CN108380208B - 2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶用Pd-Mg/C催化剂及制备方法 - Google Patents
2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶用Pd-Mg/C催化剂及制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- MAKFMOSBBNKPMS-UHFFFAOYSA-N 2,3-dichloropyridine Chemical compound ClC1=CC=CN=C1Cl MAKFMOSBBNKPMS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- GPAKJVMKNDXBHH-UHFFFAOYSA-N 2,3,6-trichloropyridine Chemical compound ClC1=CC=C(Cl)C(Cl)=N1 GPAKJVMKNDXBHH-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000011734 sodium Substances 0.000 claims abstract description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000001433 sodium tartrate Substances 0.000 claims abstract description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 7
- 229960002167 sodium tartrate Drugs 0.000 claims description 7
- 235000011004 sodium tartrates Nutrition 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- HELHAJAZNSDZJO-UHFFFAOYSA-L sodium tartrate Chemical compound [Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O HELHAJAZNSDZJO-UHFFFAOYSA-L 0.000 abstract 1
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- MEQBJJUWDCYIAB-UHFFFAOYSA-N 2-chloropyridin-3-amine Chemical compound NC1=CC=CN=C1Cl MEQBJJUWDCYIAB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
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- PWRBCZZQRRPXAB-UHFFFAOYSA-N 3-chloropyridine Chemical compound ClC1=CC=CN=C1 PWRBCZZQRRPXAB-UHFFFAOYSA-N 0.000 description 1
- 239000005886 Chlorantraniliprole Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
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- 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
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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Abstract
本发明公开了一种2,3,6‑三氯吡啶催化加氢制2,3‑二氯吡啶用Pd‑Mg/C催化剂及制备方法，该催化剂是在酒石酸钠存在下，将Na2PdCl4和MgCl2与经双氧水与盐酸处理的活性炭载体混合搅拌，干燥后再用H2还原，即得Pd‑Mg/C催化剂。本发明催化剂制备工艺实现了纳米金属高度分散在载体上，并通过助剂Mg，调整了催化剂表面的酸碱状态，提高了2,3‑二氯吡啶选择性，同时增强了贵金属钯与载体之间的相互作用，稳定性好，提高了催化剂的重复使用性能，有利于降低生产成本。
Description
技术领域
本发明属于负载型贵金属催化剂制备技术领域，具体涉及一种2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶用Pd-Mg/C催化剂及其制备方法。
