CN108636447A - 一种Pd/MCM-22催化剂及其应用 - Google Patents
一种Pd/MCM-22催化剂及其应用 Download PDFInfo
- Publication number
- CN108636447A CN108636447A CN201810495143.2A CN201810495143A CN108636447A CN 108636447 A CN108636447 A CN 108636447A CN 201810495143 A CN201810495143 A CN 201810495143A CN 108636447 A CN108636447 A CN 108636447A
- Authority
- CN
- China
- Prior art keywords
- mcm
- catalyst
- solution
- sodium hydroxide
- reaction
- 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
Classifications
-
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- C07D213/80—Acids; Esters in position 3
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
本发明公开了一种Pd/MCM‑22催化剂,所述的Pd/MCM‑22催化剂制备方法如下:将MCM‑22原粉放入石英管中,焙烧,然后置于马弗炉再焙烧以除去模板剂;将焙烧后的MCM‑22用足量的硝酸铵溶液于80℃离子交换,焙烧;取上述焙烧后得到MCM‑22加入含有氢氧化钠和无水碳酸钠的混合碱溶液里超声剧烈搅拌下,加入硝酸钯得到悬浮液;然后在晶化后溶液冷却,用去离子水洗涤,下干燥,得到Pd/MCM‑22催化剂。所述的Pd/MCM‑22催化剂在合成4‑三氟甲基烟酸的应用。
Description
技术领域
本发明涉及一种Pd/MCM-22催化剂及其应用,属于催化合成技术领域。
背景技术
4-三氟甲基烟酸是含三氟甲基芳香化合物,具有独特的生物活性,它可以作为制备其他农药或医药的前体物质。而它的衍生物4-三氟甲基烟酰胺类化合物也有着重要的用途,可以作为杀虫剂的有效成分,更有效的杀死害虫并能保护动物免受杀虫剂危害,同时也克服了虫类对其他农药具有抗药性的难题。4-三氟甲基烟酸合成过程中催化剂的选择非常重要,故需要一种高催化活性的催化剂。
发明内容
本发明的目的在于提供一种Pd/MCM-22催化剂及其应用,该催化剂在优化条件下能催化4-三氟甲基烟酰胺和氢氧化钠的反应,具有较高的产物收率。
一种Pd/MCM-22催化剂,所述的所述的Pd/MCM-22催化剂制备方法如下:
步骤1、将MCM-22原粉放入石英管中,在氮气流下以3℃/min的速度从25℃升到540℃焙烧,然后置于马弗炉540℃再焙烧3h以除去模板剂;
步骤2、将焙烧后的MCM-22用足量的2mol/L的硝酸铵溶液于80℃离子交换12h后,在马弗炉中于540℃焙烧3h;
步骤3、取上述焙烧后得到MCM-22加入含有氢氧化钠和无水碳酸钠的混合碱溶液里超声30min,剧烈搅拌下加入硝酸钯得到悬浮液;
步骤4、将的氢氧化钠溶液加入到上述悬浮液里调节溶液的PH=11,然后在60℃晶化6h后溶液冷却至室温,用去离子水洗涤三次离心,60℃下干燥24h,得到Pd/MCM-22催化剂。
所述的Pd/MCM-22催化剂在合成4-三氟甲基烟酸的应用。
有益效果:本发明提供的用于4-三氟甲基烟酸的合成的催化剂在特定环境下具有较高的催化活性,2,6-二氯-4-三氟甲基烟酰通过氢化加成机理与活性金属催化剂形成有机金属络合物,再按催化氢化机理反应的氢解产物,4-三氟甲基烟酰胺在碱性条件下水解,随后生成相应的钠盐,再用盐酸调节PH之后得到产物4-三氟甲基烟酸,底物摩尔比对反应收率的影响十分显著,当氢氧化钠与上第一步产物的摩尔比为1:3时收率最高,在催化剂的作用下,反应条件较为温和4-三氟甲基烟酸的纯度和收率都得到大幅提高,不仅降低了合成过程中的能耗,而且节约了污染物的排放,做到了绿色环保节能的理想效果。
具体实施方式
实施例1
一种4-三氟甲基烟酸的合成方法,包括以下步骤:
步骤1、称取12.95g 2,6-二氯-4-三氟甲基烟酰胺置于高压釜中,然后依次加入100ml的无水甲醇、11.65g的无水碳酸钠和5%的Pd/C 2.5g,先用氮气置换2次,然后充入氢气使高压釜的压力达到4MPa,升温至80℃,保温反应10h,冷却至室温,抽滤,滤液浓缩,得到4-三氟甲基烟酰胺;
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和40ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸。
所述的Pd/MCM-22催化剂制备方法如下:
步骤1、将500g MCM-22原粉放入石英管中,在氮气流下以3℃/min的速度从25℃升到540℃焙烧,然后置于马弗炉540℃再焙烧3h以除去模板剂;
步骤2、将焙烧后的MCM-22用足量的2mol/L的硝酸铵溶液于80℃离子交换12h后,在马弗炉中于540℃焙烧3h;
步骤3、取380g上述焙烧后得到MCM-22加入含有氢氧化钠0.5mol和无水碳酸钠0.1mol的混合碱溶液里超声30min,剧烈搅拌下加入50ml到含有Pd(NO3)2的盐溶液中得到悬浮液;
步骤4、将0.2mol的氢氧化钠溶液加入到上述悬浮液里调节溶液的PH=11,然后在60℃晶化6h后溶液冷却至室温,用去离子水洗涤三次离心,60℃下干燥24h,得到Pd/MCM-22催化剂。
实施例2
