CN1222511A - 烟酸的制造方法 - Google Patents
烟酸的制造方法 Download PDFInfo
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- CN1222511A CN1222511A CN98122936A CN98122936A CN1222511A CN 1222511 A CN1222511 A CN 1222511A CN 98122936 A CN98122936 A CN 98122936A CN 98122936 A CN98122936 A CN 98122936A CN 1222511 A CN1222511 A CN 1222511A
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- nicotinic acid
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- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B41/00—Formation or introduction of functional groups containing oxygen
- C07B41/08—Formation or introduction of functional groups containing oxygen of carboxyl groups or salts, halides or anhydrides thereof
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- 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
- C07D213/60—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 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicinal Preparation (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
本发明通过喷雾干燥烟酸铵水溶液生产烟酸。在流化床或减压下通过后热处理,所述的烟酸可以不含残留的烟酸铵。该方法尤其适合于处理用大气氧化3-甲基吡啶时所产生的反应混合物,其中的氨和水可以循环。烟酸(“维生素PP”)对食品工业和饲料工业是一种重要的添加剂。
Description
本发明涉及由烟酸铵溶液制备烟酸的方法。
制备烟酸的一个已知的方法是基于在水存在下用大气氧通过多相催化来氧化3-甲基吡啶(β-甲基吡啶)。但是,这种方法有一个缺点,就是存在副反应,在一系列的氧化和水解步骤中,一些3-甲基吡啶分裂形成氨,氨与主产品烟酸一起又形成烟酸铵。后者与游离的烟酸相反,高度溶于水并因此使产品混合物的处理更加困难,如果它不能转回成烟酸,则它意味着产率的损失。转变回烟酸是可能的,例如通过加入一种强酸,但这会生成这种酸的铵盐,必须将这种铵盐分离并作为废物除去。此外,必须注意,作为吡啶衍生物的烟酸也能作为碱进行反应,它会与过量的强酸形成盐。
因此,本发明的目的是提供一个方法,该方法在没有加入助剂和不产生废料的情况下,将烟酸铵转化成烟酸。
按照本发明,这个目的是通过喷雾干燥烟酸铵的水溶液来达到的。本发明人意外地发现烟酸铵的水溶液通过喷雾干燥可以转化为烟酸。在该方法中,氨和水一起在喷雾干燥器的废气中排出。
喷雾干燥较好是在160-250℃的干燥气体温度(在进口处)进行。合适的干燥气体是空气或惰性气体,如氮气或氩气。出口处的温度较好是保持在110℃以下,以防止产品升华。
喷雾干燥较好是在流化床喷雾干燥器内进行,这种类型的喷雾干燥器可从在DK-2860 Sφborg/Denmark的Niro A/S购得,名称为FSDTM。
在喷雾干燥之后所得到的烟酸仍然含有少量的烟酸铵,这取决于干燥的温度。已经发现,通过流化床在100-200℃,较好在130-170℃的后热处理,烟酸铵可以减少。在这种处理中所产生的烟酸粉末可以循环至喷雾干燥器。
作为流化床中后处理的一种替代方法,也可以在较低温度下进行减压(部分真空或真空)下的后处理。在这情况下所使用的压力较好是低于100毫巴,更好是低于50毫巴。合适的温度是70-150℃,更好是80-120℃。在10-15毫巴及80-90℃处理1/2-1小时则得到特别好的结果。在这样低的温度,由升华引起的损耗可以降至极小,而且可得到具有优良透明性(即不脱色)的产品。
本发明的方法较好是使用一种烟酸铵溶液来进行,这种烟酸铵溶液是把氨加入到(可能是浓缩的)3-甲基吡啶的催化氧化的粗水溶液(aqueous crude solution))而得到的。例如,将氨气体或氨水溶液计量通入吸收塔,并把来自氧化反应器的气体反应混合物加至该吸收塔中,把烟酸铵溶液作为底部产品由其中排出,过量的水由顶部排出。
制备烟酸铵溶液所需要的氨较好的是全部或部分地由喷雾干燥废气中取出。例如,为了达到这种目的,干燥器的废气可以被冷却至露点以下,而冷凝的氨水可以被分离出来并循环回至烟酸吸收过程中。因为,如上所述,在任何情况下3-甲基吡啶的氧化总会产生少量的氨作为副产品,总体来说就产生了过量的氨,在连续操作中,如果氨循环足够有效,就可以完全省去外部加入的氨。
同样,喷雾干燥废气中所存在的水最好完全或部分循环至氧化反应器中。因为1摩尔的3-甲基吡啶氧化为烟酸,在理想情况下会产生1摩尔的水,所产生的稍过量的水必须以适当的方式从装置中除去。相似地所存在的未反应的3-甲基吡啶循环至氧化反应器中去是有利的。另外,也可以在稳定态下把纯氧而不是空气作为氧化剂加入到连续装置中进行本发明的方法并且循环干燥气体,这样就得到了产生极少量废气的装置。
