JP2019104004A - Fccからのガソリンに選択的な水素化脱硫触媒 - Google Patents
Fccからのガソリンに選択的な水素化脱硫触媒 Download PDFInfo
- Publication number
- JP2019104004A JP2019104004A JP2018230487A JP2018230487A JP2019104004A JP 2019104004 A JP2019104004 A JP 2019104004A JP 2018230487 A JP2018230487 A JP 2018230487A JP 2018230487 A JP2018230487 A JP 2018230487A JP 2019104004 A JP2019104004 A JP 2019104004A
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- Prior art keywords
- catalyst
- alumina
- weight
- support
- group vib
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 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 177
- 229910052751 metal Inorganic materials 0.000 claims abstract description 92
- 239000002184 metal Substances 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 36
- 239000011574 phosphorus Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 150000002894 organic compounds Chemical class 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 28
- 229910052750 molybdenum Inorganic materials 0.000 claims description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
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- 230000008569 process Effects 0.000 claims description 18
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 125000004429 atom Chemical group 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
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- 238000001354 calcination Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
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- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
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- -1 VIB metal oxide Chemical class 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- SEQKRHFRPICQDD-UHFFFAOYSA-N N-tris(hydroxymethyl)methylglycine Chemical compound OCC(CO)(CO)[NH2+]CC([O-])=O SEQKRHFRPICQDD-UHFFFAOYSA-N 0.000 claims description 6
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- 238000004523 catalytic cracking Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002706 AlOOH Inorganic materials 0.000 claims description 4
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
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- 150000002825 nitriles Chemical class 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 claims description 3
- PLHCSZRZWOWUBW-UHFFFAOYSA-N 2-methoxyethyl 3-oxobutanoate Chemical compound COCCOC(=O)CC(C)=O PLHCSZRZWOWUBW-UHFFFAOYSA-N 0.000 claims description 3
- UZMAPBJVXOGOFT-UHFFFAOYSA-N Syringetin Natural products COC1=C(O)C(OC)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UZMAPBJVXOGOFT-UHFFFAOYSA-N 0.000 claims description 3
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- 150000001408 amides Chemical class 0.000 claims description 3
