JP2001162168A - Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalyst - Google Patents
Hydrogenation catalyst and method for hydrogenation treatment of heavy hydrocarbon oil by using that catalystInfo
- Publication number
- JP2001162168A JP2001162168A JP2000234049A JP2000234049A JP2001162168A JP 2001162168 A JP2001162168 A JP 2001162168A JP 2000234049 A JP2000234049 A JP 2000234049A JP 2000234049 A JP2000234049 A JP 2000234049A JP 2001162168 A JP2001162168 A JP 2001162168A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- hydrotreating
- heavy hydrocarbon
- oil
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 230000000737 periodic effect Effects 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 abstract description 11
- 238000009825 accumulation Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 39
- 230000000694 effects Effects 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000000499 gel Substances 0.000 description 23
- 238000006477 desulfuration reaction Methods 0.000 description 22
- 230000023556 desulfurization Effects 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000704 physical effect Effects 0.000 description 13
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- -1 vanadium and nickel Chemical class 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000001630 malic acid Substances 0.000 description 4
- 235000011090 malic acid Nutrition 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 102200118166 rs16951438 Human genes 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 101100321669 Fagopyrum esculentum FA02 gene Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013681 dietary sucrose Nutrition 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は水素化処理触媒及び
これを用いた重質炭化水素油の水素化処理方法に関し、
より詳しくは特定の物性を有する水素化処理触媒、及び
これを用いた重質炭化水素油の水素化処理方法に関す
る。The present invention relates to a hydrotreating catalyst and a method for hydrotreating heavy hydrocarbon oil using the same.
More specifically, the present invention relates to a hydrotreating catalyst having specific physical properties and a method for hydrotreating heavy hydrocarbon oil using the same.
【０００２】[0002]
【従来の技術】現在、酸性雨等からの環境保護のため、
燃料油中の硫黄分は水素化精製処理により低減されてお
り、そこで脱硫触媒が一般に使用されている。しかし、
特に常圧残油、減圧残油等の重質油を原料として低硫黄
重油を生産する場合において、触媒の脱硫性能の限界か
ら触媒寿命は短く、１年未満となっている。したがっ
て、１年以内で精製装置を停止し、触媒を交換せざるを
得ない。このように、重質油から低硫黄重油を生産する
場合、灯軽油の水素化処理に比較して、硫黄分を低減す
るためには、運転初期から高い温度を必要とする。ま
た、触媒の活性は時間とともに劣化していくため、製品
の硫黄分の量を一定に維持するためには、運転温度を徐
々に上げていく必要がある。特に、重質油にはバナジウ
ム、ニッケルといった金属分が含まれ、反応中に触媒に
堆積して活性を被毒するため、触媒の劣化が著しい。こ
のため、１年以内に装置の上限温度に達し、触媒を交換
することとなるわけである。したがって、より低温にお
ける高脱硫活性と耐金属蓄積性を有する触媒の開発が望
まれている。2. Description of the Related Art At present, to protect the environment from acid rain, etc.,
The sulfur content in fuel oils has been reduced by hydrorefining processes, where desulfurization catalysts are commonly used. But,
In particular, in the case of producing low-sulfur heavy oil from heavy oil such as atmospheric residual oil and vacuum residual oil as a raw material, the catalyst life is short and less than one year due to the limit of desulfurization performance of the catalyst. Therefore, the refining unit must be stopped within one year, and the catalyst must be replaced. As described above, when producing low-sulfur heavy oil from heavy oil, a high temperature is required from the beginning of operation in order to reduce the sulfur content as compared with the hydrotreatment of kerosene and light oil. In addition, since the activity of the catalyst deteriorates with time, it is necessary to gradually increase the operating temperature in order to keep the amount of sulfur in the product constant. In particular, heavy oil contains metals such as vanadium and nickel, and accumulates on the catalyst during the reaction and poisons the activity. Therefore, the temperature reaches the upper limit temperature of the device within one year, and the catalyst is replaced. Therefore, development of a catalyst having a high desulfurization activity and a metal accumulation resistance at a lower temperature is desired.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記観点か
らなされたもので、より低温における高脱硫活性と耐金
属蓄積性を有する水素化処理触媒を提供するとともに、
その水素化処理触媒を用いた重質炭化水素油の水素化処
理方法を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above, and provides a hydrotreating catalyst having a high desulfurization activity and a metal accumulation resistance at a lower temperature.
It is an object of the present invention to provide a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst.
【０００４】[0004]
【課題を解決するための手段】本発明者らは鋭意研究の
結果、特定の物性を有する水素化処理触媒を使用するこ
とにより、上記本発明の目的を効果的に達成しうること
を見出し本発明を完成したものである。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object of the present invention can be effectively achieved by using a hydrotreating catalyst having specific physical properties. The invention has been completed.
【０００５】すなわち、本発明の要旨は下記のとおりで
ある。 １．シリカを１〜１０質量％含有するアルミナ担体に、
周期律表第６族の金属の少なくとも一種及び周期律表第
８〜１０族の金属から選ばれる少なくとも一種を担持し
た触媒であって、該触媒の平均細孔直径（ＰＤ）が１０
０〜１７０Åで、比表面積（ＳＡ）が１４０〜２５０ｍ
2 ／ｇであり、かつ両者が下記の（１）式を満足し、さ
らに全細孔容量が０．４〜１．０ｃｃ／ｇであることを
特徴とする水素化処理触媒。 ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１） ２．周期律表第６族金属がモリブデンであり、周期律表
第８〜１０族金属がニッケルである上記１記載の水素化
処理触媒。 ３．触媒がリンを３〜５質量％含有するものである上記
１又は２に記載の水素化処理触媒。 ４．担体への金属担持が、沸点又は分解温度２００℃以
上の水溶性有機化合物を含有する含浸液を用いてなされ
たものである上記１〜３のいずれかに記載の水素化処理
触媒。 ５．水溶性有機化合物がポリエチレングリコールである
上記４記載の水素化処理触媒。 ６．上記１〜５のいずれかに記載した水素化処理触媒を
用いた重質炭化水素油の水素化処理方法。 ７．上流側に脱金属触媒、下流側に上記１〜５のいずれ
かに記載の水素化処理触媒を用いた上記６記載の重質炭
化水素油の水素化処理方法。 ８．重質炭化水素油が減圧軽油、常圧残油又は減圧残油
である上記６又は７に記載の重質炭化水素油の水素化処
理方法。That is, the gist of the present invention is as follows. 1. Alumina support containing 1 to 10% by mass of silica,
A catalyst supporting at least one metal of Group 6 of the periodic table and at least one metal selected from metals of Groups 8 to 10 of the periodic table, wherein the catalyst has an average pore diameter (PD) of 10
0-170 °, specific surface area (SA) 140-250m
2 / g, both satisfy the following formula (1), and have a total pore volume of 0.4 to 1.0 cc / g. SA + 1.65PD> 410 (1) 2. The hydrotreating catalyst according to the above 1, wherein the metal belonging to Group 6 of the periodic table is molybdenum and the metal belonging to Groups 8 to 10 of the periodic table is nickel. 3. 3. The hydrotreating catalyst according to 1 or 2, wherein the catalyst contains 3 to 5% by mass of phosphorus. 4. 4. The hydrotreating catalyst according to any one of the above 1 to 3, wherein the supporting of the metal on the carrier is performed using an impregnating liquid containing a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C or higher. 5. 5. The hydrotreating catalyst according to the above 4, wherein the water-soluble organic compound is polyethylene glycol. 6. A method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst according to any one of the above 1 to 5. 7. 7. The method for hydrotreating heavy hydrocarbon oil according to the above item 6, wherein the dehydrogenating catalyst is used on the upstream side and the hydrotreating catalyst described in any one of the above items 1 to 5 is used on the downstream side. 8. 8. The method for hydrotreating heavy hydrocarbon oil according to the above item 6 or 7, wherein the heavy hydrocarbon oil is a vacuum gas oil, a normal pressure residual oil or a vacuum residual oil.
