JP5628326B2 - メチルピリジンの調製のための触媒 - Google Patents
メチルピリジンの調製のための触媒 Download PDFInfo
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- JP5628326B2 JP5628326B2 JP2012533517A JP2012533517A JP5628326B2 JP 5628326 B2 JP5628326 B2 JP 5628326B2 JP 2012533517 A JP2012533517 A JP 2012533517A JP 2012533517 A JP2012533517 A JP 2012533517A JP 5628326 B2 JP5628326 B2 JP 5628326B2
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- Prior art keywords
- catalyst
- methylpiperidine
- dehydrogenation
- aluminum
- mixture
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/133—Preparation by dehydrogenation of hydrogenated pyridine compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- Hydrogenated Pyridines (AREA)
Description
3−メチルピペリジンおよび3−メチルピリジン(3−ピコリン)は、B−複合体の必須ビタミン(ビタミンB3)であるニコチンアミドおよびニコチン酸の工業生産の中間体である。このプロセスでは、3−メチルピペリジンは脱水素触媒の存在下で3−メチルピリジンに変換される。3−メチルピリジンは酸化性アンモノリシスによって3−シアノピリジンに変換される。3−メチルピペリジンは2−メチル−1,5−ジアミノペンタンの環化によって得ることができる。
発明の主題は、メチルピペリジンのメチルピリジンへの脱水素のための触媒の製造方法であって、(a)から(d)の順序で、
(a)65〜100重量%の酸化ケイ素および0〜35重量%の酸化アルミニウムを含む担体を用意する工程と、
(b)この担体にパラジウムを含浸させる工程であって、この担体をパラジウム−アンモニア−錯体の水溶液に接触させて触媒を得る工程と、
(c)触媒を80℃未満の温度で乾燥させる工程と、
(d)触媒を200℃未満の温度でか焼する工程と
を含む方法である。
1.脱水素触媒の製造
管状リアクタ(3mの長さ、25cmの径)に75kgの担体(シリカおよびアルミナの粒子、Grace Inc.からのDavicat E501(登録商標))を充填し、アンモニアガス(5kg)をこの固体触媒上に室温で通して、担体の酸性表面部分を中和し、それを約60℃まで温める。同時に、パラジウム溶液を、9.5kg PdCl2および14kgのアンモニアを1800lの水に溶解させることによって調製する。担体およびパラジウム溶液を室温まで冷却したのち、前記パラジウム溶液をキャリア上に16〜24時間にわたってポンプで送る。その後、残留溶液をリアクタから抜き取り、触媒を水で2回洗浄する。ほとんどの水が触媒から除去されるまで、触媒を40℃で空気で乾燥させる。乾燥後、触媒を約130℃の空気で約8時間にわたってか焼する。
300gの触媒を反応容器に充填した。触媒を、初期温度が50℃である(300℃まで高めた)50%の水素と50%の窒素との気体混合物(体積/体積)で賦活した。次に、温度が300℃であるメチルピペリジンと水素と窒素との気体混合物をこの触媒上に通した。0.9kg/時のメチルピペリジン、0.3kg/時の窒素および3g/時の水素の供給流で、以下の結果が得られた(表1):
以下に、本願の発明の実施態様を付記する。
[1]メチルピペリジンのメチルピリジンへの脱水素のための触媒の製造方法であって、(a)から(d)の順序で、(a)65〜100重量%の酸化ケイ素および0〜35重量%の酸化アルミニウムを含む担体を用意する工程と、(b)前記担体にパラジウムを含浸させる工程であって、前記担体をパラジウム−アンモニア−錯体の水溶液に接触させて触媒を得る工程と、(c)前記触媒を80℃未満の温度で空気を用いて乾燥させる工程と、(d)前記触媒を200℃未満の温度でか焼する工程とを含む方法。
[2]工程(d)のあとに(e)前記触媒を水素で賦活することをさらに含む請求項1に記載の方法。
[3]前記乾燥工程(c)を20℃〜60℃の温度で行う請求項1および2の少なくとも1項に記載の方法。
[4]前記か焼工程(d)を空気を用いておよび/または80℃〜200℃の温度で行う[1]〜[3]のいずれかに記載の方法。
[5]前記賦活工程(e)を酸素の有効な減少下で行う[1]〜[4]のいずれかに記載の方法。
[6]前記触媒は0.5〜8重量%のパラジウムを含む[1]〜[5]のいずれかに記載の方法。
[7][1]〜[6]のいずれかに記載の方法によって得ることができる、メチルピペリジンのメチルピリジンへの変換のための脱水素触媒。
[8]メチルピペリジンを[7]に記載の脱水素触媒に接触させる、メチルピペリジンからのメチルピリジンの製造方法。
[9]メチルピペリジンは3−メチルピペリジンである[8]に記載の方法。
[10]反応を水素および/または窒素雰囲気下で行う[8]または[9]の少なくとも1に記載の方法。
[11]反応を180℃〜400℃の温度で気相において行う[8]〜[10]のいずれかに記載の方法。
