０ｃｃまで希釈
して調製した含浸溶液に浸漬した後蒸発乾固し、空気中
において３５０℃の温度で１時間、次いで５５０℃の温
度で更に２時間乾燥・焼成した。焼成後、押し出し触媒
は０．１重量％Ｅｒと３．４重量％Ｃｏと１１．１重量
％Ｍｏと３．０重量％Ｐを含有していた。これを触媒Ｃ
とする。 ［試験例３］ 上記実施例１で得られた触媒Ｃおよび比較例３で得られ
た触媒Ｔを用いて下記の２種類の活性試験を行った。The results of these activity tests are shown in Table 2 below. The value of the catalyst B showing the activity effect is calculated by calculating the desulfurization rate of the catalyst S (calculated from the sulfur content before and after hydrodesulfurization of the product) by 1
It is represented by an index when 00 is set. Table 2 Desulfurization effect of each catalyst Catalyst S Catalyst B Particle density (g / cc) 1.20 1.21 Particle size (cylinder) (mm) 1.40 1.40 Co weight% 3.7 3.7 Mo weight% 12.0 11.9 Er wt% 0 0.1 Activity test-1 100 120 Activity test-2 100 112 As is clear from Table 2, the catalyst B of Reference Example 2 has a higher activity test than the conventional catalyst S. It was proved that the desulfurization activity of -1 was superior by 20% and the desulfurization activity of activity test-2 by 12% was superior. [Comparative Example 3] 36 g of ammonium molybdate, 20 g of monoethanolamine and 100 g of 200 g of an alumina extruded support containing 1.45 wt% Co and 3.2 wt% Mo were added.
An aqueous solution composed of distilled water of G, an aqueous solution composed of 27 g of an 85% phosphoric acid solution, 28 g of cobalt nitrate hexahydrate and 15 g of distilled water are mixed, and the obtained aqueous solution is mixed with distilled water.
It was impregnated with an aqueous ammonium solution containing molybdenum and cobalt prepared by diluting the solution to 00 cc. The extruded carrier was immersed in the impregnating solution, evaporated to dryness, dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for 2 hours to prepare a catalyst. 3.4 wt% Co and 11.
It contained 2% by weight Mo and 3.0% by weight P. This is designated as catalyst T. Example 1 According to the present invention, 200 g of the catalyst of Comparative Example 3 was immersed in an impregnation solution prepared by diluting 2.8 g of erbium nitrate hexahydrate with distilled water to 180 cc, then evaporated to dryness, and dried in air. At 350 ° C. for 1 hour and then at 550 ° C. for another 2 hours. After calcination, the extruded catalyst contained 0.1 wt% Er, 3.4 wt% Co, 11.1 wt% Mo, and 3.0 wt% P. This is called catalyst C
And Test Example 3 The following two types of activity tests were performed using the catalyst C obtained in Example 1 and the catalyst T obtained in Comparative Example 3.
【００３７】活性試験−１： ４１気圧（絶対圧）、３
７０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＶＧＯを液空間速度３．０ｈｒ
-1および水素／原料油の比の供給速度が３２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 70 ° C., and the feed oil VGO was supplied at a liquid hourly space velocity of 3.0 hr.
-1 and the feed rate of hydrogen / feedstock ratio is 320 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３８】活性試験−２： ２０気圧（絶対圧）、３
４０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＬＧＯを液空間速度２．０ｈｒ
-1および水素／原料油の比の供給速度が１２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 40 ° C., and the feed oil LGO was supplied at a liquid hourly space velocity of 2.0 hr.