【０００６】[0006]
【発明の実施の形態】以下に本発明について詳細に説明
する。本発明の水素化処理触媒は、シリカを１〜１０質
量％含有するアルミナ担体に、周期律表第６族の金属の
少なくとも一種及び周期律表第８〜１０族の金属から選
ばれる少なくとも一種を担持した触媒であって、該触媒
の平均細孔直径（ＰＤ）が１００〜１７０Åで、比表面
積（ＳＡ）が１４０〜２５０ｍ2 ／ｇであり、かつ両者
が下記の（１）式を満足し、さらに全細孔容量が０．４
〜１．０ｃｃ／ｇであることを特徴とする。 ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The hydrotreating catalyst of the present invention comprises, on an alumina carrier containing 1 to 10% by mass of silica, at least one metal selected from Group 6 of the periodic table and a metal selected from Groups 8 to 10 of the periodic table. A supported catalyst having an average pore diameter (PD) of 100 to 170 °, a specific surface area (SA) of 140 to 250 m 2 / g, and both satisfy the following formula (1): And a total pore volume of 0.4
~ 1.0 cc / g. SA + 1.65PD> 410 (1)
【０００７】まず、アルミナ担体に添加するシリカの量
は１〜１０質量％である。１質量％未満であると、アル
ミナの表面積を大にする効果は少なく、１０質量％を超
えると、特定の含浸液が担体に高分散に金属を担持する
能力が低下し好ましくない。担体に担持する金属につい
ては、周期律表第６族金属として、モリブデン、タング
ステンなどを挙げることができるが、モリブデンが好ま
しい。第６族金属の担持量は、触媒基準で、酸化物基準
で４〜２５質量％、好ましくは８〜２０質量％である。
周期律表第８〜１０族の金属として、コバルト、ニッケ
ルなどを挙げることができるが、ニッケルが好ましい。
第８〜１０族金属の担持量は、触媒基準で、酸化物基準
で１〜８質量％、好ましくは２〜５質量％である。ま
た、その他の成分としては、特にリンが好ましい。リン
を添加すると、触媒の水素化活性が向上し、特に重質炭
化水素油を原料とする場合においては、脱硫活性が向上
する。その効果は添加量が、触媒基準で、酸化物基準で
３〜５質量％で顕著となる。First, the amount of silica added to the alumina carrier is 1 to 10% by mass. If it is less than 1% by mass, the effect of increasing the surface area of alumina is small, and if it exceeds 10% by mass, the ability of the specific impregnating liquid to support the metal in the carrier in a highly dispersed manner is undesirably reduced. As for the metal supported on the carrier, molybdenum, tungsten, and the like can be given as Group 6 metals of the periodic table, and molybdenum is preferable. The supported amount of the Group 6 metal is 4 to 25% by mass, preferably 8 to 20% by mass on the basis of the catalyst and on the basis of the oxide.
Examples of metals belonging to Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred.
The supported amount of the Group 8 to 10 metal is 1 to 8% by mass, preferably 2 to 5% by mass on the basis of the catalyst and on the basis of the oxide. Further, as the other component, phosphorus is particularly preferable. When phosphorus is added, the hydrogenation activity of the catalyst is improved, and particularly when heavy hydrocarbon oil is used as the raw material, the desulfurization activity is improved. The effect becomes remarkable when the addition amount is 3 to 5% by mass on the basis of the catalyst and on the basis of the oxide.
【０００８】触媒の平均細孔直径（ＰＤ）は１００〜１
７０Åである。１００Å未満であると、原料の炭化水素
油中のバナジウムやニッケルの金属の堆積及びコーク前
駆体の堆積により、短時間で細孔が閉塞し脱硫活性が低
下してしまう。１７０Åを超えると、運転初期におい
て、脱硫活性が著しく低くなり好ましくない。触媒の比
表面積（ＳＡ）は１４０〜２５０ｍ2 ／ｇである。１４
０ｍ2 ／ｇ未満であると、触媒の脱硫活性が低く、２５
０ｍ2 ／ｇを超えると、脱硫活性が飽和してしまい、効
率が悪い。また、上記ＰＤとＳＡは前記式（１）を満足
する必要がある。その式（１）を満足しないと、脱硫活
性及び触媒寿命ともに劣る触媒となる。The average pore diameter (PD) of the catalyst is 100 to 1
70 °. If it is less than 100 °, the pores are closed in a short time due to the deposition of metals such as vanadium and nickel and the deposition of a coke precursor in the raw material hydrocarbon oil, and the desulfurization activity is reduced. If it exceeds 170 °, the desulfurization activity becomes extremely low in the initial stage of operation, which is not preferable. The specific surface area (SA) of the catalyst is from 140 to 250 m 2 / g. 14
If it is less than 0 m 2 / g, the desulfurization activity of the catalyst is low, and
If it exceeds 0 m 2 / g, the desulfurization activity is saturated and the efficiency is poor. Further, the PD and the SA need to satisfy the above-mentioned expression (1). If the formula (1) is not satisfied, the catalyst is inferior in both desulfurization activity and catalyst life.
【０００９】次いで、上記水素化処理触媒の製造方法に
ついて説明する。まず、担体のシリカ含有アルミナ担体
の製造法としては、一般的には、アルミナ源とシリカ源
を混合し、沈殿を熟成させ、乾燥させ、焼成する。Next, a method for producing the hydrotreating catalyst will be described. First, as a method for producing a silica-containing alumina carrier as a carrier, generally, an alumina source and a silica source are mixed, the precipitate is aged, dried, and fired.
【００１０】用いられるアルミナ源としては、硫酸アル
ミニウム，硝酸アルミニウム等の水溶性酸性アルミナ
塩、アルミン酸ソーダ等の水溶性塩基性アルミナ塩を挙
げることができる。用いられるシリカ源としては、水ガ
ラス，珪酸ナトリウム，シリカゾル等を挙げることがで
きる。アルミナ源とシリカ源を混合する場合のｐＨは３
〜１０、好ましくは３．３〜９．３である。混合温度は
３０〜９０℃、好ましくは５０〜８０℃である。Examples of the alumina source used include water-soluble acidic alumina salts such as aluminum sulfate and aluminum nitrate, and water-soluble basic alumina salts such as sodium aluminate. Examples of the silica source used include water glass, sodium silicate, silica sol and the like. When the alumina source and the silica source are mixed, the pH is 3
-10, preferably 3.3-9.3. The mixing temperature is 30 to 90 ° C, preferably 50 to 80 ° C.
【００１１】生成した沈殿の熟成方法については、一般
には、混合時と同じ温度にて酸性及びアルカリ性溶液を
交互に加える操作（スイング）を、ｐＨ３．０〜９．３
の間で３回以上、好ましくは５回以上行うことによって
行うことができる。また、ｐＨ９以上にて温度７０℃以
上、好ましくはｐＨ１０以上にて温度８０℃以上で、一
定の時間攪拌する方法を用いることもできる。これをス
イング法と組み合わせてもよい。熟成した沈殿を８０〜
２００℃（好ましくは１００〜１６０℃）で乾燥させ、
４００〜７００℃（好ましくは５００〜６００℃）で焼
成する。Regarding the ripening method of the formed precipitate, generally, an operation (swing) of alternately adding an acidic and an alkaline solution at the same temperature as during mixing is performed at pH 3.0 to 9.3.
