CN105693602A - 以改性分子筛催化生产烟酰胺的方法 - Google Patents
以改性分子筛催化生产烟酰胺的方法 Download PDFInfo
- Publication number
- CN105693602A CN105693602A CN201610172187.2A CN201610172187A CN105693602A CN 105693602 A CN105693602 A CN 105693602A CN 201610172187 A CN201610172187 A CN 201610172187A CN 105693602 A CN105693602 A CN 105693602A
- Authority
- CN
- China
- Prior art keywords
- modified molecular
- molecular screen
- nicotiamide
- catalytic
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 6
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 title abstract description 19
- 235000005152 nicotinamide Nutrition 0.000 title abstract description 11
- 239000011570 nicotinamide Substances 0.000 title abstract description 11
- 229960003966 nicotinamide Drugs 0.000 title abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 37
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 10
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 229960003512 nicotinic acid Drugs 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 235000001968 nicotinic acid Nutrition 0.000 description 3
- 239000011664 nicotinic acid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- KRGPXXHMOXVMMM-CIUDSAMLSA-N (S,S,S)-nicotianamine Chemical compound [O-]C(=O)[C@@H]([NH3+])CC[NH2+][C@H](C([O-])=O)CC[NH+]1CC[C@H]1C([O-])=O KRGPXXHMOXVMMM-CIUDSAMLSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- XJLXINKUBYWONI-NNYOXOHSSA-N NADP zwitterion Chemical compound NC(=O)C1=CC=C[N+]([C@H]2[C@@H]([C@H](O)[C@@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](OP(O)(O)=O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 XJLXINKUBYWONI-NNYOXOHSSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 229930003537 Vitamin B3 Natural products 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000013595 glycosylation Effects 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 210000002510 keratinocyte Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000002752 melanocyte Anatomy 0.000 description 1
- 210000002780 melanosome Anatomy 0.000 description 1
- KRGPXXHMOXVMMM-UHFFFAOYSA-N nicotianamine Natural products OC(=O)C(N)CCNC(C(O)=O)CCN1CCC1C(O)=O KRGPXXHMOXVMMM-UHFFFAOYSA-N 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 210000004694 pigment cell Anatomy 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 230000036548 skin texture Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000036572 transepidermal water loss Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 235000019160 vitamin B3 Nutrition 0.000 description 1