-1 and a feed rate of hydrogen / feed oil ratio of 120 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００３９】これらの活性試験の結果を下記表３に示
す。なお、活性効果を表す触媒Ｃの数値は触媒Ｔの脱硫
率（製品の水素化脱硫前後の硫黄含有率から算出）を１
００とした場合の指数で表したものである。 表３ 各触媒の脱硫効果 触媒Ｔ 触媒Ｃ 粒子密度（ｇ／ｃｃ） １．２６ １．２６ 粒径（円柱）（ｍｍ） １．４０ １．４０ Ｃｏ重量％ ３．４ ３．４ Ｍｏ重量％ １１．２ １１．１ Ｐ 重量％ ３．０ ３．０ Ｅｒ重量％ ０ ０．１ 活性試験−１ １００ １２４ 活性試験−２ １００ １１４ 表３から明らかなように、本発明の触媒Ｃは従来の触媒
Ｔに比べて、活性試験−１の脱硫活性では２４％、活性
試験−２の脱硫活性では１４％それぞれ優れていること
が裏付けられた。 ［比較例４］ １．５重量％Ｎｉと３．５重量％Ｍｏを含有するアルミ
ナ押し出し担体２００ｇに、３７ｇのモリブデン酸アン
モニウム塩と７０ｇの水酸化アンモニウムからなる水溶
液と、３０ｇの硝酸ニッケル・６水和物と１５ｇの蒸留
水からなる水溶液とを混合し、得られた水溶液を蒸留水
で２００ｃｃまで希釈して調製したモリブデンとニッケ
ルを含有するアンモニウム水溶液で含浸処理した。押し
出し担体は含浸溶液に浸漬した後蒸発乾固し、空気中に
おいて３５０℃に１時間、次いで５５０℃に更に２時間
乾燥・焼成して触媒を調製した。３．７重量％Ｎｉと１
２重量％Ｍｏを含有していた。これを触媒Ｕとする。 ［参考例３］ 比較例４の触媒２００ｇに２．８ｇ硝酸エルビウム・６
水和物を蒸留水で１８０ｃｃまで希釈して調製した含浸
溶液に浸漬した後蒸発乾固し、空気中において３５０℃
に１時間、次いで５５０℃に更に２時間乾燥・焼成し
た。焼成後、押し出し触媒は０．１重量％Ｅｒと３．７
重量％Ｎｉと１１．９重量％Ｍｏを含有していた。これ
を触媒Ｄとする。 ［試験例４］ 上記参考例３で得られた触媒Ｄおよび比較例４で得られ
た触媒Ｕを用いて下記の２種類の活性試験を行った。The results of these activity tests are shown in Table 3 below. The value of the catalyst C showing the activity effect is obtained by calculating the desulfurization rate of the catalyst T (calculated from the sulfur content before and after hydrodesulfurization of the product) by 1
It is represented by an index when 00 is set. Table 3 Desulfurization effect of each catalyst Catalyst T Catalyst C Particle density (g / cc) 1.26 1.26 Particle size (cylinder) (mm) 1.40 1.40 Co weight% 3.4 3.4 Mo weight% 11.2 11.1 P wt% 3.0 3.0 Er wt% 0 0.1 Activity test-1 100 124 Activity test-2 100 114 As is clear from Table 3, the catalyst C of the present invention is a conventional catalyst. Compared to the catalyst T, it was confirmed that the desulfurization activity of the activity test-1 was superior by 24% and the desulfurization activity of the activity test-2 was superior by 14%. Comparative Example 4 An aqueous solution comprising 37 g of ammonium molybdate and 70 g of ammonium hydroxide and 30 g of nickel nitrate · 6 were added to 200 g of an alumina extruded support containing 1.5 wt% Ni and 3.5 wt% Mo. The hydrate was mixed with an aqueous solution consisting of 15 g of distilled water, and the obtained aqueous solution was diluted with distilled water to 200 cc and impregnated with an aqueous ammonium solution containing molybdenum and nickel. The extruded carrier was immersed in the impregnating solution, evaporated to dryness, dried and calcined in air at 350 ° C. for 1 hour and then at 550 ° C. for 2 hours to prepare a catalyst. 3.7 wt% Ni and 1
It contained 2% by weight Mo. This is designated as catalyst U. [ Reference Example 3 ] 2.8 g of erbium nitrate-6 was added to 200 g of the catalyst of Comparative Example 4.
The hydrate is immersed in an impregnation solution prepared by diluting the hydrate to 180 cc with distilled water, and then evaporated to dryness, and 350 ° C. in air.
For 1 hour and then at 550 ° C. for another 2 hours. After calcination, the extruded catalyst contained 0.1 wt% Er and 3.7
% Ni and 11.9% Mo by weight. This is designated as catalyst D. [Test Example 4] The following two types of activity tests were performed using the catalyst D obtained in Reference Example 3 and the catalyst U obtained in Comparative Example 4.
【００４０】活性試験−１： ４１気圧（絶対圧）、３
７０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＶＧＯを液空間速度３．０ｈｒ
-1および水素／原料油の比の供給速度が３２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-1 : 41 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 70 ° C., and the feed oil VGO was supplied at a liquid hourly space velocity of 3.0 hr.