本发明方法的一个优点,是这样得到的烟酸不需作附加的处理就是自由流动的,并且即使在高的温度和相对湿度下也不会凝块。而且,通过改变喷雾干燥的操作参数,产品的颗粒尺寸可以设定到所需要的值。
图1表示按照本发明方法进行的一个实施例的连续装置。各个参考标号分别表示如下:
1.具有催化剂的固定床反应器
2.用于使反应混合物部分冷凝的吸收塔
3.中和(加入氨)
4.喷雾干燥器
5.干燥气体进料(热空气或惰性气体循环)
6.喷雾干燥器废气
7.使水和氨部分冷凝的冷凝塔
8.循环至反应器的气体
9.待处理的废气
10.废气处理(燃烧)
11.混合器/预热器
12.产品接取(烟酸)
13.输入至反应器的3-甲基吡啶
14.输入至反应器的氧气(空气)
15.输入至反应器的水(蒸汽)
16.去进行中和的氨
17.氨(水)循环
下列实施例用于说明按照本发明方法的步骤,但是不应理解为对本发明的限制。
实施例1
将含有40%(重量)烟酸、6%(重量)氨的烟酸铵水溶液以15升/小时的速率喷雾至流化床的喷雾干燥器(Niro FSDTM-4,直径1.2m,高2.5m),干燥气体(氮气)的进口温度为220℃,出口温度为100℃。流化床内部温度为70℃。这样产生的自由流动的产物包含89%重量的烟酸和11%重量的烟酸铵(含有0.05%残留的水分),堆积密度为0.4公斤/升,平均颗粒尺寸为451微米。
实施例2
将按照实施例1所得到的烟酸的喷雾干燥颗粒在流化床中与空气一起经45分钟加热至最高温度为170℃。经这样处理的颗粒的烟酸含量为99.3%(重量),堆积密度为0.44公斤/升。即使在50℃和100%相对湿度下储存48小时,它仍然能自由流动。
实施例3
在3-甲基吡啶与空气的气相氧化反应混合物的冷凝液中加入氨,得到浓度约为30%(重量)的烟酸铵溶液,所述氧化反应是在水存在下,在固定床催化剂作用下进行的。然后将该溶液在实验室喷雾干燥器中(Büchi AG,Switzerland)喷雾。在干燥气体进口温度为250℃,出口温度为162℃和氮的流率为600毫升/分钟的条件下,得到含量为99%(重量)至100%(重量)的烟酸。
在进口温度为200℃,出口温度为130℃和氮的流率为600毫升/分钟的条件下,得到含量为96.9%(重量)的烟酸。
Claims (8)
1.一种制备烟酸的方法,其特征在于喷雾干燥烟酸铵的水溶液。
2.如权利要求1所述的方法,其特征还在于所述的喷雾干燥是在干燥气体温度为160-250℃的条件下进行的。
3.如权利要求1或2所述的方法,其特征还在于喷雾干燥是在流化床喷雾干燥器中进行的。
4.如权利要求1-3中任一权利要求所述的方法,其特征还在于用喷雾干燥所生产的烟酸在100-200℃,更好在130-170℃的流化床中经受后热处理。
5.如权利要求1-3中任一权利要求所述的方法,其特征还在于用喷雾干燥所生产的烟酸在减压下、较好是在低于50毫巴,同时在70-150℃、更好是在80-120℃经受后热处理。
6.如权利要求1-5中任一权利要求所述的方法,其特征还在于所用的烟酸铵水溶液是通过把氨加入到可能是浓缩的3-甲基吡啶的催化氧化的粗水溶液而得到的。
7.如权利要求6所述的方法,其特征还在于制备烟酸铵的氨是全部或部分地从喷雾干燥废气中取出的。
8.如权利要求6或7所述的方法,其特征还在于将喷雾干燥废气中所存在的水全部或部分地循环至氧化反应器中。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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CH271997 | 1997-11-25 | ||
CH2719/97 | 1997-11-25 |
Related Child Applications (1)
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CNB2006101003638A Division CN100478332C (zh) | 1997-11-25 | 1998-11-25 | 烟酸的制造方法 |
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CN1222511A true CN1222511A (zh) | 1999-07-14 |
CN1272321C CN1272321C (zh) | 2006-08-30 |
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CNB2006101003638A Expired - Fee Related CN100478332C (zh) | 1997-11-25 | 1998-11-25 | 烟酸的制造方法 |
CNB981229360A Expired - Fee Related CN1272321C (zh) | 1997-11-25 | 1998-11-25 | 烟酸的制造方法 |
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CNB2006101003638A Expired - Fee Related CN100478332C (zh) | 1997-11-25 | 1998-11-25 | 烟酸的制造方法 |
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Country | Link |