- KCFYHBSOLOXZIF-UHFFFAOYSA-N dihydrochrysin Natural products COC1=C(O)C(OC)=CC(C2OC3=CC(O)=CC(O)=C3C(=O)C2)=C1 KCFYHBSOLOXZIF-UHFFFAOYSA-N 0.000 claims description 3
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- 150000004706 metal oxides Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001414 amino alcohols Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 description 33
- 239000012071 phase Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 20
- 239000000654 additive Substances 0.000 description 15
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- 230000000996 additive effect Effects 0.000 description 14
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- 238000005984 hydrogenation reaction Methods 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000007704 transition Effects 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
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- 239000011148 porous material Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical compound CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 6
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- 150000002739 metals Chemical class 0.000 description 6
- 235000011007 phosphoric acid Nutrition 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 5
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- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 4
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- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 3
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Images
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Abstract
Description
石油精製処理並びに石油化学は、現在、新しい要求にさらされている。実際に、全ての国は、厳しい硫黄仕様を徐々に採用しており、欧州および日本において市販のガソリン中、例えば硫黄10ppm(重量)を達成することを目標としている。硫黄の含有率を低減させるという課題は、本質的に、接触的(FCC(FCC Fluid Catalytic Cracking):流動接触分解)かまたは非接触的(コーキング、ビスブレーキング、水蒸気分解)かのいずれかの分解によって得られたガソリンに焦点を当てており、これらは、ガソリンプール中の硫黄の主要な前駆体である。
本発明は、それ故に、少なくとも1種の第VIB族金属と、少なくとも1種の第VIII族金属と、アルミナ担体とを含む水素化処理触媒であって、該アルミナ担体は、担体の重量に対して50重量%超かつ100重量%未満の含有率でガンマアルミナを有し、前記担体の比表面積は、25〜150m2/gである、ものに関する。
a) 770℃以下の温度でアルミナの前駆体の熱処理を行って、担体の重量に対して50重量%超かつ100重量%未満の含有率でガンマアルミナを含有する担体を得るようにする段階であって、前記担体の比表面積は、25〜150m2/gである、段階、
b) 第VIB族金属の少なくとも1種の成分と、第VIII族金属の少なくとも1種の成分と、任意のリンとを、前記担体と接触させて、触媒前駆体を得るようにする段階、
c) 段階b)を起源とする前記触媒前駆体を、200℃未満の温度で乾燥させる段階
を含む、方法にも関する。
・ 温度は200℃〜400℃であり;
・ 全圧は1〜3MPaであり;
・ 毎時空間速度は、触媒の容積に対する供給原料の容積流量であるとして定義されて、1〜10h−1であり;
・ 水素/ガソリン供給原料の容積比は、100〜600NL/Lである
において接触させられる。
(触媒)
本出願人は、それ故に、少なくとも1種の第VIB族金属と、少なくとも1種の第VIII族金属と、アルミナ担体とを含む水素化処理触媒であって、このアルミナ担体は、担体の重量に対して50重量%超かつ100重量%未満の含有率でガンマアルミナを有し、前記担体の比表面積は、25〜150m2/gである、水素化処理触媒は、硫化の後に、維持された水素化脱硫活性を有するだけではなく、オレフィンの水素化反応に対する水素化脱硫の選択性における有意な増加も有することを発見した。
式中、
・ X=第VIB族金属の重量%;
・ NA=6.022×1023に等しいアボガドロ数;
・ S=触媒の比表面積(m2/g);規格ASTM D3663に従って測定される;
・ MM=第VIB族金属のモル質量(例えば、モリブデンでは95.94g/モル)。
本発明による触媒は、当業者に知られているあらゆる調製様式によって調製されてよい。