-1 and the feed rate of hydrogen / feedstock ratio is 320 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００４１】活性試験−２： ２０気圧（絶対圧）、３
４０℃に保持された縦型管状反応管の中に触媒を固定床
として配置して、原料油ＬＧＯを液空間速度２．０ｈｒ
-1および水素／原料油の比の供給速度が１２０Ｎｍ3／
ＫＬで触媒上で水素化処理した。水素化脱硫された流出
流を１２１℃の高圧気液分離器で液相と気相に分離し、
液相は更にストリッピングカラムで処理した。８時間に
わたって採取した液相（生成油）の硫黄分について分析
した。 Activity test-2 : 20 atm (absolute pressure), 3
The catalyst was disposed as a fixed bed in a vertical tubular reaction tube maintained at 40 ° C., and the feed oil LGO was supplied at a liquid hourly space velocity of 2.0 hr.
-1 and a feed rate of hydrogen / feed oil ratio of 120 Nm 3 /
Hydrotreated on catalyst with KL. The hydrodesulfurized effluent is separated into a liquid phase and a gas phase by a 121 ° C. high pressure gas-liquid separator,
The liquid phase was further processed on a stripping column. The liquid phase (product oil) collected over 8 hours was analyzed for sulfur content.
【００４２】これらの活性試験の結果を下記表４に示
す。なお、活性効果を表す触媒Ｄの数値は触媒Ｕの脱硫
率（製品の水素化脱硫前後の硫黄含有率から算出）を１
００とした場合の指数で表したものである。表４ 各触媒の脱硫効果 触媒Ｕ 触媒Ｄ 粒子密度（ｇ／ｃｃ） １．２０ １．２１ 粒径（円柱）（ｍｍ） １．４０ １．４０ Ｎｉ重量％ ３．７ ３．７ Ｍｏ重量％ １２．０ １１．９ Ｅｒ重量％ ０ ０．１ 活性試験−１ １００ １３１ 活性試験−２ １００ １１９ 表４から明らかなように、参考例３の触媒Ｄは従来の触
媒Ｕに比べて、活性試験−１の脱硫活性では３１％、活
性試験−２の脱硫活性では１９％それぞれ優れているこ
とが裏付けられた。 ［試験例５］−触媒寿命の測定− 上記実施例１で得られた触媒Ｃおよび比較例３で得られ
た触媒Ｔを用いて、絶対圧３００ｐｓｉｇ、水素／原料
油の比の供給速度が４００ＳＣＦＢ、ＬＨＳＶ（液空間
速度）２．０ｈｒ-1の条件下で触媒の寿命を調べた。結
果を図１に示す。図１のグラフは、各触媒を水素化脱硫
触媒として使用する場合に必要な反応温度の経時変化を
表す。通常、反応温度が３６０℃を越えると水素化脱硫
触媒としては不適となるので、この温度に至る期間がそ
の触媒の寿命と考えられる。図１によれば、従来の触媒
Ｔの寿命は約４．５カ月であるのに対して、本発明の触
媒Ｃの寿命は約１年３カ月と大幅に長くなっていること
が分かる。 ［試験例６］−色相安定性− １．５５重量％の硫黄分を含有する原料油ＬＧＯを、上
記実施例１で得られた触媒Ｃを用いて水素化脱硫処理
し、硫黄含有量が０．０９重量％および０．０５重量％
の軽油を得た。対照として、上記比較例３で得られた触
媒Ｔを用いて同様に水素化脱硫処理し、硫黄含有量が
０．０９重量％および０．０５重量％の軽油を得た。そ
れぞれの触媒を用いたときの色相値（セーボルト色相）
の経時変化を図２および図３に示す。図２は本発明の触
媒Ｃを用いた場合の色相値（セーボルト色相）の経時変
化を表すグラフ、図３は従来の触媒Ｔを用いた場合の色
相値（セーボルト色相）の経時変化を表すグラフであ
る。これらのグラフによれば、本発明の触媒を用いて水
素化脱硫処理した軽油は、いずれの硫黄含有量の場合も
色相の変化が緩やかであり、しかも３５日を過ぎるとほ
とんど色相の変化が見られない。これに対して、従来の
触媒を用いた場合は、いずれの硫黄含有量の場合も色相
が急速に低下しており、この点においても本発明の触媒
の優秀性が裏付けられた。The results of these activity tests are shown in Table 4 below. The value of the catalyst D showing the activity effect is obtained by calculating the desulfurization rate of the catalyst U (calculated from the sulfur content before and after hydrodesulfurization of the product) by 1
It is represented by an index when 00 is set. Table 4 Desulfurization effect of each catalyst Catalyst U Catalyst D Particle density (g / cc) 1.20 1.21 Particle size (cylindrical) (mm) 1.40 1.40 Ni weight% 3.7 3.7 Mo weight% 12.0 11.9 Er wt% 0 0.1 Activity test-1 100 131 Activity test-2 100 119 As is clear from Table 4, the activity of the catalyst D of Reference Example 3 was higher than that of the conventional catalyst U. It was confirmed that the desulfurization activity of -1 was 31%, and the desulfurization activity of Activity Test 2 was 19%, respectively. [Test Example 5]-Measurement of catalyst life-Using the catalyst C obtained in Example 1 and the catalyst T obtained in Comparative Example 3, an absolute pressure of 300 psig and a supply rate of hydrogen / feed oil ratio of 400 SCFB