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US (2) | US6077957A (zh) |
EP (2) | EP1440967B1 (zh) |
JP (1) | JP4586214B2 (zh) |
KR (1) | KR100611542B1 (zh) |
CN (2) | CN100478332C (zh) |
AT (2) | ATE266640T1 (zh) |
CA (1) | CA2253615C (zh) |
CZ (2) | CZ296940B6 (zh) |
DE (2) | DE59813463D1 (zh) |
DK (2) | DK0919548T3 (zh) |
ES (2) | ES2259783T3 (zh) |
HK (2) | HK1019148A1 (zh) |
HU (2) | HU225089B1 (zh) |
IL (1) | IL127201A (zh) |
IN (1) | IN187776B (zh) |
MX (1) | MXPA98009833A (zh) |
NO (1) | NO311887B1 (zh) |
PL (1) | PL193360B1 (zh) |
PT (2) | PT1440967E (zh) |
SK (2) | SK284427B6 (zh) |
TW (1) | TW495503B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100386317C (zh) * | 2004-04-08 | 2008-05-07 | 长春石油化学股份有限公司 | 烟碱酸的制造方法及该方法所用的触媒 |
CN101528701B (zh) * | 2006-08-08 | 2011-10-19 | 陶氏益农公司 | 急冷含氰基吡啶的气体反应产物的方法 |
CN106086103A (zh) * | 2016-07-11 | 2016-11-09 | 江南大学 | 一种饲料级烟酸的分离提取方法 |
CN108997206A (zh) * | 2018-09-19 | 2018-12-14 | 安徽瑞邦生物科技有限公司 | 一种以烟酸铵为原料生产烟酸的方法 |
CN109134360A (zh) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | 烟酸铵溶液喷雾干燥生产烟酸的工艺 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106013660B (zh) * | 2016-07-05 | 2018-02-06 | 广州新静界消音材料有限公司 | 一种吸音板及其安装方法 |
CN112344988A (zh) * | 2020-10-15 | 2021-02-09 | 南京航空航天大学 | 一种挤压油膜阻尼器入口油压油温的测量装置 |
CN114456107A (zh) * | 2020-11-10 | 2022-05-10 | 安徽瑞邦生物科技有限公司 | 一种以异烟酸铵为原料生产异烟酸的方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL75604B1 (zh) * | 1972-05-19 | 1974-12-31 | ||
JPS4949966A (zh) * | 1972-09-18 | 1974-05-15 | ||
US3929811A (en) * | 1973-11-15 | 1975-12-30 | Lummus Co | Production of pyridine nitriles and carboxylic acids |
JPS5311073A (en) * | 1976-07-19 | 1978-02-01 | Nippon Telegr & Teleph Corp <Ntt> | Phase constant measuring method |
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1998
- 1998-11-10 CA CA002253615A patent/CA2253615C/en not_active Expired - Fee Related
- 1998-11-17 TW TW087118988A patent/TW495503B/zh not_active IP Right Cessation
- 1998-11-17 IN IN2592MA1998 patent/IN187776B/en unknown
- 1998-11-17 SK SK1581-98A patent/SK284427B6/sk not_active IP Right Cessation
- 1998-11-17 SK SK384-2004A patent/SK285375B6/sk not_active IP Right Cessation
- 1998-11-20 AT AT98122066T patent/ATE266640T1/de active
- 1998-11-20 ES ES04010155T patent/ES2259783T3/es not_active Expired - Lifetime
- 1998-11-20 AT AT04010155T patent/ATE321753T1/de active
- 1998-11-20 DK DK98122066T patent/DK0919548T3/da active