[12]前記触媒をアルミニウムと混合する[8]〜[11]のいずれかに記載の方法。
[13]メチルピリジンを最初に第1の触媒/アルミニウム混合物に接触させ、次に第2の触媒/アルミニウム混合物に接触させ、ここで前記第1の混合物中の触媒/アルミニウムの比は前記第2の混合物中よりも低い[12]に記載の方法。
[14]前記脱水素反応の前に、メチルピペリジンを環化反応でメチル−1,5−ジアミノペンタンから製造し、前記環化反応を第1のリアクタで行い、前記脱水素反応を第2のリアクタで行い、両方のリアクタは相互接続されており、両方の反応を連続プロセスで行う[8]〜[13]のいずれかに記載の方法。
[15]前記環化反応で製造したメチルピペリジンをアンモニアとの混合物として得て、この混合物をアンモニアの事前分離なしに前記第2のリアクタに供給する[8]〜[14]のいずれかに記載の方法。
Claims (14)
- メチルピペリジンのメチルピリジンへの脱水素のための触媒の製造方法であって、(a)から(d)の順序で、
(a)65〜100重量%の酸化ケイ素および0〜35重量%の酸化アルミニウムを含む担体を用意する工程と、
(b)前記担体にパラジウムを含浸させる工程であって、前記担体をパラジウム−アンモニア−錯体の水溶液に接触させて触媒を得る工程と、
(c)前記触媒を80℃未満の温度で空気を用いて乾燥させる工程と、
(d)前記触媒を200℃未満の温度でか焼する工程と
を含む方法。 - 工程(d)のあとに
(e)前記触媒を水素で賦活すること
をさらに含む請求項1に記載の方法。 - 前記乾燥工程(c)を20℃〜60℃の温度で行う請求項1および2の少なくとも1項に記載の方法。
- 前記か焼工程(d)を空気を用いておよび/または80℃〜200℃の温度で行う請求項1〜3のいずれかに記載の方法。
- 前記賦活工程(e)を酸素の有効な減少下で行う請求項1〜4のいずれかに記載の方法。
- 前記触媒は0.5〜8重量%のパラジウムを含む請求項1〜5のいずれかに記載の方法。
- メチルピペリジンの脱水素によるメチルピリジンの製造方法であって、
(i)請求項1〜6のいずれかに記載の方法によって脱水素触媒を製造する工程と、
(ii)メチルピペリジンを前記脱水素触媒に接触させる工程と、
を含む方法。 - メチルピペリジンは3−メチルピペリジンである請求項7に記載の方法。
- 脱水素反応を水素および/または窒素雰囲気下で行う請求項7または8に記載の方法。
- 脱水素反応を180℃〜400℃の温度で気相において行う請求項7〜9のいずれかに記載の方法。
- 前記触媒をアルミニウムと混合する請求項7〜10のいずれかに記載の方法。
- メチルピペリジンを最初に第1の触媒/アルミニウム混合物に接触させ、次に第2の触媒/アルミニウム混合物に接触させ、ここで前記第1の混合物中の触媒/アルミニウムの比は前記第2の混合物中よりも低い請求項11に記載の方法。
- 前記脱水素反応の前に、メチルピペリジンを環化反応でメチル−1,5−ジアミノペンタンから製造し、前記環化反応を第1のリアクタで行い、前記脱水素反応を第2のリアクタで行い、両方のリアクタは相互接続されており、両方の反応を連続プロセスで行う請求項7〜12のいずれかに記載の方法。
- 前記環化反応で製造したメチルピペリジンをアンモニアとの混合物として得て、この混合物をアンモニアの事前分離なしに前記第2のリアクタに供給する請求項13に記載の方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25233609P | 2009-10-16 | 2009-10-16 | |
EP09013123A EP2322273A1 (en) | 2009-10-16 | 2009-10-16 | Catalysts for the preparation of methylpyridine |
EP09013123.6 | 2009-10-16 | ||
US61/252,336 | 2009-10-16 | ||
PCT/EP2010/006203 WO2011045014A2 (en) | 2009-10-16 | 2010-10-12 | Catalysts for the preparation of methylpyridine |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013507246A JP2013507246A (ja) | 2013-03-04 |
JP5628326B2 true JP5628326B2 (ja) | 2014-11-19 |
Family
ID=41818607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012533517A Expired - Fee Related JP5628326B2 (ja) | 2009-10-16 | 2010-10-12 | メチルピリジンの調製のための触媒 |
Country Status (13)
Country | Link |
---|---|
EP (2) | EP2322273A1 (ja) |
JP (1) | JP5628326B2 (ja) |
KR (1) | KR101767696B1 (ja) |
CN (2) | CN106496101A (ja) |
AU (1) | AU2010306143B2 (ja) |
BR (1) | BR112012012142A2 (ja) |
CA (1) | CA2774749C (ja) |
DK (1) | DK2488296T3 (ja) |
EA (1) | EA022033B1 (ja) |
