JP6896841B2 - 低い沈殿物収率を有する重質炭化水素の高転化率のための沸騰床プロセス - Google Patents
低い沈殿物収率を有する重質炭化水素の高転化率のための沸騰床プロセス Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims description 65
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 65
- 238000009835 boiling Methods 0.000 title claims description 60
- 238000006243 chemical reaction Methods 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 55
- 230000008569 process Effects 0.000 title claims description 48
- 239000002244 precipitate Substances 0.000 title claims description 32
- 239000003054 catalyst Substances 0.000 claims description 132
- 239000002245 particle Substances 0.000 claims description 100
- 239000004215 Carbon black (E152) Substances 0.000 claims description 58
- 238000005984 hydrogenation reaction Methods 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 11
- 239000012084 conversion product Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000010998 test method Methods 0.000 claims description 4
- 239000005078 molybdenum compound Substances 0.000 claims description 3
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 3
- 150000002816 nickel compounds Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- KMPZCBWYGBGUPB-UHFFFAOYSA-N molybdenum;hydrate Chemical class O.[Mo] KMPZCBWYGBGUPB-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
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- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
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Description
この実施例1は、その特徴的な断面周囲対断面積の値が小さくなるような幾何学的形状及びその小粒子を有する、含浸された比較触媒A、本発明の一実施形態での使用される、含浸された触媒B、および特徴的な断面周囲対断面積の値が相対的に大きくなるような幾何学的形状の調製を記載する。
この実施例2では、触媒Aおよび触媒Bの性能試験の条件と性能試験の結果について記載する。
Claims (7)
- 試験方法ASTM−4870により測定された0.5重量%未満の低い沈殿物収率で重質炭化水素供給原料の高い転化率を提供する、前記重質炭化水素供給原料の水素化転化のために沸騰床反応器システムを使用するプロセスであって、
前記重質炭化水素供給原料を、沸騰床反応容器によって画定された反応器容積内に収容された沸騰床反応ゾーンに導入することであって、前記反応器容積は前記沸騰床反応ゾーンの上方の上側ゾーンと前記沸騰床反応ゾーンの下方の下側ゾーンとを含み、前記沸騰床反応ゾーンは、小さな粒子サイズの成形された水素化処理触媒粒子の触媒床を含み、前記成形された水素化処理触媒粒子は、焼成成形アルミナ担体を含み、焼成成形アルミナ担体は、さらに少なくとも1つの活性触媒金属成分で含浸され、続いて300℃〜800℃の温度でか焼され、前記成形された水素化処理触媒粒子は、前記成形された水素化処理触媒粒子に含有される350オングストロームを超える直径を有する孔が全孔容積の9%未満である低いマクロポロシティと、5mm−1〜8mm−1の範囲内である断面周囲対断面積の第1の比を提供する幾何学的形状と、を有することで更に特徴付けられる、導入することと、ここで、前記幾何学的形状は多葉断面から選択される、
水素化転化反応条件下で、前記重質炭化水素供給原料を前記沸騰床反応ゾーン内の前記成形された水素化処理触媒粒子と接触させることと、
前記上側ゾーンから、試験方法ASTM−4870により測定された0.5重量%未満の低い沈殿物含有量を有する重質炭化水素転化生成物を得ることと、を含む、プロセス。 - 前記成形された水素化処理触媒粒子は、70重量%〜99重量%の範囲内の量、3重量%〜15重量%の範囲内の無機酸化物成分の量のモリブデン化合物、0.5重量%〜6重量%の範囲内の量のニッケル化合物を更に含み、各重量%は、前記成形された水素化処理触媒粒子とその実際の形態にかかわらず酸化物としての前記金属との合計重量に基づく、請求項1に記載のプロセス。
- 前記水素化転化反応条件は、316℃(600oF)〜538℃(1,000oF)の範囲内の接触温度、500psia〜6,000psiaの範囲内の接触圧、500scf/bbl〜10,000scf/bblの範囲内の水素対油の比、および0.1hr−1〜5hr−1の範囲内の液空間速度(LHSV)を含む、請求項2に記載のプロセス。
- 前記多葉断面が、三葉断面である、請求項1に記載のプロセス。
- 前記断面周囲対断面積が5.5mm−1〜7mm−1の範囲内である、請求項4に記載のプロセス。
- 前記低マクロポロシティが、前記成形された水素化処理触媒粒子に含まれる350Aを超える直径を有する孔の全孔容積の6%未満である、請求項5に記載のプロセス。
- 前記低マクロポロシティが、前記成形された水素化処理触媒粒子に含まれる350Aを超える直径を有する孔の全孔容積の2%未満である、請求項5に記載のプロセス。
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