And at least three times, preferably at least five times. Further, a method of stirring at a temperature of 70 ° C. or higher at pH 9 or higher, preferably at a temperature of 80 ° C. or higher at pH 10 or higher for a certain period of time can also be used. This may be combined with the swing method. Aged precipitate is 80 ~
Dried at 200C (preferably 100-160C),
Baking at 400 to 700 ° C (preferably 500 to 600 ° C).
【００１２】上記の沈殿を得る方法として、アルミナ及
びシリカのゲルを各々予め製造しておき両者を混合する
方法、アルミナゲルにシリカ化合物の水溶液を混合する
方法、アルミニウム化合物を含む溶液とアルミニウム化
合物及びシリカ化合物を混合して沈殿を得る方法、アル
ミニウム化合物及びシリカ化合物を含む溶液のｐＨを変
化させて沈殿を得る方法などを採用することができる。As a method for obtaining the above-mentioned precipitate, a method of preparing alumina gel and silica gel in advance and mixing the two, a method of mixing an aqueous solution of a silica compound with an alumina gel, a solution containing an aluminum compound and an aluminum compound, A method of obtaining a precipitate by mixing a silica compound, a method of obtaining a precipitate by changing the pH of a solution containing an aluminum compound and a silica compound, and the like can be employed.
【００１３】特に望ましい担体の沈殿を得るためには、
水溶性塩基性アルミナ塩に、一旦、実質的にゲルを生じ
ない条件で水溶性シリカを混合せしめた溶液を調製し、
更に水溶性アルミナ塩を添加してゲルを生成せしめる方
法を採用すればよい。さらに詳細に述べると、実質的に
ゲルを生じない条件で水溶性塩基性アルミナ塩と水溶性
シリカの溶液を混合するには、水溶性塩基性アルミナ塩
の水溶液に、予めアンモニア水や水酸化ナトリウム等の
塩基を添加してｐＨを１０以上に高めてから、水溶性シ
リカを添加すればよい。または、ｐＨ３以下で水ガラス
と硫酸アルミニウムを混合することによっても、実質的
にゲルを生じない混合が可能である。このようにして得
られたシリカ・アルミナの水溶液に、さらに水溶性の酸
性アルミナ溶液あるいは塩基性アルミナ溶液を添加して
沈殿を生じさせる。アルカリ側で調製したシリカ・アル
ミナ透明溶液から沈殿を得るためには、水溶性の酸性ア
ルミナ溶液を添加することが有効であり、酸性側で調製
したシリカ・アルミナ透明溶液から沈殿を得るために
は、水溶性の塩基性アルミナ溶液を添加することが有効
である。In order to obtain a particularly desirable precipitation of the carrier,
A solution prepared by mixing a water-soluble silica with a water-soluble basic alumina salt under conditions that do not substantially cause gelation,
Further, a method of forming a gel by adding a water-soluble alumina salt may be adopted. More specifically, in order to mix a solution of a water-soluble basic alumina salt and a water-soluble silica under conditions that do not substantially form a gel, an aqueous solution of a water-soluble basic alumina salt is added to an aqueous solution of ammonia or sodium hydroxide in advance. The base may be added to raise the pH to 10 or more, and then water-soluble silica may be added. Alternatively, by mixing water glass and aluminum sulfate at a pH of 3 or less, mixing that does not substantially produce a gel is possible. A water-soluble acidic alumina solution or basic alumina solution is further added to the silica-alumina aqueous solution thus obtained to cause precipitation. In order to obtain a precipitate from the silica-alumina transparent solution prepared on the alkali side, it is effective to add a water-soluble acidic alumina solution. It is effective to add a water-soluble basic alumina solution.
【００１４】以上のようにして得られたシリカ含有アル
ミナ担体に、以下の方法で金属を担持することができ
る。担持法は含浸法が好ましい。周期律表第６族のモリ
ブデン化合物としては、三酸化モリブデン，パラモリブ
デン酸アンモニウム等が使用され、タングステン化合物
としては、三酸化タングステン，タングステン酸アンモ
ニウム等が使用される。また、周期律表第８〜１０族の
ニッケル化合物としては、硝酸ニッケル，塩基性炭酸ニ
ッケル等が使用され、コバルト化合物としては、硝酸コ
バルト，塩基性炭酸コバルト等が使用される。さらに、
リン化合物としては、五酸化リン，リン酸等が使用され
る。上記の金属化合物を、周期律表第６族金属は０．７
〜４．３モル／リットル、周期律表第８〜１０族の金属
は０．３〜２．４モル／リットル、リン化合物は１．１
〜２．０モル／リットルの割合で純水に溶解させ、さら
に沸点又は分解温度２００℃以上の水溶性有機化合物を
５０〜２００ｇ／リットルの割合で溶解させたものを含
浸液とし、担体に吸水率と等量になるように調整後含浸
させる。その沸点又は分解温度２００℃以上の水溶性有
機化合物として、１，３−ブタンジオール，１，４−ブ
タンジオール，ポリエチレングリコール，ポリオキシエ
チレンフェニルエーテル，ポリオキシエチレンオクチル
フェニルエーテル等のエーテル基含有水溶性高分子、ポ
リビニルアルコール等のアルコール水溶性高分子、サッ
カロース，グリコース等の各種糖類、メチルセルロー
ス，水溶性でんぷん等の水溶性多糖類及びこれらの誘導
体を使用することができるが、分子量４００以上のポリ
エチレングリコールが好ましい。沸点又は分解温度２０
０℃以上の水溶性有機化合物を使用することにより、金
属の担体での凝集を抑制することができる。A metal can be supported on the silica-containing alumina carrier obtained as described above by the following method. The supporting method is preferably an impregnation method. Molybdenum trioxide, ammonium paramolybdate and the like are used as molybdenum compounds of Group 6 of the periodic table, and tungsten trioxide and ammonium tungstate are used as tungsten compounds. Nickel nitrate, basic nickel carbonate or the like is used as a nickel compound belonging to Groups 8 to 10 of the periodic table, and cobalt nitrate or basic cobalt carbonate is used as a cobalt compound. further,
As the phosphorus compound, phosphorus pentoxide, phosphoric acid and the like are used. The above-mentioned metal compound is represented by the following formula:
To 4.3 mol / l, metals of groups 8 to 10 of the periodic table are 0.3 to 2.4 mol / l, and phosphorus compounds are 1.1
A solution in which pure water is dissolved at a rate of about 2.0 mol / L and a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or more is dissolved at a rate of 50 to 200 g / L is used as an impregnation liquid, and the carrier absorbs water. Impregnation is carried out after adjustment so as to have the same amount as the ratio. Examples of the water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher include ether group-containing water-soluble compounds such as 1,3-butanediol, 1,4-butanediol, polyethylene glycol, polyoxyethylene phenyl ether, and polyoxyethylene octyl phenyl ether. Water-soluble polymers such as water-soluble polymers, alcohol-soluble polymers such as polyvinyl alcohol, various sugars such as saccharose and glucose, water-soluble polysaccharides such as methylcellulose and water-soluble starch, and derivatives thereof can be used, but polyethylene having a molecular weight of 400 or more can be used. Glycols are preferred. Boiling point or decomposition temperature 20
By using a water-soluble organic compound having a temperature of 0 ° C. or higher, aggregation of the metal on the carrier can be suppressed.