were used. , LHSV (liquid hourly space velocity) of 2.0 hr -1 , and the life of the catalyst was examined. The results are shown in FIG. The graph of FIG. 1 shows the change over time of the reaction temperature required when each catalyst is used as a hydrodesulfurization catalyst. Usually, if the reaction temperature exceeds 360 ° C., it becomes unsuitable as a hydrodesulfurization catalyst, and the period up to this temperature is considered to be the life of the catalyst. According to FIG. 1, it can be seen that the life of the conventional catalyst T is about 4.5 months, whereas the life of the catalyst C of the present invention is significantly longer, about one year and three months. [Test Example 6]-Hue stability-A raw oil LGO containing 1.55% by weight of sulfur was hydrodesulfurized using the catalyst C obtained in Example 1 described above, and the sulfur content was reduced to 0. 0.09% and 0.05% by weight
Light oil was obtained. As a control, hydrodesulfurization treatment was similarly performed using the catalyst T obtained in Comparative Example 3 to obtain light oils having a sulfur content of 0.09% by weight and 0.05% by weight. Hue value when each catalyst is used (Saebold hue)
Are shown in FIGS. 2 and 3. FIG. 2 is a graph showing the change over time of the hue value (Saybolt hue) when the catalyst C of the present invention is used, and FIG. 3 is a graph showing the change over time of the hue value (Saybolt hue) when the conventional catalyst T is used. It is. According to these graphs, the gas oil hydrodesulfurized using the catalyst of the present invention shows a gradual change in hue at any sulfur content, and a change in hue is almost observed after 35 days. I can't. On the other hand, when the conventional catalyst was used, the hue was rapidly reduced at any sulfur content, and this also supported the superiority of the catalyst of the present invention.
【００４３】[0043]
【発明の効果】本発明の水素化脱硫触媒は、従来の水素
化脱硫触媒と比べて、脱硫活性が大幅に高く、触媒寿命
が著しく延び、色相の低下が少なくしかも長期安定性に
優れているという顕著な効果を奏する。したがって、本
発明の水素化脱硫触媒は軽油中の硫黄分と芳香族分の第
二段階規制に十分対応できるものであり、これらの成分
に起因する環境問題の解決のために大いに寄与するもの
と言える。The hydrodesulfurization catalyst of the present invention has remarkably high desulfurization activity, significantly prolongs the catalyst life, has a small decrease in hue, and is excellent in long-term stability, as compared with conventional hydrodesulfurization catalysts. It has a remarkable effect. Therefore, the hydrodesulfurization catalyst of the present invention can sufficiently cope with the second-stage regulation of the sulfur content and aromatic content in light oil, and greatly contributes to solving environmental problems caused by these components. I can say.
【図１】本発明の水素化脱硫触媒と従来の水素化脱硫触
媒の反応温度の経時変化を示すグラフである。FIG. 1 is a graph showing the change over time in the reaction temperature of a hydrodesulfurization catalyst of the present invention and a conventional hydrodesulfurization catalyst.
【図２】本発明の触媒を用いた場合の色相値（セーボル
ト色相）の経時変化を表すグラフである。FIG. 2 is a graph showing a change over time of a hue value (Saebold hue) when the catalyst of the present invention is used.
