JP2014528974A - スルホン分解と統合される酸化的脱硫のプロセス - Google Patents
スルホン分解と統合される酸化的脱硫のプロセス Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000008569 process Effects 0.000 title claims abstract description 47
- 150000003457 sulfones Chemical class 0.000 title abstract description 37
- 230000001590 oxidative effect Effects 0.000 title abstract description 32
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 29
- 230000023556 desulfurization Effects 0.000 title abstract description 29
- 238000005336 cracking Methods 0.000 title description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 58
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 58
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000003518 caustics Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 26
- -1 sulfur oxide compound Chemical class 0.000 claims description 26
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000004523 catalytic cracking Methods 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 24
- 239000003513 alkali Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 description 39
- 239000011593 sulfur Substances 0.000 description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 37
- 239000000446 fuel Substances 0.000 description 21
- 239000011949 solid catalyst Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 239000007800 oxidant agent Substances 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 150000003464 sulfur compounds Chemical class 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- 239000000295 fuel oil Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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Abstract
Description
本願は、その内容がそのまま本明細書にて引用される、2011年7月31日出願の米国仮特許出願第61/513620号の利益を主張する。
本発明は、炭化水素と、酸化的脱硫によって形成される酸化硫黄化合物との混合物より硫黄含量を軽減することに関する。
含硫サワー原油より得られる石油生成物を処理および最終的に使用する間の、硫黄化合物の大気中への放出は、健康および環境問題を提起する。輸送燃料および他の燃料の生成物に適用され得る厳格な低硫黄仕様は精油業に衝撃を与え、精油業者らは軽油中の硫黄含量を100万分の10重量部(10ppmw)以下に大きく下げるために設備投資を行う必要がある。米国、日本および欧州連合の国々などの先進工業国では、精油業者らは既に環境的にクリーンな輸送燃料を生成するように規制されている。例えば、2007年に、米環境保護庁は、道路用ディーゼル燃料の硫黄含量を500ppmw(低硫黄ディーゼル)から15ppmw(超低硫黄ディーゼル)に97%減少させることを規制した。欧州連合はさらにより厳格な基準を制定し、2009年に販売されるディーゼルおよびガソリン燃料は硫黄含量が10ppmwよりも低いことを規制した。他の国々は米国および欧州連合に倣い、精油業者らが超低硫黄レベルの輸送用燃料を生成することを要求する規制に取り組んでいる。
Al2O3+2NaOH→2NaAlO2+H2O [1]
苛性ソーダはアルミナをアルミン酸ナトリウムに変え、それは以下に示されるように塩基性材料である。アルミン酸ナトリウムは活性種である。濃度は化学量論的である。変換のために十分な量を固体触媒に加える。
Claims (26)
- 液体炭化水素と酸化硫黄化合物の混合物より該酸化硫黄化合物の濃度を減らすプロセスであって、
a.炭化水素と酸化硫黄化合物の混合物を、苛性溶液の存在下で、有効量の固体塩基触媒組成物と接触させ、