【００１５】なお、含浸液のｐＨ調整は特に限定されな
いが、硝酸，塩酸，硫酸等の無機酸、りんご酸，エチレ
ンジアミン４酢酸等の有機酸、アンモニアなどを使用し
て行うことができる。含浸後乾燥、焼成するが、乾燥温
度は８０〜２００℃（好ましくは１００〜１５０℃）、
焼成温度は３００〜６００℃（好ましくは４００〜５５
０℃）である。焼成温度が低すぎると、担持成分と担体
と十分な結合を持つことができない場合があり、高すぎ
ると、担持成分の凝集が起こり易くなる。The pH of the impregnating solution is not particularly limited, but can be adjusted by using an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, etc., an organic acid such as malic acid, ethylenediaminetetraacetic acid, or ammonia. After impregnation, drying and firing are performed, and the drying temperature is 80 to 200 ° C (preferably 100 to 150 ° C),
The firing temperature is 300 to 600 ° C (preferably 400 to 55 ° C).
0 ° C). If the firing temperature is too low, it may not be possible to have a sufficient bond between the support component and the carrier, and if it is too high, the support component is likely to aggregate.
【００１６】次に、本発明の水素化処理触媒を用いて水
素化処理を行う際には、予め安定化処理として予備硫化
を行うことが望ましい。この予備硫化処理の条件は特に
限定されないが、通常、予備硫化剤として、硫化水素，
二硫化炭素，チオフェン，ジメチルジスルフィド等を挙
げることができ、処理温度２００〜４００℃、処理圧力
常圧〜３０ＭＰａの範囲で行われる。Next, when performing the hydrotreating using the hydrotreating catalyst of the present invention, it is desirable to perform preliminary sulfurization as a stabilizing process in advance. The conditions for this pre-sulfurization treatment are not particularly limited, but usually, hydrogen sulfide,
Examples thereof include carbon disulfide, thiophene, and dimethyl disulfide. The treatment is performed at a treatment temperature of 200 to 400 ° C. and a treatment pressure of normal pressure to 30 MPa.
【００１７】触媒の形状については、特に重質炭化水素
油の水素化処理に使用される触媒は、通常押出成形で製
造されるものが多く、その形状は実質的に柱状をしてい
る。その断面は円形のものが多いが、三葉型、四葉型な
ど外表面を多くする工夫のあるものもある。また、球状
触媒もよく用いられる。球状触媒は圧縮強度や耐磨耗性
が特に要求される場合に使用される。Regarding the shape of the catalyst, most of the catalysts used particularly for hydrotreating heavy hydrocarbon oils are usually produced by extrusion, and the shape is substantially columnar. The cross-section is often circular, but there are also three-lobed and four-lobed designs that have a large outer surface. Also, spherical catalysts are often used. The spherical catalyst is used when compressive strength and abrasion resistance are particularly required.
【００１８】水素化処理条件については、原料油の種類
や目的により異なるが、一般的には反応温度２００〜５
５０℃（好ましくは２２０〜５００℃）、水素分圧５〜
３０ＭＰａ（好ましくは１０〜２５ＭＰａ）の範囲で行
われる。The hydrotreating conditions vary depending on the type and purpose of the feedstock oil, but generally the reaction temperature is 200 to 5 hours.
50 ° C. (preferably 220-500 ° C.), hydrogen partial pressure 5-5
It is performed in a range of 30 MPa (preferably 10 to 25 MPa).
【００１９】反応形式は特に限定されないが、通常は、
固定床，移動床，沸騰床，懸濁床等の種々のプロセスか
ら選択できるが、固定床が好ましい。固定床の場合の温
度、圧力以外の反応条件としては、液空間速度（ＬＨＳ
Ｖ）は０．０５〜１０ｈｒ-1（好ましくは０．１〜５ｈ
ｒ-1）、水素／オイル比は５００〜２，５００Ｎｍ3 ／
ｋｌ（好ましくは７００〜２，０００Ｎｍ3 ／ｋｌ）で
ある。The type of reaction is not particularly limited, but usually,
The process can be selected from various processes such as a fixed bed, a moving bed, a boiling bed, and a suspended bed, but a fixed bed is preferred. Reaction conditions other than temperature and pressure in the case of a fixed bed include liquid hourly space velocity (LHS
V) is 0.05 to 10 hr -1 (preferably 0.1 to 5 h)
r -1 ), the hydrogen / oil ratio is from 500 to 2,500 Nm 3 /
kl (preferably 700 to 2,000 Nm 3 / kl).
【００２０】本願の第二発明は、前記水素化処理触媒を
用いた重質炭化水素油の水素化処理方法である。該重質
炭化水素として、常圧残油，減圧残油，減圧軽油，脱蝋
減圧残油，アスファルテン油，タールサンド油及びこれ
らを一旦予備的二水素化処理した残油を挙げることがで
きる。また、上記残油と接触分解軽油との混合油（残油
／接触分解油（容量比）は１以上、好ましくは１．５以
上）も使用することができる。原料油の性状として、特
に限定されないが、代表的な性状としては下記のとおり
である。[0020] The second invention of the present application is a method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst. Examples of the heavy hydrocarbons include atmospheric residual oil, vacuum residual oil, vacuum gas oil, dewaxed vacuum residual oil, asphaltene oil, tar sands oil, and residual oils which have been subjected to preliminary dihydrogenation. Also, a mixed oil of the above-mentioned residual oil and catalytic cracking gas oil (residual oil / catalytic cracking oil (volume ratio) is 1 or more, preferably 1.5 or more) can be used. The properties of the feedstock are not particularly limited, but typical properties are as follows.
【００２１】 比重（１５／４℃）：０．９５３０〜０．９９４０ 動粘度（５０℃）：２５０〜３，０００ｃＳｔ 硫黄分：２．８〜４．５質量％ 窒素分：１，５００〜４，２００ｐｐｍ 金属分（Ｖ，Ｎｉ）：３０〜２５０ｐｐｍ 残炭分：５〜１８質量％ アスファルテン分：０．５〜１２．０質量％ 反応条件としては、上記の原料油を、単層の水素化処理
触媒を充填して水素化処理してもよいが、より高脱硫活
性で長寿命な触媒にするために、上流側にアルミナ担体
に周期律表第６族の少なくとも一種及び周期律表第８〜
１０族から選ばれる少なくとも一種を担持した脱金属触
媒を用い、下流側に本発明の水素化処理触媒を用いた触
媒システムにすればよい。Specific gravity (15/4 ° C.): 0.9530 to 0.9940 Kinematic viscosity (50 ° C.): 250 to 3,000 cSt Sulfur content: 2.8 to 4.5 mass% Nitrogen content: 1,500 to 4 , 200 ppm Metal content (V, Ni): 30 to 250 ppm Residual carbon content: 5 to 18 mass% Asphaltene content: 0.5 to 12.0 mass% The reaction conditions are as follows: Hydrotreating may be carried out by filling the treated catalyst, but in order to obtain a catalyst with higher desulfurization activity and longer life, at least one member of Group 6 of the Periodic Table and Group 8 of the Periodic Table 8 are provided on the alumina carrier on the upstream side. ~
What is necessary is just to make the catalyst system using a demetallization catalyst carrying at least one member selected from Group 10 and using the hydrotreating catalyst of the present invention on the downstream side.
【００２２】上記の上流側に使用する脱金属触媒の物性
等の例を下記に示す。周期律表第６族の金属として、モ
リブデン、タングステンなどを挙げることができるが、
モリブデンが好ましい。第６族金属の担持量は、触媒基
準で、酸化物基準で２〜１５質量、好ましくは４〜１２
質量％である。周期律表第８〜１０族の金属として、コ
バルト、ニッケルなどを挙げることができるが、ニッケ
ルが好ましい。第８〜１０族金属の担持量は、触媒基準
で、酸化物基準で１〜４質量％、好ましくは１．５〜
２．５質量％である。担体としては、アルミナが望まし
く、触媒の細孔径は１００〜２５０Å（好ましくは１５
０〜２２０Å）、比表面積は、８０〜２００ｍ2 ／ｇ
（好ましくは１００〜１８０ｍ2 ／ｇ）、細孔容積は
０．４〜１．０ｃｃ／ｇ（好ましくは０．５〜０．９ｃ
ｃ／ｇ）である。Examples of the physical properties of the demetalization catalyst used on the upstream side are shown below. Molybdenum, tungsten, and the like can be given as metals of Group 6 of the periodic table.