背景技术
2,3-二氯吡啶是重要的精细化工中间体，广泛应用于医药与农药研究领域，特别是农药领域，它是合成新型杀虫剂氯虫苯甲酰的重要中间体，具有广阔的应用前景。
2,3-二氯吡啶可以以2-氯-3-氨基吡啶为起始原料，经重氮化及Sandmeyer氯代两步反应得到，该方法的缺点在于产率较低，并且原料2-氯-3-氨基吡啶成本较高，而且重氮化产生大量废液，环境污染严重。2,3-二氯吡啶还可以通过吡啶或者3-氯吡啶的液相氯化得到，但仍存在收率低问题，没有工业应用价值。以2,3,6-三氯吡啶为原料通过催化加氢的方法制备2,3-二氯吡啶，具有原料价格便宜、工艺简单、生产清洁等优点，是一条非常具有应用前景的合成路线。该方法最早见于日本专利JP1193246，以Pd/C为催化剂，常压50℃反应14h，2,3-二氯吡啶选择性达88％，但原料转化率只有33％，生产效率低；专利CN103145609A中报道以甲酸铵为供氢体，利用催化氢转移的方法，尽管工艺简单，操作安全，但2,3-二氯吡啶收率只有40.83％。
目前，2,3,6-三氯吡啶催化加氢制备2,3-二氯吡啶主要存在原料转化率及2,3-二氯吡啶选择性低的问题，从而限制了其工业化应用。
发明内容
本发明所要解决的技术问题在于针对上述现有技术的不足，提供一种2,3-二氯吡啶选择性及收率较高的2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶用Pd-Mg/C催化剂及其制备方法。
为解决上述技术问题，本发明采用的Pd-Mg/C催化剂由下述方法制备而成：
1、将活性炭经过双氧水与盐酸改性处理，得到改性活性炭。
2、按照以改性活性炭质量计，Pd的负载量为4％～7％，Mg的负载量为0.2％～0.5％，将酒石酸钠溶于蒸馏水中，再加入改性活性炭搅拌均匀，在50～80℃下搅拌0.5～1小时，然后加入完全溶解于蒸馏水的Na2PdCl4和MgCl2溶液，继续搅拌2～3小时，静置，倾去上清液，80～120℃烘干。
3、将烘干后的样品在氢气气氛下还原，得到Pd-Mg/C催化剂。
上述步骤1中，改性处理的具体方法为：将活性炭加入双氧水与盐酸的混合溶液中，室温浸泡40～60分钟，然后煮沸20～30分钟，用蒸馏水洗涤至中性，得到改性活性炭，其中，所述活性炭的比表面积为1200m2/g～2000m2/g，所述混合溶液中H2O2质量浓度为5％～15％、HCl质量浓度为4％～6％，所述活性炭与混合溶液的质量体积比为1g:15～25mL。
上述步骤2中，所述酒石酸钠的加入量为Na2PdCl4摩尔量的4～8倍。
上述步骤3中，将烘干后的样品在氢气气氛下，200～300℃还原1～2小时。
本发明与现有技术相比具有以下优点：
1、本发明用双氧水与盐酸对活性炭载体进行处理，不仅除去了活性炭本身的杂质，而且有利于扩孔作用，从而有利于反应物分子在催化剂表面的扩散传质，避免了采用硝酸处理活性炭，减少了环境污染。
2、本发明采用酒石酸钠实现了纳米金属高度分散在载体上，并通过助剂Mg，调整了催化剂表面的酸碱状态，提高了2,3-二氯吡啶选择性，同时增强了贵金属钯与载体之间的相互作用，稳定性好，提高了催化剂的重复使用性能，有利于降低生产成本。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
1、将10g比表面积为1562m2/g的活性炭加入200mL双氧水与盐酸的混合水溶液中，该混合溶液中H2O2质量浓度为10％、HCl质量浓度为5％，室温浸泡1小时，然后煮沸20分钟，用蒸馏水洗涤至中性，得到改性活性炭。
2、将6.49g(2.82×10-2mol)Na2C4H4O6·2H2O溶于200mL蒸馏水中，再加入9.5g改性活性炭，搅拌均匀，升温至60℃，恒温搅拌40分钟，然后加入20mL含1.38g Na2PdCl4(4.69×10-3mol)和0.29g MgCl2·6H2O的水溶液，60℃继续搅拌2.5小时，静置分层后倾去上清液，120℃烘干。
3、将烘干后的样品在氢气气氛下，200℃还原2小时，自然冷却并用氮气吹扫至室温，得到Pd-Mg/C催化剂，以改性活性炭计，Pd的负载量为5％、Mg的负载量为0.35％。
实施例2
1、将10g比表面积为1218m2/g的活性炭加入200mL双氧水与盐酸的混合水溶液中，该混合溶液中H2O2质量浓度为5％、HCl质量浓度为5％，室温浸泡1小时，然后煮沸20分钟，用蒸馏水洗涤至中性，得到改性活性炭。
2、将4.32g(1.88×10-2mol)Na2C4H4O6·2H2O溶于200mL蒸馏水中，再加入9.5g改性活性炭，搅拌均匀，升温至80℃，恒温搅拌60分钟，然后加入20mL含1.38g Na2PdCl4(4.69×10-3mol)和0.17g MgCl2·6H2O的水溶液，80℃继续搅拌3小时，静置分层后倾去上清液，120℃烘干。