a) 770℃以下の温度でアルミナの前駆体の熱処理を行って、担体を得る段階であって、該担体は、該担体の重量に対して50重量%超かつ100重量%未満の含有率でガンマアルミナを有し、前記担体は、25〜150m2/gの比表面積を有する、段階;
b) 第VIB族金属の少なくとも1種の成分と、第VIII族金属の少なくとも1種の成分と、任意のリンとを、前記担体と接触させて、触媒前駆体を得る段階;
c) 段階b)を起源とする前記触媒前駆体を、200℃未満の温度で乾燥させる段階
を含む、方法にも関する。
アルミナの前駆体は、場合によっては、乾燥させられた後に、熱処理を経る。例えば、乾燥処理が行われる際の温度は、100〜200℃である。
本発明による触媒を調製する方法の段階b)によると、少なくとも1種の第VIB族金属の成分と、少なくとも1種の第VIII族金属の成分と、任意のリンとは、担体と接触させられて、これにより、触媒前駆体が得られる。
第VIII族、第VIB族の金属および任意のリンの含浸の1回または複数回の段階の終わりに、触媒前駆体は、乾燥処理の段階c)に付され、この乾燥処理は、当業者に知られているあらゆる技術によって行われる。それは、有利には、大気圧または減圧で行われる。好ましくは、この段階は、大気圧で行われる。この段階c)が行われる際の温度は、200℃未満、好ましくは50〜180℃、好ましくは60℃〜150℃、非常に好ましくは75℃〜140℃である。
本発明は、炭化水素留分についての水素化処理方法にも関する。特に、本方法は、蒸留範囲が30〜260℃である炭化水素留分の水素化脱硫である。好ましくは、この炭化水素留分は、ガソリンタイプの留分である。非常に好ましくは、ガソリン留分は、オレフィン性ガソリン留分であり、例えば、接触分解ユニット(流動接触分解:Fluid Catalytic Cracking)を起源とするものである。
・ 温度は、200〜400℃、好ましくは230〜330℃であり;
・ その際の全圧は、1〜3MPa、好ましくは1.5〜2.5MPaであり;
・ 毎時空間速度(hourly space velocity:HSV)は、触媒の容積に対する供給原料の容積流量であるとして定義されて、1〜10h−1、好ましくは2〜6h−1であり;
・ 水素/ガソリン供給原料の容積比は、100〜600NL/L、好ましくは200〜400NL/Lである。
(実施例1(比較例):BET比表面積が100m2/g未満である高温アルミナS1の調製)
アルミナ担体の調製は、高温(1000℃)でアルミナの前駆体(ベーマイト)を直接的に焼成することによって行われる。担体S1のBET表面積は、窒素により規格ASTM D3663−03に従って決定される。ビーム[440]の相および非対称性の確認は、XRDによって以前に記載された方法に従って行われる。
アルミナ担体の調製は、低温(540℃)でアルミナの前駆体(ベーマイト)を直接的に焼成することによって行われる。担体S2のBET表面積は、窒素により規格ASTM D3663−03に従って決定される。XRD分析は、θおよびαの相を示さない。ビーム[440]の非対称性は1.25である。したがって、このサンプルは、82重量%のγアルミナからなる。
アルミナ担体の調製は、ガンマアルミナの押出物に1%の酢酸を乾式含浸させた後に、8時間にわたって180℃でオートクレーブ処理し、次いで、低温焼成(700℃)することによって行われる。担体S3のBET表面積は、窒素により規格ASTM D3663−03に従って決定される。XRD分析は、θおよびαの相を示さない。ビーム[440]の非対称性は1.36である。したがって、このサンプルは、74重量%のγアルミナからなる。
アルミナ担体の調製は、水中懸濁液中10重量%にあるベーマイト粉体を6時間にわたって225℃で熱処理することによって行われる。固体は、次いで、ろ過によって分離され、次いで、低温焼成(600℃)に付される。担体S4のBET表面積は、窒素により規格ASTM D3663−03に従って決定される。XRD分析は、θおよびαの相を示さない。ビーム[440]の非対称性は、1.20である。このサンプルは、したがって、87%のγアルミナからなる。
アルミニウム トリ−n−ヘキサノラートの溶液が、水の添加によって90℃で加水分解される。次いで、ヘキサノールが、共沸蒸留によって除去される。残渣は、反応器内で24時間にわたって110℃で加熱される。次いで、この固体は、ろ過によって分離され、次いで、低温焼成(700℃)に付される。
ソーダ溶液が、塩化アルミニウム水溶液に加えられる。反応媒体は、24時間にわたって200℃で加熱される。次いで、この固体は、ろ過によって分離され、次いで、低温焼成(560℃)に付される。
触媒A1は、酸化モリブデン、水酸化コバルト、リン酸およびクエン酸から調製された水溶液の乾式含浸によって得られ、コバルト、モリブデンおよびリンの前駆体およびクエン酸有機添加物を含有する前記溶液の容積は、固体アルミナ担体S1の細孔容積に厳密に等しい。水溶液中の前駆体および有機添加物の濃度の調節は、モリブデンの固定表面密度:触媒の面積(nm2)当たりモリブデン原子4.5個、それぞれ0.4および0.55に等しいCo/MoおよびP/Moの原子比および1に等しい添加物/Moのモル比を得るような重量含有率でCo、MoおよびPをアルミナ担体上に沈着させるようになされる。12時間にわたる熟成の段階の後、この固体は、12時間にわたって120℃で乾燥させられる。
触媒A2は、酸化モリブデン、水酸化コバルト、リン酸およびクエン酸から調製された水溶液の乾式含浸によって得られ、コバルト、モリブデンおよびリンの前駆体およびクエン酸有機添加物を含有する前記溶液の容積は、固体アルミナ担体S2の細孔容積に厳密に等しい。水溶液中の前駆体および有機添加物の濃度の調節は、モリブデンの固定表面密度:触媒の面積(nm2)当たりモリブデン原子5.2個、それぞれ0.4および0.55に等しいCo/MoおよびP/Moの原子比および1に等しい添加物/Moのモル比を得るような重量含有率でCo、MoおよびPをアルミナ担体上に沈着させるようになされる。12時間にわたる熟成の段階の後に、この固体は、12時間にわたって120℃で乾燥させられる。