Molybdenum is preferred. The supported amount of the Group 6 metal is 2 to 15 mass, preferably 4 to 12 mass on the basis of the catalyst and on the basis of the oxide.
% By mass. Examples of metals belonging to Groups 8 to 10 of the periodic table include cobalt and nickel, with nickel being preferred. The supported amount of the Group 8 to 10 metal is 1 to 4% by mass, preferably 1.5 to 4% by mass, based on the catalyst and the oxide.
2.5% by mass. As the support, alumina is desirable, and the pore size of the catalyst is 100 to 250 ° (preferably 15 to 250 °).
0 to 220 °), and the specific surface area is 80 to 200 m 2 / g.
(Preferably 100 to 180 m 2 / g) and a pore volume of 0.4 to 1.0 cc / g (preferably 0.5 to 0.9 c / g).
c / g).
【００２３】脱金属触媒と本発明の水素化処理触媒の充
填割合は、脱金属触媒が１０〜５０容量％（好ましくは
２０〜４０容量％）に対して、本発明の水素化処理触媒
は５０〜９０容量％（好ましくは６０〜８０容量％）で
ある。The filling ratio of the demetallizing catalyst and the hydrotreating catalyst of the present invention is such that the demetallizing catalyst is 10 to 50% by volume (preferably 20 to 40% by volume) and the hydrotreating catalyst of the present invention is 50% by volume. To 90% by volume (preferably 60 to 80% by volume).
【００２４】[0024]
【実施例】次に、本発明を実施例により具体的に説明す
るが、本発明はこれらの実施例によりなんら制限される
ものではない。 〔実施例１〕純水２．３８リットルを７０℃に加温し、
攪拌しながら、水ガラス１６ｇを添加してシリカ溶液Ｓ
１を得た。溶液のｐＨは９．３であった。また、純水１
リットルに、水酸化ナトリウム３５．４ｇを溶解させ、
さらに、アルミン酸ソーダ９９．３ｇを添加して、均一
なアルミナ溶液Ｂ１を得た。さらに、純水１リットルに
硝酸アルミニウム５００ｇを溶解させ、アルミナ溶液Ａ
１を得た。次に、シリカ溶液Ｓ１にアルミナ溶液Ａ１を
ｐＨ３．６になるまで添加した。この時、溶液中には白
色のゲルが生成した。次にアルミナ溶液Ｂ１をｐＨ９．
０になるまで添加して、５分間攪拌しながらゲルを熟成
させた。続いて再びアルミナ溶液Ａ１を添加して、ｐＨ
を３．６とし、攪拌しながら５分間ゲルを熟成させた。
このようにｐＨを３．６から９．０の間で変化させる操
作を１０回繰り返した。その後、得られたゲルをろ過、
洗浄してシリカ含有アルミナゲルを５８０ｇ得た。この
ゲルを１２０℃、１６時間乾燥させ、さらに５００℃で
２時間焼成してシリカ含有アルミナ担体Ｃ１を得た。EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [Example 1] 2.38 liters of pure water was heated to 70 ° C,
While stirring, 16 g of water glass was added and silica solution S was added.
1 was obtained. The pH of the solution was 9.3. Also, pure water 1
Dissolve 35.4 g of sodium hydroxide in liter,
Further, 99.3 g of sodium aluminate was added to obtain a uniform alumina solution B1. Further, 500 g of aluminum nitrate was dissolved in 1 liter of pure water, and alumina solution A was used.
1 was obtained. Next, the alumina solution A1 was added to the silica solution S1 until the pH reached 3.6. At this time, a white gel was formed in the solution. Next, the alumina solution B1 was adjusted to pH9.
The mixture was added to 0, and the gel was aged while stirring for 5 minutes. Subsequently, alumina solution A1 was added again, and the pH was adjusted.
Was adjusted to 3.6, and the gel was aged for 5 minutes with stirring.
The operation of changing the pH between 3.6 and 9.0 was repeated 10 times. Then, the obtained gel is filtered,
After washing, 580 g of a silica-containing alumina gel was obtained. This gel was dried at 120 ° C. for 16 hours, and calcined at 500 ° C. for 2 hours to obtain a silica-containing alumina support C1.
【００２５】三酸化モリブデン８３ｇ、塩基性炭酸ニッ
ケル３７ｇ（ＮｉＯとして２０ｇ）、正リン酸（純度８
５％）３８ｇとポリエチレングリコール（分子量４０
０，分解温度２００℃以上）３０ｇをイオン交換水に溶
解させ、全量を２７５ｃｃの含浸液とした。次にその含
浸液５５ｃｃを前記のシリカ含有アルミナ担体Ｃ１の吸
水量に見合った量に調製し、１００ｇに常圧含浸させ
た。この担持物を、１２０℃で３時間乾燥させて、空気
中５００℃、３時間焼成して触媒Ｉを得た。その物性を
第１表に示す。83 g of molybdenum trioxide, 37 g of basic nickel carbonate (20 g as NiO), orthophosphoric acid (purity 8
5 g) and polyethylene glycol (molecular weight 40)
(0, decomposition temperature of 200 ° C. or higher) 30 g was dissolved in ion-exchanged water, and the total amount was 275 cc. Next, 55 cc of the impregnating liquid was adjusted to an amount corresponding to the water absorption of the silica-containing alumina carrier C1, and 100 g of the impregnated liquid was impregnated at normal pressure. This supported material was dried at 120 ° C. for 3 hours, and calcined in air at 500 ° C. for 3 hours to obtain Catalyst I. The physical properties are shown in Table 1.
【００２６】上記のようにして得られた触媒Ｉについ
て、下記の方法で脱硫活性試験を実施した。超小型高圧
固定床反応装置の反応管に、粉砕しメッシュにより粒径
を揃えた触媒２００ｍｇを充填し、硫化水素／水素ガス
（１０％硫化水素）を５０ミリリットル／分で４００
℃、２時間流通させて、予備硫化した。そして、温度３
５０℃でチオフェン（６％）を常圧水素気流中にて５０
ミリリットル／分流通させて３時間後のチオフェンの転
化率を測定した。結果を第１表に示す。なお、脱硫活性
の評価としてはチオフェン転化の触媒質量あたりの速度
定数を用いた。The catalyst I obtained as described above was subjected to a desulfurization activity test by the following method. A reaction tube of an ultra-small high-pressure fixed-bed reactor is filled with 200 mg of a crushed and meshed catalyst having a uniform particle size, and hydrogen sulfide / hydrogen gas (10% hydrogen sulfide) is supplied at a rate of 50 ml / min.
The mixture was allowed to flow at 2 ° C. for 2 hours to carry out preliminary sulfurization. And temperature 3
At 50 ° C., thiophene (6%) was added at 50 ° C.
The thiophene conversion was measured 3 hours after flowing at a flow rate of milliliter / minute. The results are shown in Table 1. The rate constant per thiophene conversion per catalyst mass was used to evaluate the desulfurization activity.