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入5.5g 4-三氟甲基烟酰胺和40ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例3
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入2.5g 4-三氟甲基烟酰胺和40ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例4
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入13.5g 4-三氟甲基烟酰胺和40ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例5
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入16.5g 4-三氟甲基烟酰胺和40ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例6
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和30ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例7
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和20ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例8
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和10ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例9
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和50ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
实施例10
步骤2、在室温下,向250ml装有1.5gPd/MCM-22催化剂的烧瓶中,依次加入9.5g 4-三氟甲基烟酰胺和60ml浓度25%氢氧化钠的水溶液,将反应液加热至100℃,保温反应4h,固体溶解并变为淡黄色澄清溶液,反应结束后,冷却至室温,用浓盐酸调PH=2,搅拌,抽滤,滤渣用水洗涤,干燥,得到白色粉末状固体4-三氟甲基烟酸;其余步骤同实施例1。
对照例1
与实施例1不同点在于:中间体的合成步骤1中,用2.5g石英粉取代5%的Pd/C,其余步骤与实施例1完全相同。
对照例2
与实施例1不同点在于:中间体的合成步骤1中,不再加入5%的Pd/C,其余步骤与实施例1完全相同。
对照例3
与实施例1不同点在于:中间体的合成步骤1中,用等量的碳酸氢钠取代无水碳酸钠,其余步骤与实施例1完全相同。
对照例4
与实施例1不同点在于:中间体的合成步骤1中,用等量的氢氧化钠取代无水碳酸钠,其余步骤与实施例1完全相同。
对照例5
与实施例1不同点在于:中间体的合成步骤1中,2,6-二氯-4-三氟甲基烟酰胺和无水碳酸钠质量比为1:10,其余步骤与实施例1完全相同。
对照例6
与实施例1不同点在于:中间体的合成步骤1中,2,6-二氯-4-三氟甲基烟酰胺和无水碳酸钠质量比为10:1,其余步骤与实施例1完全相同。
对照例7
与实施例1不同点在于:中间体的合成步骤2中,用稀盐酸调PH=7;其余步骤与实施例1完全相同。
对照例8
与实施例1不同点在于:中间体的合成步骤2中,用氨水调PH=11;其余步骤与实施例1完全相同。
对照例9
与实施例1不同点在于:催化剂的合成步骤1中,MCM-22、硝酸钯质量比为1:5,其余步骤与实施例1完全相同。
对照例10
与实施例1不同点在于:催化剂的合成步骤1中,MCM-22、硝酸钯质量比为5:1,其余步骤与实施例1完全相同。
实施例和对照例不同条件下的反应结果如表所示
实验结果表明催化剂对4-三氟甲基烟酰胺和氢氧化钠的合成反应具有良好的催化效果,在反应条件一定时,中间体收率越高,催化性能越好,反之越差;4-三氟甲基烟酰胺、氢氧化钠质量比为实施例1和2时,合成效果最好,与实施例1不同点在于,实施例3至实施例10分别改变主要原料4-三氟甲基烟酰胺、氢氧化钠的用量和配比,对合成产物的收率有不同的影响;对照例1至对照例 2不再加入5%的Pd/C并用石英粉取代,其他步骤完全相同,导致产物收率明显降低,说明5%的Pd/C对第一步反应的产物影响很大;对照例3至对照例6用碳酸氢钠和氢氧化钠分别取代无水碳酸钠,改变了无水碳酸钠的用量效果依然不好,说明无水碳酸钠过多过少都不利于反应的进行;对照例7至对照例8提高溶液的PH值,催化反应的效果明显变差,说明PH对反应影响很大;对照例9至对照例10MCM-22、硝酸钯质量比发生变化,金属的负载量发生改变,反应的转化率和选择性很低,反应效果明显变差,产物收率依然不高;因此使用本发明的催化剂对4-三氟甲基烟酸的合成反应具有优异的催化效果。
Claims (2)
1.一种Pd/MCM-22催化剂,其特征在于 ,所述的Pd/MCM-22催化剂制备方法如下:
步骤1、将MCM-22原粉放入石英管中,在氮气流下以3℃/min的速度从25℃升到540℃焙烧,然后置于马弗炉540℃再焙烧3h以除去模板剂;
步骤2、将焙烧后的MCM-22用足量的2mol/L的硝酸铵溶液于80℃离子交换12h后,在马弗炉中于540℃焙烧3h;
步骤3、取上述焙烧后得到MCM-22加入含有氢氧化钠和无水碳酸钠的混合碱溶液里超声30min,剧烈搅拌下加入硝酸钯得到悬浮液;
步骤4、将的氢氧化钠溶液加入到上述悬浮液里调节溶液的PH=11,然后在60℃晶化6h后溶液冷却至室温,用去离子水洗涤三次离心,60℃下干燥24h,得到Pd/MCM-22催化剂。