ここで固体塩基触媒組成物は、酸化亜鉛、酸化アルミニウム、アルミン酸亜鉛、層状複水酸化物、および層状複水酸化マグネシウム/アルミニウムの別個の成分またはその混合物を含み、
接触反応は、一部の酸化硫黄化合物のSOx化合物への接触分解を促進するのに効果的な条件下で起こり;
b.SOx化合物を炭化水素混合物より除去し;および
c.酸化硫黄化合物の濃度の減少した炭化水素生成物を回収する
ことを含む、プロセス。 - 固体塩基触媒組成物が、効果的な割合を占める一般式(I):
ZnAl2O4・x(ZnO)・y(Al2O3) (I)
[式中、xおよびyは、独立して、0〜2であり、式(I)におけるZnAl2O4の全割合は少なくとも10重量%である]
で示される層状複水酸化物を含む、請求項1記載のプロセス。 - 効果的な割合を占める層状複水酸化物が組成物全体の少なくとも100重量%を構成する、請求項2記載のプロセス。
- 効果的な割合を占める層状複水酸化物が組成物全体の少なくとも50重量%を構成する、請求項2記載のプロセス。
- 効果的な割合を占める層状複水酸化物が組成物全体の少なくとも1重量%を構成する、請求項2記載のプロセス。
- 固体塩基触媒が、粉末、押出成形物または球体の形態をした多孔性材料である、請求項1記載のプロセス。
- 固体塩基触媒が、10m2/g〜600m2/gの範囲にある表面積を有する、請求項1記載のプロセス。
- 固体塩基触媒が、50m2/g〜600m2/gの範囲にある表面積を有する、請求項1記載のプロセス。
- 固体塩基触媒が、0.1cm3/g〜0.5cm3/gの範囲にある細孔容量を有する、請求項1記載のプロセス。
- 固体塩基触媒が、0.3cm3/g〜0.5cm3/gの範囲にある細孔容量を有する、請求項1記載のプロセス。
- 固体塩基触媒が、0.001ミクロン〜0.1ミクロンの孔径分布を有する、請求項1記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を200℃〜600℃の範囲の温度で接触させる、請求項1記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を300℃〜400℃の範囲の温度で接触させる、請求項1記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を300℃〜350℃の範囲の温度で接触させる、請求項1記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を、苛性溶液の存在下、有効量の固体塩基触媒と接触させることにおいて、該塩基が炭化水素と酸化硫黄化合物の混合物に溶解している、請求項1記載のプロセス。
- 苛性溶液の量が、固体塩基触媒の総量に基づいて0.05〜30重量%の範囲にある、請求項15記載のプロセス。
- 一般式(I):
ZnAl2O4・x(ZnO)・y(Al2O3) (I)
[式中、xおよびyは、独立して、0〜2であり、式(I)におけるZnAl2O4の全割合は少なくとも10重量%である]
で示される層状複水酸化物を含む、固体塩基触媒組成物を準備し;
該固体塩基触媒組成物を反応装置に充填し;
該反応装置を効果的な温度に加熱し;および
該固体塩基触媒にアルカリ性を付与するのに十分な時間、液体の苛性溶液を反応装置中の該固体塩基触媒上に通す、
ことを含む、固体塩基触媒の製造方法。 - 効果的な温度が約250℃〜約350℃の範囲にある、請求項17記載のプロセス。
- 液体の苛性溶液が、固体塩基触媒1リットルに付き約0.25〜約7モルの範囲にある濃度での水酸化ナトリウムである、請求項17記載のプロセス。
- 液体の苛性溶液が0.1h−1〜10h−1の範囲にある液空間速度で固体塩基触媒組成物上を通る、請求項17記載のプロセス。
- 液体の苛性溶液が0.5h−1〜2h−1の範囲にある液空間速度で固体塩基触媒組成物上を通る、請求項17記載のプロセス。
- 液体炭化水素と酸化硫黄化合物の混合物から該酸化硫黄化合物の濃度を減らすプロセスであって、
a.炭化水素と酸化硫黄化合物との混合物を、苛性溶液で予め処理された有効量の固体塩基触媒組成物と接触させ、
ここで固体塩基触媒組成物は、酸化亜鉛、酸化アルミニウム、アルミン酸亜鉛、層状複水酸化物、および層状複水酸化マグネシウム/アルミニウムの別個の成分またはその混合物を含み、
接触反応は、一部の酸化硫黄化合物のSOx化合物への接触分解を促進するのに効果的な条件下で起こり;
b.SOxを炭化水素混合物より除去し;および
c.酸化硫黄化合物の濃度の減少した炭化水素生成物を回収する
ことを含む、プロセス。 - 炭化水素と酸化硫黄化合物との混合物を200℃〜600℃の範囲にある温度で接触させる、請求項22記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を300℃〜400℃の範囲にある温度で接触させる、請求項22記載のプロセス。
- 炭化水素と酸化硫黄化合物との混合物を300℃〜350℃の範囲にある温度で接触させる、請求項22記載のプロセス。
- 一般式(I):
ZnAl2O4・x(ZnO)・y(Al2O3) (I)
[式中、xおよびyは、独立して、0〜2であり、式(I)におけるZnAl2O4の全割合は少なくとも10重量%である]
で示される層状複水酸化物を含む固体塩基触媒組成物であって、
該層状複水酸化物が液体の苛性溶液でアルカリ処理されている、固体塩基触媒組成物。
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CN107022371A (zh) | 2017-08-08 |
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