【００２７】〔実施例２〕三酸化モリブデン１０８ｇ、
塩基性炭酸ニッケル４８ｇ（ＮｉＯとして２６ｇ）、正
リン酸（純度８５％）３８ｇ、りんご酸５ｇとポリエチ
レングリコール（分子量４００，分解温度２００℃以
上）３０ｇをイオン交換水に溶解させ、全量を２７５ｃ
ｃの含浸液とした。次にその含浸液５５ｃｃを実施例１
で調製したシリカ含有アルミナ担体Ｃ１の吸水量に見合
った量に調製し、１００ｇに常圧含浸させた。この担持
物を、１２０℃で３時間乾燥させて、空気中５００℃、
３時間焼成して触媒IIを得た。その物性を第１表に示
す。その触媒IIについて、実施例１と同様に脱硫活性試
験を実施した。結果を第１表に示す。Example 2 108 g of molybdenum trioxide,
48 g of basic nickel carbonate (26 g as NiO), 38 g of orthophosphoric acid (85% purity), 5 g of malic acid and 30 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or higher) are dissolved in ion-exchanged water, and the total amount is 275 c.
The impregnating liquid of c was used. Next, 55 cc of the impregnating liquid was used in Example 1.
Was adjusted to an amount corresponding to the amount of water absorption of the silica-containing alumina carrier C1 prepared in the above section, and 100 g of the carrier was impregnated at normal pressure. The support was dried at 120 ° C. for 3 hours, and then dried in air at 500 ° C.
After calcining for 3 hours, catalyst II was obtained. The physical properties are shown in Table 1. The catalyst II was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００２８】〔実施例３〕実施例１において、ポリエチ
レングリコール３０ｇを添加しなかったこと以外は同様
にして触媒III を得た。その物性を第１表に示す。その
触媒III について、実施例１と同様に脱硫活性試験を実
施した。結果を第１表に示す。Example 3 A catalyst III was obtained in the same manner as in Example 1 except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst III was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００２９】〔実施例４〕実施例２において、ポリエチ
レングリコール３０ｇを添加しなかったこと以外は同様
にして触媒IVを得た。その物性を第１表に示す。その触
媒IVについて、実施例１と同様に脱硫活性試験を実施し
た。結果を第１表に示す。Example 4 A catalyst IV was obtained in the same manner as in Example 2 except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst IV was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３０】〔実施例５〕実施例２において、ポリエチ
レングリコール３０ｇの代わりに、１，３−ブタンジオ
ール（沸点２０４℃）を使用したこと以外は同様にして
触媒Ｖを得た。その物性を第１表に示す。その触媒Ｖに
ついて、実施例１と同様に脱硫活性試験を実施した。結
果を第１表に示す。Example 5 A catalyst V was obtained in the same manner as in Example 2, except that 1,3-butanediol (boiling point: 204 ° C.) was used instead of 30 g of polyethylene glycol. The physical properties are shown in Table 1. The catalyst V was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３１】〔比較例１〕純水１リットルに、水酸化ナ
トリウム３５．４ｇを溶解させ、さらに、アルミン酸ソ
ーダ９９．３ｇを添加して、均一なアルミナ溶液Ｂ２を
得た。さらに、純水１リットルに硝酸アルミニウム５０
０ｇを溶解させ、アルミナ溶液Ａ２を得た。純水２．３
８リットルを７０℃に加温し、攪拌しながら、アルミナ
溶液Ａ２をｐＨ３．６になるまで添加した。次にアルミ
ナ溶液Ｂ２をｐＨ９．０になるまで添加して、５分間攪
拌しながら熟成させた。続いて再びアルミナ溶液Ａ２を
添加して、ｐＨを３．６とし、攪拌しなが５分間熟成さ
せた。このようにｐＨを３．６から９．０の間で変化さ
せる操作を８回繰り返した。その後、得られたゲルをろ
過、洗浄してアルミナゲルを５８０ｇ得た。このゲルを
１２０℃、１６時間乾燥させ、さらに５００℃で２時間
焼成してアルミナ担体Ｃ２を得た。Comparative Example 1 35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.3 g of sodium aluminate was added to obtain a uniform alumina solution B2. Furthermore, 50 l of aluminum nitrate is added to 1 liter of pure water.
0 g was dissolved to obtain an alumina solution A2. 2.3 pure water
Eight liters were heated to 70 ° C., and while stirring, alumina solution A2 was added until pH 3.6. Next, alumina solution B2 was added until the pH became 9.0, and the mixture was aged while stirring for 5 minutes. Subsequently, alumina solution A2 was added again to adjust the pH to 3.6, and the mixture was aged for 5 minutes with stirring. The operation of changing the pH between 3.6 and 9.0 was repeated eight times. Thereafter, the obtained gel was filtered and washed to obtain 580 g of an alumina gel. The gel was dried at 120 ° C. for 16 hours and calcined at 500 ° C. for 2 hours to obtain an alumina carrier C2.
【００３２】三酸化モリブデン８３ｇ、塩基性炭酸ニッ
ケル３７ｇ（ＮｉＯとして２０ｇ）、正リン酸（純度８
５％）３８ｇとポリエチレングリコール（分子量４０
０，分解温度２００℃以上）３０ｇをイオン交換水に溶
解させ、全量を２７５ｃｃの含浸液とした。次にその含
浸液５５ｃｃを前記のアルミナ担体Ｃ２の吸水量に見合
った量に調製し、１００ｇに常圧含浸させた。この担持
物を、１２０℃で３時間乾燥させて、空気中５００℃、
３時間焼成して触媒VIを得た。その物性を第１表に示
す。その触媒VIについて、実施例１と同様に脱硫活性試
験を実施した。結果を第１表に示す。83 g of molybdenum trioxide, 37 g of basic nickel carbonate (20 g as NiO), orthophosphoric acid (purity 8
5 g) and polyethylene glycol (molecular weight 40)
(0, decomposition temperature of 200 ° C. or higher) 30 g was dissolved in ion-exchanged water, and the total amount was 275 cc. Next, 55 cc of the impregnating liquid was adjusted to an amount corresponding to the water absorption of the alumina carrier C2, and 100 g of the impregnated liquid was impregnated at normal pressure. The support was dried at 120 ° C. for 3 hours, and then dried in air at 500 ° C.
After calcining for 3 hours, catalyst VI was obtained. The physical properties are shown in Table 1. The catalyst VI was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３３】〔比較例２〕純水２．３８リットルを７０
℃に加温し、攪拌しながら、水ガラス３．３ｇを添加し
てシリカ溶液Ｓ２を得た。溶液のｐＨは８．５であっ
た。また、純水１リットルに水酸化ナトリウム３５．４
ｇを溶解させ、さらにアルミン酸ソーダ９９．３ｇを添
加して均一なアルミナ溶液Ｂ３を得た。さらに、純水１
リットルに硝酸アルミニウム５００ｇを溶解させ、アル
ミナ溶液Ａ３を得た。次に、シリカ溶液Ｓ２にアルミナ
溶液Ａ３をｐＨ３．６になるまで添加した。この時、溶
液中には白色のゲルが生成した。次に、アルミナ溶液Ｂ
３をｐＨ９．０になるまで添加して、５分間攪拌しなが
らゲルを熟成させた。続いて再びアルミナ溶液Ａ３を添
加してｐＨを３．６とし、攪拌しながら５分間ゲルを熟
成させた。このようにｐＨを３．６〜９．０の間で変化
させる操作を１０回繰り返した。その後、得られたゲル
をろ過、洗浄してシリカ含有アルミナゲルを５８０ｇ得
た。このゲルを１２０℃、１６時間乾燥させ、さらに５
００℃で２時間焼成してシリカ含有アルミン担体Ｃ３を
得た。[Comparative Example 2] 2.38 liters of pure water was added to 70
The mixture was heated to ℃ and stirred, 3.3 g of water glass was added to obtain a silica solution S2. The pH of the solution was 8.5. Also, 35.4% sodium hydroxide was added to 1 liter of pure water.
g, and 99.3 g of sodium aluminate was further added to obtain a uniform alumina solution B3. Furthermore, pure water 1
500 g of aluminum nitrate was dissolved in 1 liter to obtain an alumina solution A3. Next, the alumina solution A3 was added to the silica solution S2 until the pH reached 3.6. At this time, a white gel was formed in the solution. Next, alumina solution B
3 was added until pH 9.0, and the gel was aged while stirring for 5 minutes. Subsequently, alumina solution A3 was added again to adjust the pH to 3.6, and the gel was aged for 5 minutes with stirring. The operation of changing the pH between 3.6 and 9.0 in this manner was repeated 10 times. Thereafter, the obtained gel was filtered and washed to obtain 580 g of a silica-containing alumina gel. The gel was dried at 120 ° C. for 16 hours, and further dried for 5 hours.