2.一种权利要求1所述的Pd/MCM-22催化剂在合成4-三氟甲基烟酸的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810495143.2A CN108636447A (zh) | 2018-05-22 | 2018-05-22 | 一种Pd/MCM-22催化剂及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810495143.2A CN108636447A (zh) | 2018-05-22 | 2018-05-22 | 一种Pd/MCM-22催化剂及其应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108636447A true CN108636447A (zh) | 2018-10-12 |
Family
ID=63757264
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810495143.2A Pending CN108636447A (zh) | 2018-05-22 | 2018-05-22 | 一种Pd/MCM-22催化剂及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108636447A (zh) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1254883A1 (en) * | 1995-05-26 | 2002-11-06 | Ishihara Sangyo Kaisha, Ltd. | Process for producing sobstituted 1,1,1-trifluoro-3-butene-2-ones |
CN101851193A (zh) * | 2009-10-20 | 2010-10-06 | 西华大学 | 一种4-三氟甲基烟酸的制备方法 |
CN107604220A (zh) * | 2017-10-01 | 2018-01-19 | 新沂市中诺新材料科技有限公司 | 一种高塑性铝合金加工工艺 |
-
2018
- 2018-05-22 CN CN201810495143.2A patent/CN108636447A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1254883A1 (en) * | 1995-05-26 | 2002-11-06 | Ishihara Sangyo Kaisha, Ltd. | Process for producing sobstituted 1,1,1-trifluoro-3-butene-2-ones |
CN101851193A (zh) * | 2009-10-20 | 2010-10-06 | 西华大学 | 一种4-三氟甲基烟酸的制备方法 |
CN107604220A (zh) * | 2017-10-01 | 2018-01-19 | 新沂市中诺新材料科技有限公司 | 一种高塑性铝合金加工工艺 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107721913B (zh) | 一种2,3-二氯吡啶的制备方法 | |
CN109369478B (zh) | 一种蛋氨酸锌螯合物的合成方法 | |
CN106316810B (zh) | 一种提高1,1,3-三氯丙酮合成收率的制备方法 | |
CN103130657B (zh) | 一种2-氯-4-氨基苯酚的合成方法 | |
CN105924428A (zh) | 一种合成吡虫啉的方法 | |
CN108586328A (zh) | 一种4-三氟甲基烟酸的合成方法 | |
CN103613535A (zh) | 一种5-(甲氧基甲基)-2,3-吡啶二甲酸二甲酯的合成方法 | |
CN106518645A (zh) | 一种高顺式功夫菊酸的合成工艺 | |
CN108636447A (zh) | 一种Pd/MCM-22催化剂及其应用 | |
CN100537552C (zh) | 一种制备瑞格列奈的方法 | |
CN102351800A (zh) | 一种5-甲基苯并咪唑-2-氨基甲酸甲酯的制备方法 | |
CN104447758A (zh) | 吡唑并[3,4-d]嘧啶类化合物的合成工艺 | |
CN105461580A (zh) | 一种异丙甲草胺的合成方法 | |
CN105348323A (zh) | 一种以三氯乙酰氯为初始原料水相合成毒死蜱的方法 | |
CN102249993A (zh) | 对生产3-氰基吡啶所产生的废水处理及回收烟酸的方法 | |
CN109879813A (zh) | 一种2-巯基-5-甲氧基苯并咪唑的新工艺合成方法 | |
CN109053551A (zh) | 4-哌啶乙酸甲酯的高效合成方法 | |
CN106140288B (zh) | 一种二甲醚直接制备六甲基苯的催化剂及其制备方法和应用 | |
CN109251169B (zh) | 一种利用2-op精馏残渣制备吡啶-2-甲酸铬的方法 | |
CN107597175A (zh) | 一种合成碳酸二甲酯的无氯CuI/Y催化剂及制法和应用 | |
CN110092783A (zh) | 一种噻虫嗪的制备方法 | |
CN108530352A (zh) | 一种2,6-二氯-4-三氟甲基烟酰胺的合成方法 | |
CN109320472B (zh) | 一种3,4-二氯5-氰基异噻唑的制备方法 | |
CN115141139B (zh) | 一种液相催化氯化制备五氯吡啶的方法 | |
CN107474018A (zh) | 一种高活性腈菌唑的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181012 |