ES (1) | ES2691420T3 (ja) |
MY (1) | MY156199A (ja) |
PL (1) | PL2488296T3 (ja) |
WO (1) | WO2011045014A2 (ja) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2503156A1 (fr) | 1981-04-01 | 1982-10-08 | Rhone Poulenc Spec Chim | Procede de preparation de pyridine et de pyridines substituees |
GEP20012441B (en) * | 1993-04-02 | 2001-05-25 | Lonza Ag | Process for Preparing 3-Methylpiperidine and 3-Methylpyridine |
ZA968485B (en) | 1995-11-01 | 1997-05-20 | Lonza Ag | Process for preparing nicotinamide |
CN1903842A (zh) | 2005-07-29 | 2007-01-31 | 浙江爱迪亚营养科技开发有限公司 | 3-甲基吡啶的制备方法 |
-
2009
- 2009-10-16 EP EP09013123A patent/EP2322273A1/en not_active Ceased
-
2010
- 2010-10-12 AU AU2010306143A patent/AU2010306143B2/en not_active Ceased
- 2010-10-12 JP JP2012533517A patent/JP5628326B2/ja not_active Expired - Fee Related
- 2010-10-12 PL PL10768411T patent/PL2488296T3/pl unknown
- 2010-10-12 EA EA201200598A patent/EA022033B1/ru not_active IP Right Cessation
- 2010-10-12 CN CN201610791734.5A patent/CN106496101A/zh active Pending
- 2010-10-12 DK DK10768411.0T patent/DK2488296T3/en active
- 2010-10-12 KR KR1020127008909A patent/KR101767696B1/ko active IP Right Grant
- 2010-10-12 BR BR112012012142A patent/BR112012012142A2/pt not_active IP Right Cessation
- 2010-10-12 CA CA2774749A patent/CA2774749C/en not_active Expired - Fee Related
- 2010-10-12 MY MYPI2012001261A patent/MY156199A/en unknown
- 2010-10-12 EP EP10768411.0A patent/EP2488296B1/en not_active Not-in-force
- 2010-10-12 ES ES10768411.0T patent/ES2691420T3/es active Active
- 2010-10-12 WO PCT/EP2010/006203 patent/WO2011045014A2/en active Application Filing
- 2010-10-12 CN CN2010800463094A patent/CN102548655A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
BR112012012142A2 (pt) | 2019-09-24 |
EP2322273A1 (en) | 2011-05-18 |
ES2691420T3 (es) | 2018-11-27 |
WO2011045014A3 (en) | 2011-07-14 |
CN102548655A (zh) | 2012-07-04 |
WO2011045014A2 (en) | 2011-04-21 |
EP2488296B1 (en) | 2018-08-15 |
PL2488296T3 (pl) | 2019-01-31 |
CA2774749A1 (en) | 2011-04-21 |
CN106496101A (zh) | 2017-03-15 |
CA2774749C (en) | 2018-07-24 |
JP2013507246A (ja) | 2013-03-04 |
AU2010306143A1 (en) | 2012-05-10 |
KR20120084728A (ko) | 2012-07-30 |
KR101767696B1 (ko) | 2017-08-11 |
EA022033B1 (ru) | 2015-10-30 |
MY156199A (en) | 2016-01-29 |
EP2488296A2 (en) | 2012-08-22 |
EA201200598A1 (ru) | 2012-11-30 |
AU2010306143B2 (en) | 2016-03-03 |
DK2488296T3 (en) | 2018-12-03 |
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