The mixture was calcined at 00 ° C. for 2 hours to obtain a silica-containing alumina carrier C3.
【００３４】三酸化モリブデン１０８ｇ、塩基性炭酸ニ
ッケル４８ｇ（ＮｉＯとして２６ｇ）、正リン酸（純度
８５％）３８ｇ、りんご酸５ｇとポリエチレングリコー
ル（分子量４００，分解温度２００℃以上）４０ｇをイ
オン交換水に溶解させ、全量を２７５ｃｃの含浸液とし
た。次にその含浸液５５ｃｃをシリカ含有アルミナ担体
Ｃ３の吸水量に見合った量に調製し、１００ｇに常圧含
浸させた。この担持物を、１２０℃で３時間乾燥させ
て、空気中５００℃、３時間焼成して触媒VII を得た。
その物性を第１表に示す。その触媒VII について、実施
例１と同様に脱硫活性試験を実施した。結果を第１表に
示す。108 g of molybdenum trioxide, 48 g of basic nickel carbonate (26 g as NiO), 38 g of orthophosphoric acid (purity 85%), 5 g of malic acid and 40 g of polyethylene glycol (molecular weight 400, decomposition temperature 200 ° C. or more) were ion-exchanged with water. To make 275 cc of the impregnating liquid. Next, 55 cc of the impregnating liquid was adjusted to an amount corresponding to the water absorption of the silica-containing alumina carrier C3, and 100 g of the impregnating liquid was impregnated at normal pressure. The supported material was dried at 120 ° C. for 3 hours and calcined in air at 500 ° C. for 3 hours to obtain a catalyst VII.
The physical properties are shown in Table 1. The catalyst VII was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３５】〔比較例３〕比較例１において、ポリエチ
レングリコール３０ｇを添加しなかったこと以外は同様
にして触媒VIIIを得た。その物性を第１表に示す。その
触媒VIIIについて、実施例１と同様に脱硫活性試験を実
施した。結果を第１表に示す。Comparative Example 3 A catalyst VIII was obtained in the same manner as in Comparative Example 1, except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst VIII was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３６】〔比較例４〕比較例２において、ポリエチ
レングリコール３０ｇを添加しなかったこと以外は同様
にして触媒IXを得た。その物性を第１表に示す。その触
媒IXについて、実施例１と同様に脱硫活性試験を実施し
た。結果を第１表に示す。Comparative Example 4 A catalyst IX was obtained in the same manner as in Comparative Example 2, except that 30 g of polyethylene glycol was not added. The physical properties are shown in Table 1. The catalyst IX was subjected to a desulfurization activity test in the same manner as in Example 1. The results are shown in Table 1.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【表３】 [Table 3]
【００４０】〔実施例６〕上流側に充填する脱金属触媒の調製 純水１リットルに、水酸化ナトリウム３５．４ｇを溶解
させ、さらに、アルミン酸ソーダ９９．３ｇを添加し
て、均一なアルミナ溶液Ｂ４を得た。また、純水１リッ
トルに硝酸アルミニウム５００ｇを溶解させ、アルミナ
溶液Ａ４を得た。純水２．３８リットルを７０℃に加温
し、攪拌しながら、アルミナ溶液Ａ４をｐＨ２．６にな
るまで添加した。次にアルミナ溶液Ｂ４をｐＨ９．０に
なるまで添加して、５分間攪拌しながら熟成させた。続
いて再びアルミナ溶液Ａ４を添加して、ｐＨを３．６と
し、攪拌しなが５分間熟成させた。このようにｐＨを
３．６から９．０の間で変化させる操作を１３回繰り返
した。その後、得られたゲルをろ過、洗浄してアルミナ
ゲルを１，０７５ｇ得た。このゲルを１２０℃、１６時
間乾燥させ、さらに５００℃で２時間焼成してアルミナ
担体Ｃ４を得た。Example 6 Preparation of Demetallizing Catalyst Filled Upstream 35.4 g of sodium hydroxide was dissolved in 1 liter of pure water, and 99.3 g of sodium aluminate was added. Solution B4 was obtained. Further, 500 g of aluminum nitrate was dissolved in 1 liter of pure water to obtain an alumina solution A4. 2.38 liters of pure water was heated to 70 ° C., and while stirring, alumina solution A4 was added until pH 2.6. Next, alumina solution B4 was added until the pH became 9.0, and the mixture was aged while stirring for 5 minutes. Subsequently, alumina solution A4 was added again to adjust the pH to 3.6, and the mixture was aged for 5 minutes with stirring. The operation of changing the pH between 3.6 and 9.0 in this way was repeated 13 times. Thereafter, the obtained gel was filtered and washed to obtain 1,075 g of an alumina gel. This gel was dried at 120 ° C. for 16 hours and calcined at 500 ° C. for 2 hours to obtain an alumina carrier C4.
【００４１】三酸化モリブデン３１ｇ、塩基性炭酸ニッ
ケル１１ｇ（ＮｉＯとして６ｇ）、りんご酸５０ｇをイ
オン交換水に溶解させ、全量を２００ｃｃの含浸液とし
た。次にその含浸液５５ｃｃを前記のアルミナ担体Ｃ４
の吸水量に見合った量に調製し、１００ｇに常圧含浸さ
せた。この担持物を、１２０℃で３時間乾燥させて、空
気中５００℃、３時間焼成して触媒Ｘを得た。その物性
を第２表に示す。31 g of molybdenum trioxide, 11 g of basic nickel carbonate (6 g as NiO) and 50 g of malic acid were dissolved in ion-exchanged water to make a total amount of 200 cc. Next, 55 cc of the impregnating liquid was added to the alumina carrier C4.
Was adjusted to an amount corresponding to the water absorption, and 100 g was impregnated at normal pressure. The supported material was dried at 120 ° C. for 3 hours, and calcined in air at 500 ° C. for 3 hours to obtain a catalyst X. The physical properties are shown in Table 2.
【００４２】[0042]
【表４】 [Table 4]
【００４３】上流側に触媒Ｘの脱金属触媒を３０容量
％、下流側に触媒Ｉの水素化処理触媒を７０容量％を反
応管に充填して、下記のとおり触媒の性能を評価した。
結果を第４表に示す。The reaction tube was charged with 30% by volume of the demetallizing catalyst of the catalyst X on the upstream side and 70% by volume of the hydrotreating catalyst of the catalyst I on the downstream side, and the performance of the catalyst was evaluated as follows.
The results are shown in Table 4.
