JP5511378B2 - 接触分解ガソリン中の硫黄分を低減させる触媒添加剤 - Google Patents
接触分解ガソリン中の硫黄分を低減させる触媒添加剤 Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 68
- 229910052717 sulfur Inorganic materials 0.000 title claims description 68
- 239000011593 sulfur Substances 0.000 title claims description 68
- 239000003054 catalyst Substances 0.000 title claims description 56
- 239000000654 additive Substances 0.000 title claims description 45
- 230000000996 additive effect Effects 0.000 title claims description 32
- 230000001603 reducing effect Effects 0.000 title claims description 17
- 238000004523 catalytic cracking Methods 0.000 title description 2
- 239000000203 mixture Substances 0.000 claims description 48
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 45
- 238000005336 cracking Methods 0.000 claims description 19
- 239000002841 Lewis acid Substances 0.000 claims description 17
- 239000011701 zinc Substances 0.000 claims description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- -1 Lewis acid compound Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000012876 carrier material Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- 239000004927 clay Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000009467 reduction Effects 0.000 description 13
- 150000007517 lewis acids Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 239000011959 amorphous silica alumina Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
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Description
本発明に係る硫黄分低減添加剤は有効な割合で含有されるようにすることができ、例えば、FCC分解触媒の全重量に基づき10重量%から20重量%の割合とすることができる。
通常のFCC触媒を使用して得られたガソリン留分の硫黄分の含有量
焼結された(steamed)、通常の商用FCCのゼオライト触媒(任意のFCC触媒サプライヤーから利用可能な、典型的な低RE-USYタイプ)は、ASTM D 3907に従ったMATについて評価された。図1は、添加剤のない通常の触媒だけで得られたパーセント変換に対するガソリンの硫黄分の含有量のプロット(対照)を示す。当該硫黄分の含有量は、対照として得られる。
商用として利用可能な添加剤組成物を用いた硫黄分の低減
例えばAlbemarle、CCIC、Englehard、Grace DavisonまたはIntercatのような、典型的な触媒サプライヤーから通常使用できる商用の硫黄分低減添加剤(表において比較添加剤と)が、例1における通常のFCC触媒、いわゆる低RE−USYに添加され(10重量%)、例1と同じ条件下、MATについて試験された。本例のガソリン留分中の硫黄分の含有量は、対照である図1中の硫黄分と比較される。71%の変換で、ベンゾチオフェンを含んで達成された全体的な硫黄分の低減は16%だった。表2は、すべての添加剤についてのガソリン留分の硫黄分の含有量を記載する。
特許請求の範囲に記載した新規な組成物の基底物質がFCCナフサの硫黄分の含有量を大きく低減することについて。