- 1998-11-20 JP JP33061698A patent/JP4586214B2/ja not_active Expired - Fee Related
- 1998-11-20 DE DE59813463T patent/DE59813463D1/de not_active Expired - Lifetime
- 1998-11-20 DK DK04010155T patent/DK1440967T3/da active
- 1998-11-20 PT PT04010155T patent/PT1440967E/pt unknown
- 1998-11-20 EP EP04010155A patent/EP1440967B1/de not_active Expired - Lifetime
- 1998-11-20 EP EP98122066A patent/EP0919548B1/de not_active Expired - Lifetime
- 1998-11-20 DE DE59811380T patent/DE59811380D1/de not_active Expired - Lifetime
- 1998-11-20 PT PT98122066T patent/PT919548E/pt unknown
- 1998-11-20 ES ES98122066T patent/ES2221110T3/es not_active Expired - Lifetime
- 1998-11-23 CZ CZ0381698A patent/CZ296940B6/cs not_active IP Right Cessation
- 1998-11-23 US US09/197,477 patent/US6077957A/en not_active Expired - Lifetime
- 1998-11-23 KR KR1019980050257A patent/KR100611542B1/ko not_active IP Right Cessation
- 1998-11-23 CZ CZ20041093A patent/CZ296894B6/cs not_active IP Right Cessation
- 1998-11-23 IL IL12720198A patent/IL127201A/xx not_active IP Right Cessation
- 1998-11-24 NO NO19985489A patent/NO311887B1/no not_active IP Right Cessation
- 1998-11-24 PL PL329865A patent/PL193360B1/pl not_active IP Right Cessation
- 1998-11-24 MX MXPA98009833A patent/MXPA98009833A/es not_active IP Right Cessation
- 1998-11-25 CN CNB2006101003638A patent/CN100478332C/zh not_active Expired - Fee Related
- 1998-11-25 CN CNB981229360A patent/CN1272321C/zh not_active Expired - Fee Related
- 1998-11-25 HU HU9802719A patent/HU225089B1/hu not_active IP Right Cessation
- 1998-11-25 HU HU0501124A patent/HU226169B1/hu not_active IP Right Cessation
-
1999
- 1999-10-04 HK HK99104304A patent/HK1019148A1/xx not_active IP Right Cessation
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2000
- 2000-06-20 US US09/597,244 patent/US6376677B1/en not_active Expired - Lifetime
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- 2007-07-17 HK HK07107627.9A patent/HK1103234A1/xx not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100386317C (zh) * | 2004-04-08 | 2008-05-07 | 长春石油化学股份有限公司 | 烟碱酸的制造方法及该方法所用的触媒 |
CN101528701B (zh) * | 2006-08-08 | 2011-10-19 | 陶氏益农公司 | 急冷含氰基吡啶的气体反应产物的方法 |
CN106086103A (zh) * | 2016-07-11 | 2016-11-09 | 江南大学 | 一种饲料级烟酸的分离提取方法 |
CN108997206A (zh) * | 2018-09-19 | 2018-12-14 | 安徽瑞邦生物科技有限公司 | 一种以烟酸铵为原料生产烟酸的方法 |
CN109134360A (zh) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | 烟酸铵溶液喷雾干燥生产烟酸的工艺 |
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