3、将烘干后的样品在氢气气氛下，300℃还原1小时，自然冷却并用氮气吹扫至室温，得到Pd-Mg/C催化剂，以改性活性炭计，Pd的负载量为5％、Mg的负载量为0.2％。
实施例3
1、将10g比表面积为1989m2/g的活性炭加入200mL双氧水与盐酸的混合水溶液中，该混合溶液中H2O2质量浓度为15％、HCl质量浓度为5％，室温浸泡1小时，然后煮沸20分钟，用蒸馏水洗涤至中性，得到改性活性炭。
2、将8.64g(3.75×10-2mol)Na2C4H4O6·2H2O溶于200mL蒸馏水中，再加入9.5g改性活性炭，搅拌均匀，升温至50℃，恒温搅拌30分钟，然后加入20mL含1.38g Na2PdCl4(4.69×10-3mol)和0.42g MgCl2·6H2O的水溶液，50℃继续搅拌2小时，静置分层后倾去上清液，120℃烘干。
3、将烘干后的样品在氢气气氛下，250℃还原1.5小时，自然冷却并用氮气吹扫至室温，得到Pd-Mg/C催化剂，以改性活性炭计，Pd的负载量为5％、Mg的负载量为0.5％。
对比例1
在实施例1的步骤2中，不添加Na2C4H4O6·2H2O，其他步骤与实施例1相同，得到Pd-Mg/C催化剂。
对比例2
在实施例1的步骤2中，不添加MgCl2·6H2O，其他步骤与实施例1相同，得到Pd/C催化剂。
对上述实施例1～3和对比例1～2制备的催化剂性能进行评价：将5.0g 2,3,6-三氯吡啶、3.5g NaHCO3、0.05g催化剂、30mL甲醇加入高压反应釜中，检查气密性，用N2置换釜内空气三次，再用H2置换氮气3次，然后升温至50℃，继续通H2至压力为2MPa，反应4小时，取样进行GC分析，结果见表1。
表1不同催化剂催化2,3,6-三氯吡啶加氢制2,3-二氯吡啶色谱结果
由表1可以明显看出，本发明催化剂在2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶反应中具有较高的活性和选择性。与实施例1相比，对比例1在催化剂制备过程中不加入酒石酸钠，其催化反应的转化率和收率均较低；与实施例1相比，对比例2在催化剂制备过程中不加入助剂Mg，催化剂的活性虽然高，但目标产物的选择性及收率较低。因此，吸附过程中酒石酸钠的加入能够提高催化剂的活性；同时助剂Mg能够提高催化剂的选择性。两者同时具备时，催化剂的活性和选择性同时提高。
发明人将上述反应完后实施例1的催化剂从反应液中过滤出来进行重复性试验，试验结果见表2。
表2实施例1催化剂的重复使用结果
由表2可见，本发明催化剂重复使用4次，催化剂的活性基本不变，说明催化剂的稳定性好，提高了催化剂的重复使用性能。
Claims (5)
1.一种2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶的方法，其特征在于：将5.0g 2,3,6-三氯吡啶、3.5g NaHCO3、0.05g催化剂、30mL甲醇加入高压反应釜中，检查气密性，用N2置换釜内空气三次，再用H2置换氮气3次，然后升温至50℃，继续通H2至压力为2MPa，反应4小时；其中，所述催化剂为Pd-Mg/C催化剂，该催化剂由下述方法制备得到：
（1）将活性炭经过双氧水与盐酸改性处理，所述改性处理的具体方法为：将活性炭加入双氧水与盐酸的混合溶液中，室温浸泡40～60分钟，然后煮沸20～30分钟，用蒸馏水洗涤至中性，得到改性活性炭；
（2）按照以改性活性炭质量计，Pd的负载量为4%～7%，Mg的负载量为0.2%～0.5%，将酒石酸钠溶于蒸馏水中，再加入改性活性炭搅拌均匀，在50～80℃下搅拌0.5～1小时，然后加入完全溶解于蒸馏水的Na2PdCl4和MgCl2溶液，继续搅拌2～3小时，静置，倾去上清液，80～120℃烘干；其中，所述酒石酸钠的加入量为Na2PdCl4摩尔量的4～8倍；
（3）将烘干后的样品在氢气气氛下还原，得到Pd-Mg/C催化剂。
2.根据权利要求1所述的2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶的方法，其特征在于：所述活性炭的比表面积为1200m2/g～2000m2/g。
3.根据权利要求1所述的2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶的方法，其特征在于：所述混合溶液中H2O2质量浓度为5%～15%、HCl质量浓度为4%～6%。
4.根据权利要求1所述的2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶的方法，其特征在于：所述活性炭与混合溶液的质量体积比为1g:15～25mL。
5.根据权利要求1所述的2,3,6-三氯吡啶催化加氢制2,3-二氯吡啶的方法，其特征在于：在步骤（3）中，将烘干后的样品在氢气气氛下，200～300℃还原1～2小时。
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