- 239000011708 vitamin B3 Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明涉及烟酰胺合成领域，具体地说是一种以改性分子筛催化生产烟酰胺的方法。3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为10~15mL：100g：2~9g：3~8g，制备得到烟酰胺。本发明制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产。产品收率达99.5%以上，纯度在99.5以上。
Description
技术领域
本发明属于烟酰胺合成领域，具体地说是一种以改性分子筛催化生产烟酰胺的方法。
背景技术
烟酰胺（英语：Nicotinamide）是烟酸（维生素B3）的酰胺，属于B族维生素，化学名为3-吡啶甲酰胺，又名烟碱酰胺和尼克酰胺，简称VB3或NsA。烟酰胺为白色结晶或结晶性粉末，无臭或几乎无臭，味苦。该品在水或乙醇中易溶，在甘油中溶解；在乙醚中几乎不溶;在碳酸钠试液或氢氧化钠试液中易溶。是辅酶工和辅酶Ⅱ等的组成部分之一，它参与氧化还原过程，具有促进细胞新陈代谢和扩展血管的功能，能促进人体和动物生长发育。烟酰胺也具有美容效果，可以迅速穿过角质层，改善皮肤的屏障作用，降低经表皮失水率；抑制黑素小体从色素细胞转移到角质形成细胞，抑制黑素输送途径，减少面部红斑、色素沉积；阻止蛋白质非酶糖化，改善面部发黄的状况;促进真皮胶原蛋白和调节真皮中黏多糖的含量，减少皱纹；通过减少油脂的分泌，减小毛孔使皮肤纹理细腻光滑。
人们生活水平的提高和动物饲料产品的需求增长促进了全球烟酸/烟酰胺的快速发展。有数据显示,2007年全球吡啶总产量的35%以上都是用来满足烟酰胺/烟酸的生产消耗。目前，全球烟酸／烟酰胺总生产能力近6万t/a。其中，美国和欧洲的产能在2．85万～2．95万以．其余的超过3万t／a的产能主要分布在亚洲，主要生产国家为中国、印度和日本。
目前工业上的生产烟酰胺的方法主要有液相直接氧化法（高锰酸钾法、重铬酸钾法）；催化氧化法主要有氨氧化法、空气氧化法等，液相直接氧化生产烟酸、烟酰胺工艺一般属于间歇生产，该工艺简单，但是环境污染严重，原料和辅助材料消耗高，生产质量不稳定，难以大规模生产，目前国内大多数生产单位使用该工艺，该工艺已经趋于淘汰。催化氧化法适应工业化大规模生产，技术含量高、一次性投资大、原料消耗低、产品质量稳定、环境污染轻，国内企业普遍使用，很多企业和科研单位也正在积极开发。但是目前催化氧化法制备烟酰胺的产品的工艺中仍普遍存在制备时间长、反应不充分、工序复杂、生产效率低、生产转化率低等问题，研发一种高效并且高转化率的催化氧化法合成烟酰胺系列产品成为趋势。
发明内容
本发明的目的是克服现有烟酰胺的催化氧化法存在制备时间长、反应不充分、工序复杂、生产效率低、生产转化率低等问题，提供一种以改性分子筛催化生产烟酰胺的方法。
本发明的方案是通过这样实现的：一种以改性分子筛催化生产烟酰胺的方法，3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，制备得到烟酰胺，其反应方程式如下：
作为本发明的进一步限定，所述的催化氧化剂为高锰酸钾KMnO4、次氯酸钠NaClO、双氧水H2O2、硫酸铵（NH4）2SO4、过氧乙酸C2H4O3中的任一种或是它们的混合物。
作为本发明的进一步限定，所述的改性分子筛为MCM-41、MCM-22、HY以及HZSM-5，优选MCM-41、MCM-22分子筛中的任一种，经过600℃高温活化6h，冷却后于45℃～60℃的硅烷化试剂中隔氧搅拌反应12~24h得到。
作为本发明的进一步限定，所述的水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为10~15mL：100g：2~9g：3~8g。
作为本发明的进一步限定，所述的水解反应是在温度为60~80℃条件下水解1~3h。
本发明具备以下良好效果：利用氧化催化剂和改性分子筛促进烟酰胺的氧化反应的发生，在催化剂存在的情况下降低生产的能耗和缩短反应的时间，实现生产成本的降低，提高产品的质量，减小环境污染。本发明使用的改性分子筛具有结构稳定、催化活性和选择性高的特点，使得水解反应过程温和，制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产。产品收率达99.5%以上，纯度在99.5以上。
附图说明
图1.本发明烟酰胺水解反应方程式图。
具体实施方式
以下结合实施例和附图描述本发明制备烟酰胺的方法，这些描述并不是对本发明内容作进一步的限定。
实施例1
本实施例用到的所述的催化氧化剂为高锰酸钾KMnO4。改性分子筛为MCM-22，经过600℃高温活化6h，冷却后于60℃的硅烷化试剂中隔氧搅拌反应20h得到。
本实施例3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为13mL：100g：7g：6g，水解反应是在温度为80℃条件下水解2h，制备得到烟酰胺。
