JP4942536B2 - FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 - Google Patents
FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 Download PDFInfo
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- JP4942536B2 JP4942536B2 JP2007104004A JP2007104004A JP4942536B2 JP 4942536 B2 JP4942536 B2 JP 4942536B2 JP 2007104004 A JP2007104004 A JP 2007104004A JP 2007104004 A JP2007104004 A JP 2007104004A JP 4942536 B2 JP4942536 B2 JP 4942536B2
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
- C10G11/182—Regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/83—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 rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/405—Limiting CO, NOx or SOx emissions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
含有させる。セリアが好適な酸素貯蔵用酸化物である。
(a)多孔質の酸性酸化物支持体粒子にアルカリ/アルカリ土類金属酸化物源および酸素貯蔵用酸化物源を含浸させることで所望のアルカリ/アルカリ土類金属含有量および酸素貯蔵用酸化物含有量を達成し、
(b)段階(a)の含浸支持体の焼成を行い、
(c)段階(b)で得られる焼成支持体にIb/IIb族金属源またはパラジウム金属源を含浸させ、そして
(d)段階(c)で得られる含浸支持体の焼成を行う。
シリカを6重量%含有する非晶質のシリカアルミナ粒子支持体に炭酸ナトリウム溶液を含浸させ、乾燥させた後、焼成を受けさせることにより、このシリカアルミナの重量を基準にしたNa2Oとして測定して3.6重量%のNa含有量を達成した。次に、このNa含有シリカアルミナ粒子に硝酸セリウム溶液を含浸させた後、乾燥させることにより、このシリカアルミナ粒子の重量を基準にして約1重量%のセリア含有量を達成した。次に、このCe含有組成物に硝酸銀溶液を含浸させることにより、このシリカアルミナ粒子の重量を基準にして約5重量%(酸化物を基準)の銀含有量を達成した。次に、この含浸させた粒子を乾燥させた後、焼成を約704℃で受けさせることにより、本発明に従う粒子組成物を生じさせた。
シリカを6重量%含有する非晶質のシリカアルミナ粒子支持体に炭酸ナトリウム溶液を含浸させ、乾燥させた後、焼成を受けさせることにより、このシリカアルミナの重量を基準にしたNa2Oとして測定して6重量%のNa含有量を達成した。次に、このNa含有シリカアルミナ粒子に硝酸セリウム溶液を含浸させた後、乾燥させることにより、このシリカアルミナ粒子の重量を基準にして約22重量%のセリア含有量を達成した。次に、このCe含有組成物に硝酸銅溶液を含浸させることにより、このシリカアルミナ粒子の重量を基準にして約2重量%(酸化物を基準)の銅含有量を達成した。次に、この含浸させた粒子を乾燥させた後、焼成を約704℃で受けさせることにより、本発明に従う粒子組成物を生じさせた。
実施例1の組成物152gを市販FCC触媒(Grace Davison Orion(商標)842平衡触媒(ECAT))2908gおよび燃焼促進剤(Grace Davison CP−5)10gと混合した。次に、この混合物をDCRパイロットプラントFCC装置で用いて、窒素が0.3重量%入っている炭化水素原料の分解を生じさせた。この分解を75%変換率および1000g/時の触媒供給率で実施した。対照実施例として、実施例1の組成物を用いないで同じ触媒混合物を実験した。このFCC装置の再生装置から放出される測定NOx量は、実施例1の組成物を用いると対照実施例に比較して65%低くかった。
実施例2の組成物10gを市販FCC触媒(Grace Davison Orion(商標)922G ECAT)2000gおよび燃焼促進剤(Grace Davison CP−5)5gと混合した。次に、この混合物をFCCパイロットプラント(DCR)装置で用いて、Countrymark炭化水素原料(0.13重量%のN)の分解を生じさせた。この分解を75%変換率および1000g/時の触媒供給率で実施した。対照実施例として、実施例2の組成物を用いないで同じ触媒混合物を実験した。このFCC装置の再生装置から放出される測定NOx量は、実施例2の組成物を用いると対照実施例に比較して46%低くなった。
シリカを6重量%含有するシリカアルミナ粒子支持体に炭酸ナトリウム溶液を含浸させ、乾燥させた後、焼成を受けさせることにより、このシリカアルミナの重量を基準にしたNa2Oとして測定して6重量%のNa含有量を達成した。次に、このNa含有シリカアルミナ粒子に硝酸セリウム溶液を含浸させた後、乾燥させることにより、このシリカアルミナ粒子の重量を基準にして約22重量%のセリア含有量を達成した。次に、このセリア含有組成物に硝酸パラジウム溶液を含浸させることにより、このシリカアルミナ粒子の重量を基準にして約0.1重量%のパラジウム含有量を達成した。次に、この含浸させた粒子を乾燥させた後、焼成を約704℃で受けさせることにより、本発明に従う粒子組成物を生じさせた。