担体の硫黄分低減能を測定するために、モンモリロナイトクレーが通常の触媒(任意のFCC触媒サプライヤーから利用可能な典型的なRE-USYタイプ)と混合され、MATについて評価された。図2において示す、得られた結果は、対照と比較された。 モンモリロナイトクレーは大きな硫黄分低減能を有している。ガソリン留分生成物の硫黄分の含有量は、21%低減された(表2)。
亜鉛含浸クレーの使用により得られた結果
組成物は、単純湿潤法(incipient wetness method)に従って例3に示したクレーに2%の亜鉛を含浸させることにより、調製された。10重量%で当該組成物が例1で示したものと同じ商用の触媒(任意のFCC触媒サプライヤーから利用可能な典型的なRE-USYタイプ)に混合され、MATについて試験された。図3は、例4の組成物により得られたガソリンの硫黄分の含有量と、対照の触媒および添加剤の使用により得られたガソリンの硫黄分の含有量とを比較する。当該組成物の硫黄分の低減能は、例3の組成物と同様であった。71%の変換において、対照の触媒のみの使用と比較して、ガソリン生成物の硫黄分は、21%低減された。
クレーの細孔へのジルコニウムの取り込みの効果
Zr-クレー組成物は、イオン交換によりモンモリロナイトクレーの細孔に2%のジルコニウムを取り込ませることにより、調製された。およそ2重量%のジルコニウムが取り込まれた。当該組成物は、1:10の割合で、商用のゼオライト触媒(任意のFCC触媒サプライヤーから利用可能な典型的なRE-USYタイプ)に混合された。
ジルコニウムが取り込まれたモンモリロナイトクレーに含浸された亜鉛の適用の結果
組成物は、単純湿潤法により例5に記載した組成物(Zrが取り込まれたクレー)に2重量%の亜鉛が含浸されることにより、調製された。10重量%で当該物質が任意のFCC触媒サプライヤーから利用可能な、典型的なRE−USYタイプに混合され、例1に記載したものと同じ条件下でMATについて試験された。
亜鉛が含浸された、ジルコニウムが取り込まれたモンモリロナイトクレーからなる組成物(硫黄化合物の分布)
接触分解ガソリンは、メルカプタン、飽和物質(saturates)、チオフェンおよびベンゾチオフェンのような、様々な硫黄化合物を含んでいる。例6において得られたガソリン留分生成物の硫黄化合物の分布は、GC-SCDを使用して決定された。それについては表3において示す。本発明の組成物は、様々な種類の硫黄化合物について、異なる低減結果を示す。本発明の組成物を用いた場合に、硫黄分低減は、飽和物質およびC2-C4チオフェンに対してが最も有効であった。
新規な添加剤の使用はガソリンの収量に影響を与えない。
表4は、71%の変換で、通常の触媒、すなわち低RE-USYR(登録商標)、比較添加剤および本発明の添加剤組成物を用いてえら得たガソリン、ガス、LCO、HCOおよびコークスの生成物の収量を示す。ガソリン収量およびコークス収量は、本発明の添加剤組成物の使用によってそれぞれ影響されず、それぞれ50%および3.1%であった。
Claims (10)
- 流動接触分解(FCC)混合物であって、
FCC分解触媒と、
ジルコニウム成分および周期表の第IIB族のルイス酸化合物を含有する多孔質のモンモリロナイトクレー担体を有する独立した硫黄分低減添加剤の粒子と、を備え、
前記担体における前記ジルコニウム成分は前記担体の表面積を増加させるとともに、前記ルイス酸化合物は前記担体の表面にその後に含浸されているFCC混合物。 - 前記担体の表面に含浸されている前記周期表第IIB族のルイス酸化合物が亜鉛である請求項1に記載のFCC混合物。
- 前記硫黄分低減添加剤が、前記硫黄分低減添加剤の全重量に基づき1重量%から5重量%のジルコニウムを含有する請求項1に記載のFCC混合物。
- 前記硫黄分低減添加剤が、前記硫黄分低減添加剤の全重量に基づき1重量%から10重量%の亜鉛を含有する請求項2に記載のFCC混合物。
- 前記硫黄分低減添加剤の割合が、前記分解触媒の10重量%から20重量%である請求項1に記載のFCC混合物。
- FCC分解処理から得られたガソリン留分の硫黄分の含有量を低減させる処理であって、
炭化水素原料を、硫黄分低減添加剤の独立した粒子と組み合わせた通常のFCC分解触媒と接触させることを備え、
前記硫黄分低減添加剤は、ジルコニウム化合物が、細孔に取り込まれ、担体の表面積が増加しているとともに、当該担体の表面において周期表の第IIB族から選択されたルイス酸化合物がその後に含浸されている多孔質のモンモリロナイトクレー担体を有する処理。 - 前記担体物質の表面に含浸された周期表第IIB族のルイス酸化合物が亜鉛である請求項6に記載の処理。
- 前記硫黄分低減添加剤が、前記硫黄分低減添加剤の全重量に基づき1重量%から5重量
%のジルコニウムを含有する請求項6に記載の処理。 - 前記硫黄分低減添加剤が、前記硫黄分低減添加剤の全重量に基づき1重量%から10重
量%の亜鉛を含有する請求項7に記載の処理。 - 前記硫黄分低減添加剤の割合が、前記分解触媒の10重量%から20重量%である請求
項6に記載の処理。
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