触媒A3は、酸化モリブデン、水酸化コバルト、リン酸およびクエン酸から調製された水溶液の乾式含浸によって得られ、コバルト、モリブデンおよびリンの前駆体およびクエン酸有機添加物を含有する前記溶液の容積は、固体アルミナ担体S3の細孔容積に厳密に等しい。水溶液中の前駆体および有機添加物の濃度の調節は、モリブデンの固定表面密度:触媒の面積(nm2)当たりモリブデン原子7個、それぞれ0.4および0.55に等しいCo/MoおよびP/Moの原子比および1に等しい添加物/Moのモル比を得るような重量含有率でCo、MoおよびPをアルミナ担体上に沈着させるようになされる。12時間にわたる熟成の段階の後に、この固体は、12時間にわたって120℃で乾燥させられる。
触媒A4は、酸化モリブデン、水酸化コバルトおよびリン酸から調製された水溶液の乾式含浸によって得られ、コバルト、モリブデンおよびリンの前駆体を含有する前記溶液の容積は、固体アルミナ担体S5の細孔容積に厳密に等しい。水溶液中の前駆体の濃度の調節は、モリブデンの固定表面密度:触媒の面積(nm2)当たりモリブデン原子4.5個、それぞれ0.4および0.32に等しいCo/MoおよびP/Moの原子比を得るような重量含有率でCo、MoおよびPをアルミナ担体上に沈着させるようになされる。12時間にわたる熟成の段階の後に、この固体は、12時間にわたって120℃で乾燥させられ、次いで、4時間にわたって450℃で焼成される。
接触分解(FCC)ガソリンを代表するモデル供給原料は、10重量%の2,3−ジメチルブタ−2−エンおよび0.33重量%の3−メチルチオフェンを含有し(すなわち、供給原料中の硫黄は1000重量ppmである)、このものが、異なる触媒の触媒性能の評価のために用いられる。用いられた溶媒はヘプタンである。
Claims (19)
- 少なくとも1種の第VIB族金属と、少なくとも1種の第VIII族金属と、アルミナ担体とを含む水素化処理触媒であって、該アルミナ担体のガンマアルミナの含有率は、担体の重量に対して50重量%超かつ100重量%未満であり、前記担体の比表面積は、25〜150m2/gである、触媒。
- アルミナ担体のガンマアルミナの含有率は、担体の重量に対して60重量%〜95重量%である、請求項1に記載の触媒。
- 第VIB族金属の含有率は、触媒の全重量に対する前記第VIB族金属の酸化物の重量で3〜35%であり、第VIII族金属の含有率は、触媒の全重量に対する前記第VIII族金属の酸化物の重量で0.1〜10%である、請求項1または2に記載の触媒。
- モル比(第VIII族金属)/(第VIB族金属)は、0.1〜0.8である、請求項1〜3のいずれか1つに記載の触媒。
- リンも含有し、リンの含有率は、触媒の全重量に対してP2O5として表される重量で0.3〜10%であり、触媒中のリン/(第VIB族金属)のモル比は、0.1〜0.7である、請求項1〜4のいずれか1つに記載の触媒。
- 担体の比表面積は、60〜100m2/gである、請求項1〜5のいずれか1つに記載の触媒。
- 第VIB族金属の密度は、触媒の単位面積当たりの第VIB族金属の原子の数として表されて、触媒の面積(nm2)当たり第VIB族金属の原子3〜30個である、請求項1〜6のいずれか1つに記載の触媒。
- 第VIB族金属は、タングステンおよびモリブデンから選択され、第VIII族金属は、ニッケルおよびコバルトから選択される、請求項1〜7のいずれか1つに記載の触媒。
- アルミナ担体は、アルミナの前駆体を770℃以下の温度で熱処理することによって得られる、請求項1〜8のいずれか1つに記載の触媒。
- 酸素および/または窒素を含有する少なくとも1種の有機化合物も含む、請求項1〜9のいずれか1つに記載の触媒。
- 有機化合物は、カルボン酸、アルコール、アルデヒド、エステル、アミン、アミノカルボン酸、アミノアルコール、ニトリルおよびアミドから選択される、請求項10に記載の触媒。
- 有機化合物は、γ−バレロラクトン、2−アセチルブチロラクトン、トリエチレングリコール、ジエチレングリコール、エチレングリコール、エチレンジアミンテトラ酢酸(EDTA)、マレイン酸、マロン酸、クエン酸、γ−ケト吉草酸、ジメチルホルムアミド、N−メチルピロリドン、炭酸プロピレン、3−オキソブタン酸2−メトキシエチル、3−オキソブタン酸2−(メタクリロイルオキシ)エチル、ビシン、またはトリシンから選択される、請求項11に記載の触媒。
- 硫化されていることを特徴とする請求項1〜12のいずれか1つに記載の触媒。
- 請求項1〜13のいずれか1つによる水素化処理触媒を調製する方法であって、以下の段階:
a) アルミナの前駆体を770℃以下の温度で熱処理して、ガンマアルミナの含有率が、担体の重量に対して50重量%超かつ100重量%未満である担体を得る段階であって、前記担体の比表面積は25〜150m2/gである、段階、
b) 第VIB族金属の少なくとも1種の成分と、第VIII族金属の少なくとも1種の成分と、任意のリンとを、前記担体と接触させて、触媒前駆体を得る段階、
c) 段階b)を起源とする前記触媒前駆体を、200℃未満の温度で乾燥させる段階
を含む、方法。 - 段階a)の熱処理を、アルミナの前駆体の全重量に対して最低50重量%のベーマイトAlOOHを含有するアルミナの前駆体から行う、請求項14に記載の調製方法。
- 200℃〜600℃の温度での焼成の段階d)も含み、段階c)の後にこの工程を行う、請求項14または15に記載の触媒の調製方法。
- 硫化の段階も含み、段階c)またはd)の後にこの工程を行う、請求項14〜16のいずれか1つに記載の触媒の調製方法。
- ガソリン留分の水素化脱硫方法であって、前記ガソリン留分と、水素と、請求項1〜13のいずれか1つに記載の触媒とを接触させ、前記触媒は硫化させられ、該接触が行われる際に:
・ 温度は200℃〜400℃であり;
・ 全圧は1〜3MPaであり;
・ 毎時空間速度は、触媒の容積に対する供給原料の容積流量であるとして定義されて、1〜10h−1であり;
・ 水素/ガソリン供給原料の容積比は、100〜600NL/Lである
とされる、方法。 - ガソリンは、接触分解ユニットを起源とするガソリンである、請求項18に記載の方法。
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JP2022524904A (ja) * | 2020-02-11 | 2022-05-11 | ヒンドゥスタン ペトロリアム コーポレーション リミテッド | 分散型水素化脱硫触媒用組成物およびその製造方法 |
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