実施例5の組成物10gを市販FCC触媒(Grace Davison Orion(商標)922G ECAT)2000gと混合した。次に、この混合物をFCCパイロットプラント(DCR)装置で用いて、Countrymark炭化水素原料の分解を生じさせた。この分解を75%変換率および1000g/時の触媒供給率で実施した。比較実施例として、実施例5の組成物を用いないで同じ触媒を実験した。このFCC装置の再生装置から放出される測定NOx量は、実施例5の組成物を用いた場合、対照実施例に比較して実質的に変化しないままであった。実施例5の組成物は典型的な市販燃焼促進剤よ
り高いか或はそれに匹敵するCO燃焼活性を示した。
Claims (10)
- 流動接触分解方法でNOx放出の生成を最少限にしながらCOの燃焼を促進するのに適切な粒子状組成物であって、該組成物が20−200μmの範囲の粒子サイズ及び0−45のダビソンアトリションインデックスを有し、
(i)少なくとも50重量%のアルミナを含有する粒子状酸性酸化物、
(ii)アルカリ金属酸化物として計量して1から10重量部のアルカリ金属、
(iii)1から50重量部の酸素貯蔵能力を有する遷移金属酸化物 及び
(iv)0.05−5.0重量部のパラジウム
を含み、
ここで、成分(ii)−(iv)が成分(i)に含浸され焼成されて支持されており、成分(ii)−(iv)の全ての上記重量部は100重量部の成分(i)を基準とし、
該粒子状組成物がNOx放射物の生成を最低にしながら流動接触分解法におけるCOの燃焼を促進するのに適しており、該組成物が流動接触分解の触媒粒子の一体部分としてか、或いは触媒粒子と混合される個別の添加剤である、組成物。 - 上記酸性酸化物支持体がアルミナ、シリカアルミナ、ランタナアルミナ及びそれらの混合物から成る群から選択される請求項1の組成物。
- 上記酸性酸化物支持体がアルミナである請求項1の組成物。
- 上記酸性酸化物支持体がアルミナ:シリカのモル比が3−50:1のシリカアルミナである請求項2の組成物。
- 上記組成物が、ナトリウム、カリウム及びこれらの混合物から成る群から選択されるアルカリ金属を含有する請求項1の組成物。
- 上記酸素貯蔵酸化物がセリアを含有する請求項1の組成物。
- (a)炭化水素の接触分解で用いるに適切な分解用成分、
(b)請求項1−6のいずれか記載の組成物を含有する成分
を含む流動分解触媒。 - 上記分解触媒が成分(a)と成分(b)の粒子状混和物を含む請求項7の分解触媒。
- 炭化水素原料を分解させて低分子量成分を生じさせる方法であって、請求項7及び請求項8記載のいずれかに従う分解触媒に上記炭化水素をFCC条件で接触させることで、上記低分子量成分を生じさせることを含む方法。
- 上記接触を行っている間上記触媒を流動させ、そして上記方法が、使用済み分解触媒を上記接触段階から回収しそして上記使用済み触媒を上記触媒の再生に適切な条件下で処理することを更に含む請求項9の方法。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US43712395A | 1995-05-05 | 1995-05-05 | |
US43568795A | 1995-05-05 | 1995-05-05 | |
US435687 | 1995-05-05 | ||
US437123 | 1995-05-05 |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP13255296A Division JP4044629B2 (ja) | 1995-05-05 | 1996-05-01 | FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 |
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JP2007260675A JP2007260675A (ja) | 2007-10-11 |
JP4942536B2 true JP4942536B2 (ja) | 2012-05-30 |
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JP13255296A Expired - Fee Related JP4044629B2 (ja) | 1995-05-05 | 1996-05-01 | FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 |
JP2007104004A Expired - Fee Related JP4942536B2 (ja) | 1995-05-05 | 2007-04-11 | FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 |
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JP13255296A Expired - Fee Related JP4044629B2 (ja) | 1995-05-05 | 1996-05-01 | FCC方法でNOx量を低くし燃焼を促進する組成物、触媒及びFCC方法 |
Country Status (6)
Country | Link |
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EP (1) | EP0741180B1 (ja) |
JP (2) | JP4044629B2 (ja) |
AU (1) | AU718321B2 (ja) |
CA (1) | CA2175774C (ja) |
DE (1) | DE69624028T2 (ja) |
ES (1) | ES2181844T3 (ja) |