【図３】従来の触媒を用いた場合の色相値（セーボルト
色相）の経時変化を表すグラフである。FIG. 3 is a graph showing a temporal change of a hue value (Saebold hue) when a conventional catalyst is used.
Claims (2)
素換算で４〜３０重量％のモリブデンと、１〜１０重量
％のコバルトおよび／またはニッケルと、１〜１０重量
％のリンと、０．０５〜５重量％のエルビウムとを耐火
性担体上に担持させたことを特徴とする炭化水素の水素
化脱硫触媒。1. An elemental conversion of 4 to 30% by weight of molybdenum, 1 to 10% by weight of cobalt and / or nickel and 1 to 10% by weight of phosphorus, based on the weight of all supported catalysts; A hydrocarbon hydrodesulfurization catalyst comprising 0.05 to 5% by weight of erbium supported on a refractory carrier.
素換算で４〜３０重量％のモリブデンと、１〜１０重量
％のコバルトおよび／またはニッケルと、１〜１０重量
％のリンと、０．０５〜５重量％のエルビウムとを耐火
性担体上に担持する水素化脱硫触媒を製造するにあた
り、（ａ）まず耐火性無機酸化物と最終担持量の各々１
０〜１００重量％となる量のモリブデン化合物、コバル
トおよび／またはニッケル化合物、リン化合物およびエ
ルビウム化合物とを混練して押し出し可能な軟塊を形成
し、（ｂ）この軟塊を押し出し、押し出された軟塊を酸
化雰囲気において乾燥、焼成した後、（ｃ）焼成した押
し出し成形体にモリブデン化合物、コバルトおよび／ま
たはニッケル化合物、リン化合物およびエルビウム化合
物の残量を含浸担持させた後、含浸担持させた押し出し
成形体を酸化雰囲気において乾燥、焼成することを特徴
とする炭化水素の水素化脱硫触媒の製造方法。2. An elemental conversion of 4 to 30% by weight of molybdenum, 1 to 10% by weight of cobalt and / or nickel and 1 to 10% by weight of phosphorus, based on the weight of all supported catalysts. In producing a hydrodesulfurization catalyst in which 0.05 to 5% by weight of erbium is supported on a refractory carrier, (a) first, a refractory inorganic oxide and a final loading amount of 1 respectively.
An amount of 0 to 100% by weight of a molybdenum compound, a cobalt and / or nickel compound, a phosphorus compound and an erbium compound is kneaded to form an extrudable soft mass, and (b) the soft mass is extruded and extruded. After the soft lump was dried and fired in an oxidizing atmosphere, (c) the fired extruded body was impregnated with the remaining amount of the molybdenum compound, cobalt and / or nickel compound, phosphorus compound and erbium compound, and then impregnated. A method for producing a hydrocarbon hydrodesulfurization catalyst, comprising drying and calcining an extruded product in an oxidizing atmosphere.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12376692A JP3333230B2 (en) | 1992-05-15 | 1992-05-15 | Hydrodesulfurization catalyst and method for producing the same |
| GB9309674A GB2267233B (en) | 1992-05-15 | 1993-05-11 | Hydrodesulfurization catalyst and preparation thereof |
| NL9300822A NL193985C (en) | 1992-05-15 | 1993-05-13 | Catalyst and Hydrodesulfurization Process Using the Catalyst. |
| FR9305874A FR2691078B1 (en) | 1992-05-15 | 1993-05-14 | HYDRODESULFURATION CATALYST, PROCESSES FOR PREPARING THE SAME, AND HYDRODESULFURATION METHOD USING THE SAME. |
| US08/061,242 US5484756A (en) | 1992-05-15 | 1993-05-17 | Hydrodesulfurization catalyst and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12376692A JP3333230B2 (en) | 1992-05-15 | 1992-05-15 | Hydrodesulfurization catalyst and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05317710A JPH05317710A (en) | 1993-12-03 |
| JP3333230B2 true JP3333230B2 (en) | 2002-10-15 |
Family
ID=14868756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12376692A Expired - Fee Related JP3333230B2 (en) | 1992-05-15 | 1992-05-15 | Hydrodesulfurization catalyst and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3333230B2 (en) |
-
1992
- 1992-05-15 JP JP12376692A patent/JP3333230B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05317710A (en) | 1993-12-03 |
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