【００４４】・触媒の性能評価 小型高圧固定床反応装置の反応管に、上記の脱メタル触
媒と水素化処理触媒を充填した。中東系軽質軽油（ＬＧ
Ｏ，硫黄分１．１８質量％、窒素分７０ｐｐｍ）にジメ
チルジスルフィドを添加して硫黄濃度を２．５質量％に
調整した予備硫化油を調製した。この予備硫化油を、上
記の触媒に、水素ガスとともに２５０℃で２４時間流通
させて予備硫化した。また、原料油としては、金属（バ
ナジウム，ニッケル）含有量が非常に多い中東系原油の
常圧残油を用いた。その性状を第３表に示す。Evaluation of catalyst performance A reaction tube of a small-sized high-pressure fixed-bed reactor was filled with the above-mentioned demetallizing catalyst and hydrotreating catalyst. Middle Eastern light oil (LG
O, sulfur content 1.18 mass%, nitrogen content 70 ppm) and dimethyl disulfide were added to prepare a preliminary sulfurized oil whose sulfur concentration was adjusted to 2.5 mass%. This pre-sulfurized oil was pre-sulfurized by flowing it through the above-mentioned catalyst together with hydrogen gas at 250 ° C. for 24 hours. In addition, as the raw material oil, an ordinary pressure residual oil of Middle Eastern crude oil having a very large metal (vanadium, nickel) content was used. The properties are shown in Table 3.
【００４５】[0045]
【表５】 [Table 5]
【００４６】この原料油を、上記の予備硫化後の触媒
に、水素ガスとともに流通させて、以下の条件で水素化
処理を行った。 生成油のターゲット硫黄分：０．５質量％ 水素分圧：１３．５ＭＰａ 液空間速度（ＬＨＳＶ）：０．６ｈｒ-1 水素／オイル比：８５０Ｎｍ3 ／ｋｌThe feedstock was passed through the catalyst after the preliminary sulfurization together with hydrogen gas, and was subjected to hydrotreatment under the following conditions. Target sulfur content of generated oil: 0.5% by mass Hydrogen partial pressure: 13.5 MPa Liquid hourly space velocity (LHSV): 0.6 hr -1 Hydrogen / oil ratio: 850 Nm 3 / kl
【００４７】〔比較例５〕上流側に触媒Ｘの脱メタル触
媒を３０容量％、下流側に触媒VIIIの水素化処理触媒を
７０容量％を反応管に充填して、実施例６と同様に触媒
の性能を評価した。結果を第４表に示す。Comparative Example 5 A reaction tube was charged with 30% by volume of a demetalization catalyst for the catalyst X on the upstream side and 70% by volume of a hydrogenation catalyst for the catalyst VIII on the downstream side, in the same manner as in Example 6. The performance of the catalyst was evaluated. The results are shown in Table 4.
【００４８】[0048]
【表６】 [Table 6]
【００４９】[0049]
【発明の効果】本発明は、より低温における高脱硫活性
と耐金属蓄積性を有する水素化処理触媒であるので、そ
の水素化処理触媒を使用し重質炭化水素油を水素化処理
を行うと、従来より運転初期温度を低くでき、また触媒
の劣化速度を緩和できるため、触媒の寿命が長くなり、
原料油の増処理と触媒交換頻度の低減につながる。The present invention is a hydrotreating catalyst having high desulfurization activity and metal accumulation resistance at lower temperatures. Therefore, when the hydrotreating catalyst is used to hydrotreat heavy hydrocarbon oil, In addition, since the initial operation temperature can be lowered and the deterioration rate of the catalyst can be reduced, the life of the catalyst is prolonged,
This leads to an increase in the amount of feedstock and a reduction in the frequency of catalyst replacement.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｂ０１Ｊ 35/10 ３０１ Ｃ１０Ｇ 45/08 Ａ Ｃ１０Ｇ 45/08 65/04 65/04 Ｂ０１Ｊ 23/64 １０３Ｍ Ｆターム(参考） 4G069 AA03 BA03A BA03B BA03C BC57A BC59A BC59B BC59C BC65A BC68A BC68B BC68C BC69A CC02 DA06 EA02Y EC03X EC07X EC15X FA02 FB14 4H029 CA00 DA00 DA09 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI Theme coat ゛ (Reference) B01J 35/10 301 C10G 45/08 A C10G 45/08 65/04 65/04 B01J 23/64 103M F-term (Reference) 4G069 AA03 BA03A BA03B BA03C BC57A BC59A BC59B BC59C BC65A BC68A BC68B BC68C BC69A CC02 DA06 EA02Y EC03X EC07X EC15X FA02 FB14 4H029 CA00 DA00 DA09
Claims (8)
ナ担体に、周期律表第６族の金属の少なくとも一種及び
周期律表第８〜１０族の金属から選ばれる少なくとも一
種を担持した触媒であって、該触媒の平均細孔直径（Ｐ
Ｄ）が１００〜１７０Åで、比表面積（ＳＡ）が１４０
〜２５０ｍ2 ／ｇであり、かつ両者が下記の（１）式を
満足し、さらに全細孔容量が０．４〜１．０ｃｃ／ｇで
あることを特徴とする水素化処理触媒。 ＳＡ＋１．６５ＰＤ ＞ ４１０ ・・・（１）1. A catalyst in which at least one metal selected from Group 6 of the periodic table and at least one metal selected from Group 8 to 10 of the periodic table are supported on an alumina carrier containing 1 to 10% by mass of silica. Then, the average pore diameter (P
D) is 100-170 ° and the specific surface area (SA) is 140
水 素 250 m 2 / g, both satisfy the following formula (1), and have a total pore volume of 0.4 to 1.0 cc / g. SA + 1.65PD> 410 (1)
り、周期律表第８〜１０族金属がニッケルである請求項
１記載の水素化処理触媒。2. The hydrotreating catalyst according to claim 1, wherein the metal belonging to Group 6 of the periodic table is molybdenum, and the metal belonging to Groups 8 to 10 of the periodic table is nickel.
である請求項１又は２に記載の水素化処理触媒。3. The hydrotreating catalyst according to claim 1, wherein the catalyst contains 3 to 5% by mass of phosphorus.
度２００℃以上の水溶性有機化合物を含有する含浸液を
用いてなされたものである請求項１〜３のいずれかに記
載の水素化処理触媒。4. The hydrogen according to claim 1, wherein the supporting of the metal on the carrier is performed using an impregnating liquid containing a water-soluble organic compound having a boiling point or a decomposition temperature of 200 ° C. or higher. Conversion catalyst.
ールである請求項４記載の水素化処理触媒。5. The hydrotreating catalyst according to claim 4, wherein the water-soluble organic compound is polyethylene glycol.
化処理触媒を用いた重質炭化水素油の水素化処理方法。6. A method for hydrotreating heavy hydrocarbon oil using the hydrotreating catalyst according to any one of claims 1 to 5.
〜５のいずれかに記載の水素化処理触媒を用いた請求項
６記載の重質炭化水素油の水素化処理方法。7. The demetalization catalyst on the upstream side, and the demetalization catalyst on the downstream side.
The method for hydrotreating heavy hydrocarbon oil according to claim 6, wherein the hydrotreating catalyst according to any one of (5) to (5) is used.
は減圧残油である請求項６又は７に記載の重質炭化水素
油の水素化処理方法。8. The method for hydrotreating heavy hydrocarbon oil according to claim 6, wherein the heavy hydrocarbon oil is a vacuum gas oil, a normal pressure residual oil or a vacuum residual oil.
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| CN103861627A (en) * | 2012-12-18 | 2014-06-18 | Ifp新能源公司 | Residue hydrotreatment catalyst comprising vanadium, and its use in a residue hydroconversion process |
| FR2999454A1 (en) * | 2012-12-18 | 2014-06-20 | IFP Energies Nouvelles | New catalyst comprising at least one element of group VIB, optionally at least one element of group VIII, phosphorous and at least one aluminosilicate oxide support, useful for hydrotreating heavy hydrocarbon feedstocks |
| CN112973717A (en) * | 2019-12-16 | 2021-06-18 | 北京中能炜业科技发展有限公司 | Hydrofining catalyst and preparation method thereof |
| CN116060022A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and production method thereof |
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