JP2021511951A - 重油中の金属及び硫黄の削減のための水素化処理触媒 - Google Patents
重油中の金属及び硫黄の削減のための水素化処理触媒 Download PDFInfo
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- JP2021511951A JP2021511951A JP2020539077A JP2020539077A JP2021511951A JP 2021511951 A JP2021511951 A JP 2021511951A JP 2020539077 A JP2020539077 A JP 2020539077A JP 2020539077 A JP2020539077 A JP 2020539077A JP 2021511951 A JP2021511951 A JP 2021511951A
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- Prior art keywords
- metal
- catalyst
- catalyst according
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- Granted
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 136
- 239000002184 metal Substances 0.000 title claims abstract description 136
- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- 238000005984 hydrogenation reaction Methods 0.000 title description 36
- 229910052717 sulfur Inorganic materials 0.000 title description 14
- 239000011593 sulfur Substances 0.000 title description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 13
- 239000000295 fuel oil Substances 0.000 title description 3
- 239000011148 porous material Substances 0.000 claims abstract description 141
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 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 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 239000011733 molybdenum Substances 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- 239000010948 rhodium Substances 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 238000010586 diagram Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 58
- 230000000052 comparative effect Effects 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000002253 acid Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000012438 extruded product Nutrition 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000000877 morphologic effect Effects 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
- 238000001935 peptisation Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- -1 porphyrin compounds Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001432959 Chernes Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 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
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- RVRCFVVLDHTFFA-UHFFFAOYSA-N heptasodium;tungsten;nonatriacontahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W].[W] RVRCFVVLDHTFFA-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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Abstract
Description
本出願は、2018年1月31日に提出された米国仮特許出願第62/624236号の優先権出願日の利益を主張し、その開示は参照により本明細書に組み込まれる。