本实施例得到的烟酰胺产品收率达99.8%，纯度在99.5%。
实施例2
本实施例用到的所述的催化氧化剂为过氧乙酸C2H4O3。改性分子筛为HY，经过600℃高温活化6h，冷却后于45℃的硅烷化试剂中隔氧搅拌反应18h得到。
本实施例3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为12mL：100g：6.5g：5.5g，水解反应是在温度为60℃条件下水解1.5h，制备得到烟酰胺。
本实施例得到的烟酰胺产品收率达99.9，纯度在99.8。
实施例3
本实施例用到的所述的催化氧化剂为氯酸钠NaClO。改性分子筛为HZSM-5，经过600℃高温活化6h，冷却后于50℃的硅烷化试剂中隔氧搅拌反应12h得到。
本实施例3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为12mL：100g：7g：5g，水解反应是在温度为70℃条件下水解2h，制备得到烟酰胺。
本实施例得到的烟酰胺产品收率达99.8，纯度在99.7%。
实施例4
本实施例用到的所述的催化氧化剂为硫酸铵（NH4）2SO4和过氧乙酸C2H4O3按照质量比1：1的混合物。改性分子筛为MCM-41，经过600℃高温活化6h，冷却后于60℃的硅烷化试剂中隔氧搅拌反应20h得到。
本实施例3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为10mL：100g：2g：3g，水解反应是在温度为65℃条件下水解1h，制备得到烟酰胺。
本实施例得到的烟酰胺产品收率达99.8%，纯度在99.9%上。
实施例5
本实施例用到的所述的催化氧化剂为双氧水H2O2。改性分子筛为MCM-22，经过600℃高温活化6h，冷却后于55℃的硅烷化试剂中隔氧搅拌反应24h得到。
本实施例3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为15mL：100g：9g：8g，水解反应是在温度为70℃条件下水解3h，制备得到烟酰胺。
本实施例得到的烟酰胺产品收率达99.6%，纯度在99.7%。
本发明上述实施例方案仅是对本发明的说明而不能限制本发明，权利要求中指出了本发明产品组成成分、成分比例、制备方法参数的范围，而上述的说明并未指出本发明参数的范围，因此，在与本发明的权利要求书相当的含义和范围内的任何改变，都应当认为是包括在权利要求书的范围内。
本发明是经过多位烟酰胺合成反应研发人员长期工作经验积累，并通过创造性劳动创作而出，本发明使用的改性分子筛具有结构稳定、催化活性和选择性高的特点，使得水解反应过程温和，制备得到的产品易分离纯度高、收率高、三废污染少，有利于工业规模化生产。产品收率达99.5%以上，纯度在99.5%以上。
Claims (5)
1.一种以改性分子筛催化生产烟酰胺的方法，其特征在于，3-氰基吡啶与水，在催化氧化剂、改性分子筛存在的条件下，发生水解反应，制备得到烟酰胺，其反应方程式如下：
。
2.根据权利要求1所述的以改性分子筛催化生产烟酰胺的方法，其特征在于，所述的催化氧化剂为高锰酸钾KMnO4、次氯酸钠NaClO、双氧水H2O2、硫酸铵（NH4）2SO4、过氧乙酸C2H4O3中的任一种或是它们的混合物。
3.根据权利要求1所述的以改性分子筛催化生产烟酰胺的方法，其特征在于，所述的改性分子筛为MCM-41、MCM-22、HY以及HZSM-5，优选MCM-41、MCM-22分子筛中的任一种，经过600℃高温活化6h，冷却后于45℃～60℃的硅烷化试剂中隔氧搅拌反应12~24h得到。
4.根据权利要求1所述的以改性分子筛催化生产烟酰胺的方法，其特征在于，所述的水解反应过程中水、3-氰基吡啶、催化氧化剂、改性分子筛三者的重量或体积份数比为10~15mL：100g：2~9g：3~8g。
5.根据权利要求1所述的以改性分子筛催化生产烟酰胺的方法，其特征在于，所述的水解反应是在温度为60~80℃条件下水解1~3h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172187.2A CN105693602A (zh) | 2016-03-24 | 2016-03-24 | 以改性分子筛催化生产烟酰胺的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172187.2A CN105693602A (zh) | 2016-03-24 | 2016-03-24 | 以改性分子筛催化生产烟酰胺的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105693602A true CN105693602A (zh) | 2016-06-22 |
Family
ID=56231344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610172187.2A Pending CN105693602A (zh) | 2016-03-24 | 2016-03-24 | 以改性分子筛催化生产烟酰胺的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105693602A (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004056776A1 (en) * | 2002-12-23 | 2004-07-08 | Council Of Scientific And Industrial Research | Process for conversion of cyanopyridines to nicotinamides and catalyst therefor, process for preparing said catalyst |