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AU2006241425B2 (en) * | 2005-04-29 | 2011-09-15 | W.R. Grace & Co.-Conn. | NOx reduction compositions for use in partial burn FCC processes |
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AU547232B2 (en) * | 1980-07-29 | 1985-10-10 | W.R. Grace & Co.-Conn. | Regeneration of cracking catalysts to effect a reduction the emission of sulphur oxides |
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US4866019A (en) * | 1987-01-13 | 1989-09-12 | Akzo N.V. | Catalyst composition and absorbent which contain an anionic clay |
DE3830319C1 (ja) * | 1988-09-07 | 1989-07-20 | Degussa Ag, 6000 Frankfurt, De | |
JPH0483535A (ja) * | 1990-07-26 | 1992-03-17 | Univ Beijing | ペロブスカイト型希土複合酸化物燃焼触媒 |
JPH05245378A (ja) * | 1990-09-25 | 1993-09-24 | Riken Corp | 排ガス浄化材及び排ガス浄化方法 |
EP0532024B1 (en) * | 1991-09-12 | 1998-08-12 | Sakai Chemical Industry Co., Ltd., | Catalyst for catalytic reduction of nitrogen oxide |
US5364517A (en) * | 1993-02-19 | 1994-11-15 | Chevron Research And Technology Company | Perovskite-spinel FCC NOx reduction additive |
ES2092429B1 (es) * | 1993-07-29 | 1997-08-01 | Univ Valencia Politecnica | Catalizador para la eliminacion de sox y nox de gases, especialmente de unidades fcc, y manera de prepararlo. |
FR2729090A1 (fr) * | 1995-01-11 | 1996-07-12 | Inst Francais Du Petrole | Catalyseurs de reduction selective des oxydes d'azote en azote en milieu oxydant, procede de preparation et utilisation |
-
1996
- 1996-03-12 AU AU48007/96A patent/AU718321B2/en not_active Ceased
- 1996-04-15 DE DE1996624028 patent/DE69624028T2/de not_active Expired - Lifetime
- 1996-04-15 EP EP96250085A patent/EP0741180B1/en not_active Expired - Lifetime
- 1996-04-15 ES ES96250085T patent/ES2181844T3/es not_active Expired - Lifetime
- 1996-05-01 JP JP13255296A patent/JP4044629B2/ja not_active Expired - Fee Related
- 1996-05-03 CA CA 2175774 patent/CA2175774C/en not_active Expired - Fee Related
-
2007
- 2007-04-11 JP JP2007104004A patent/JP4942536B2/ja not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP4044629B2 (ja) | 2008-02-06 |
DE69624028T2 (de) | 2003-08-14 |
AU4800796A (en) | 1996-11-14 |
CA2175774C (en) | 2009-09-29 |
EP0741180A3 (en) | 1997-02-05 |
ES2181844T3 (es) | 2003-03-01 |
EP0741180A2 (en) | 1996-11-06 |
JP2007260675A (ja) | 2007-10-11 |
CA2175774A1 (en) | 1996-11-06 |
EP0741180B1 (en) | 2002-10-02 |
AU718321B2 (en) | 2000-04-13 |
JPH08299794A (ja) | 1996-11-19 |
DE69624028D1 (de) | 2002-11-07 |
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