本発明は、水素化処理触媒に関する。より具体的には、本発明は、三金属組成を有する水素化処理触媒、ならびに改善された脱金属能力及び硫黄除去のために特に設計された細孔ネットワークに関する。
k=各個々の反応(HDM、HDNi、HDV
又はHDS)の反応速度定数
E=活性化エネルギー
R=気体定数
A=頻度因子
T=温度、ケルビン
Claims (36)
- 担体と、前記担体に含浸された金属成分と、を含む、触媒であって、
−前記担体が、アルミナを含み、
−前記金属成分が、第1の金属画分及び第2の金属画分を含み、前記第1の金属画分が、クロム、モリブデン、又はタングステンから選択される少なくとも1つの金属を含み、前記第2の金属画分が、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、又はプラチナから選択される少なくとも2つの金属を含み、
前記触媒が、12nm〜16nm未満の細孔径を有する細孔に対して0.28〜0.45mL/gの第1の細孔容積、及び2.0nm〜12.0nm未満の細孔に対して0.15〜0.28mL/gの第2の細孔容積を有する、触媒。 - 2.0〜6.0の範囲の前記第2の金属画分に対する前記第1の金属画分の比を更に含む、請求項1に記載の触媒。
- 前記比が、3.0〜5.0の範囲である、請求項2に記載の触媒。
- 前記比が、3.5〜4.5の範囲である、請求項3に記載の触媒。
- 前記第2の金属画分が、コバルト、ロジウム、又はイリジウムから選択される第1の金属サブグループからの少なくとも1つの金属と、ニッケル、パラジウム、又は白金から選択される第2の金属サブグループからの少なくとも1つの金属と、を含む、請求項1に記載の触媒。
- 前記第1の金属サブグループが、前記触媒の総重量に基づいて0.5〜2.0重量%の量で存在し、前記第2の金属サブグループが、前記触媒の総重量に基づいて0.3〜1.0重量%の量で存在する、請求項5に記載の触媒。
- 前記触媒の総重量に基づいて、前記第1の金属サブグループが、0.80〜1.20重量%の量で存在し、前記第2の金属サブグループが、0.40〜0.60重量%の量で存在する、請求項6に記載の触媒。
- 前記第2の金属画分が、前記第1の金属サブグループからの1つの金属と、前記第2の金属サブグループからの1つの金属と、を含む、請求項5に記載の触媒。
- 前記第1の金属画分及び前記第2の金属画分の総重量が、前記触媒の総重量に基づいて3.0〜12.0重量%である、請求項1に記載の触媒。
- 前記第1の金属画分及び前記第2の金属画分の総重量が、5.0〜10.0重量%である、請求項9に記載の触媒。
- 前記第1の金属画分及び前記第2の金属画分の総重量が、6.0〜8.0重量%である、請求項10に記載の触媒。
- 前記第1の金属画分が、モリブデンである、請求項1に記載の触媒。
- 前記第2の金属画分が、コバルト及びニッケルを含む、請求項1に記載の触媒。
- 前記金属成分が、モリブデン、コバルト及びニッケルを含む、請求項1に記載の触媒。
- 前記第1の細孔容積が、0.30〜0.40mL/gである、請求項1に記載の触媒。
- 前記第1の細孔容積が、0.32〜0.36mL/gである、請求項15に記載の触媒。
- 前記第2の細孔容積が、0.16〜0.25mL/gである、請求項1に記載の触媒。
- 前記第2の細孔容積が、0.17〜0.22mL/gである、請求項17に記載の触媒。
- 16nm〜60nmの細孔に対して、0.01〜0.20mL/gの第3の細孔容積を更に含む、請求項1に記載の触媒。
- 前記第3の細孔容積が、0.02〜0.19mL/gである、請求項19に記載の触媒。
- 前記第3の細孔容積が、0.10〜0.18mL/gである、請求項20に記載の触媒。
- 前記第1の細孔容積及び前記第3の細孔容積の総計が、0.32〜0.60mL/gである、請求項1に記載の触媒。
- 前記第1の細孔容積及び前記第3の細孔容積の総計が、0.42〜0.55mL/gである、請求項22に記載の触媒。
- 前記第1の細孔容積及び前記第3の細孔容積の総計が、0.46〜0.52mL/gである、請求項23に記載の触媒。
- 0.63〜0.75mL/gの総細孔容積を更に含む、請求項1に記載の触媒。
- 総細孔容積が、0.64〜0.74mL/gである、請求項25に記載の触媒。
- 総細孔容積が、0.65〜0.73mL/gである、請求項26に記載の触媒。
- 180〜230m2/gの比表面積を更に含む、請求項1に記載の触媒。
- 前記比表面積が、185〜225m2/gである、請求項28に記載の触媒。
- 前記比表面積が、190〜220m2/gである、請求項29に記載の触媒。
- 10.0〜16.0nmの中央細孔径を更に含む、請求項1に記載の触媒。
- 前記中央細孔径が、11.0〜15.0nmである、請求項31に記載の触媒。
- 前記中央細孔径が、13.4〜14.3nmである、請求項32に記載の触媒。
- 前記触媒の総重量に基づいて、1000ppmの最大リン含有量を更に含む、請求項1に記載の触媒。
- 前記最大リン含有量が、200ppmである、請求項34に記載の触媒。
- 触媒を生成するためのプロセスであって、金属成分を担体上へ含侵させることを含み、
−前記担体が、アルミナを含み、
−前記金属成分が、第1の金属画分及び第2の金属画分を含み、前記第1の金属画分が、クロム、モリブデン、タングステン、又はそれらの混合物から選択される少なくとも1つの金属を含み、前記第2の金属画分が、コバルト、ロジウム、イリジウム、ニッケル、パラジウム、プラチナ、又はそれらの混合物から選択される少なくとも2つの異なる金属を含み、
前記触媒が、12nm〜16nm未満の細孔径を有する細孔に対して0.28〜0.45mL/gの第1の細孔容積、及び2.0nm〜12.0nm未満の細孔に対して0.15〜0.28mL/gの第2の細孔容積を有する、プロセス。
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