| CN101851194A (zh) * | 2010-06-03 | 2010-10-06 | 浙江新赛科药业有限公司 | 一种烟酰胺的制备方法 |
| CN104072409A (zh) * | 2014-06-27 | 2014-10-01 | 温州大学 | 一种吡啶酰胺类化合物的合成方法 |
| CN104592106A (zh) * | 2014-10-23 | 2015-05-06 | 华中药业股份有限公司 | 一种烟酰胺的改进制备方法 |
-
2016
- 2016-03-24 CN CN201610172187.2A patent/CN105693602A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004056776A1 (en) * | 2002-12-23 | 2004-07-08 | Council Of Scientific And Industrial Research | Process for conversion of cyanopyridines to nicotinamides and catalyst therefor, process for preparing said catalyst |
| CN101851194A (zh) * | 2010-06-03 | 2010-10-06 | 浙江新赛科药业有限公司 | 一种烟酰胺的制备方法 |
| CN104072409A (zh) * | 2014-06-27 | 2014-10-01 | 温州大学 | 一种吡啶酰胺类化合物的合成方法 |
| CN104592106A (zh) * | 2014-10-23 | 2015-05-06 | 华中药业股份有限公司 | 一种烟酰胺的改进制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 张淑蓉，等: "酶法水解3-氰基吡啶制备烟酸", 《西南大学学报(自然科学版)》 * |
| 肖志斌，等: "二氧化锰催化水解3 -氰基吡啶生成烟酰胺", 《南昌大学学报(理科版)》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103658673B (zh) | 一种铑钯合金纳米晶的制备方法及其产品 | |
| CN107382844A (zh) | 一种以烟酸胺为原料生产烟酸的方法 | |
| CN104549234B (zh) | 一种具有过氧化氢酶催化特性的CDs-Pt纳米材料 | |
| CN105498756B (zh) | 二氧化碳加氢制甲醇的催化剂 | |
| CN102702093B (zh) | 一种吡啶硫酮锌的合成方法 | |
| CN108220595B (zh) | 利用木薯干粉和甲醛还原浸出氧化锰矿的方法 | |
| CN105602701A (zh) | 一种亚麻籽深加工新方法 | |
| CN108786797A (zh) | 一种PtAu@Ag核-壳纳米晶体电催化剂及其制备方法 | |
| CN105693602A (zh) | 以改性分子筛催化生产烟酰胺的方法 | |
| CN103539657A (zh) | 一种栀子来源的藏红花酸的制备方法 | |
| CN102516142B (zh) | 一种蛋氨酸铬螯合物的制备方法 | |
| CN104310471B (zh) | 一种合成氯氧化铋珠光颜料的方法 | |
| CN103933979A (zh) | 一种用于控制TiO2纳米管负载金属价态的制备方法 | |
| CN102898338A (zh) | 一种α-氨基酸铬（III）螯合物及其制备方法 | |
| CN113999171B (zh) | 一种高含量双吡啶硫酮的合成方法 | |
| CN101717345A (zh) | 一种苏氨酸铬化合物及其制备方法 | |
| CN102527408B (zh) | 一种二甲基砜的制备方法及其固体催化剂 | |
| CN101580756B (zh) | 一种微乳化香精的制备方法 | |
| CN108251663A (zh) | 利用木薯淀粉还原浸出氧化锰矿的方法 | |
| CN105274560A (zh) | 一种新型Ce-La共掺杂的高催化活性Ti/Ce-Lanano-TiO2修饰电极的制备及其电催化还原L-胱氨酸的方法 | |
| CN104496894A (zh) | 一种高纯度烟酰胺及烟酸的制备方法 | |
| CN105906560A (zh) | 一种生产均匀片晶吡啶硫酮锌的方法 | |
| CN109232404A (zh) | 一种吡啶甲酸铬的制备方法 | |
| CN104327082B (zh) | 一种从结晶母液中高效环保回收核黄素的方法 | |
| CN102417495A (zh) | 一种方酸铜催化空气氧化糠偶姻制备糠偶酰的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160622 |