CN114805259B - 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 - Google Patents
一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 Download PDFInfo
- Publication number
- CN114805259B CN114805259B CN202210499544.1A CN202210499544A CN114805259B CN 114805259 B CN114805259 B CN 114805259B CN 202210499544 A CN202210499544 A CN 202210499544A CN 114805259 B CN114805259 B CN 114805259B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- furfuryl
- nickel
- amine
- 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.)
- Active
Links
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 238000005576 amination reaction Methods 0.000 title claims abstract description 19
- 230000009849 deactivation Effects 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000002779 inactivation Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 4
- 229910052593 corundum Inorganic materials 0.000 abstract 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 abstract 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006268 reductive amination reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 nitrile compound Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种耐失活镍基催化剂上选择性制备糠胺的方法，包括以下步骤：(1)镍基催化剂的制备：将含镍前驱体化合物与铝盐混合后煅烧，然后将所得混合物进行还原即可，将制得的催化剂记为Ni@Al2O3；(2)催化糠醇胺化反应：催化剂为步骤(1)中制得的Ni@Al2O3催化剂，反应原料为溶于有机溶剂的糠醇溶液，反应气由H2和NH3组成；其中，H2的分压为0～0.2MPa，NH3的分压为0.2～1.0MPa，反应温度为150～250℃。反应结果表明：本发明所提供的方法在Ni@Al2O3催化剂上糠胺转化率可达30％以上，同时保持选择性可达99％。此外，本发明所提供的Ni@Al2O3催化剂能在多次重复反应后仍能保持较高的糠胺选择性以及转化率。
Description
技术领域
本发明涉及糠醇胺化生成糠胺的方法，具体涉及一种耐失活镍基催化剂催化糠醇选择性胺化制备糠胺的方法。
背景技术
有机胺是一种重要的含氮基础化学品，在农药、医药、食品及高分子材料等领域应用广泛。然而，自然界中存在的有机胺在种类和产量上均不足以满足工业生产需求，需要大规模人工合成(Froidevaux,V.；Negrell,C.；Caillol,S.；Pascault,J.P.；Boutevin,B.Biobased Amines:From Synthesis to Polymers；Present and Future[J].Chem Rev,2016,116(22):14181-14224.)。工业上合成有机胺的方法主要包括腈类化合物加氢法、硝基芳香化合物还原法、卤代烃氨(胺)解法、酮/醛和醇的还原胺化法等方法；；其中，前几种合成方法因原料来源强烈依赖于传统石化资源而生产成本高。近年来，随着生物质制醇技术的发展，醇类分子的来源更加广泛且成本降低，这使得以醇为反应物来合成有机胺具有巨大的发展潜力(刘迎新,舒慧敏,刘海燕等.非均相金属催化剂催化醇类还原胺化合成伯胺的研究进展[J].高校化学工程学报,2018,32(3):487-498.)。
在众多胺类化合物中，糠胺及其衍生物是一类非常重要的有机化工原料/中间体，在农药、医药、树脂及合成纤维等方面均有着重要应用。目前，糠胺主要是以糠醛作为原料，在金属催化剂上通过还原胺化法来制备。例如，Chatterjee等以Al2O3负载的金属Rh作为催化剂，在80℃和2MPa H2下反应，100％糠醛转化率时糠胺选择性达85％；然而，该催化剂在循环使用5次后(即累积反应时间达10h)，存在明显失活现象且糠胺收率显著下降的缺点(Maya Chatterjee,Takayuki Ishizaka,Hajime Kawanami.Reductive amination offurfural to furfurylamine using aqueous ammonia solution and molecularhydrogen:an environmentally friendly approach.Green Chem.,2016,18,487-496)。此外，以糠醛作为原料虽然具有反应条件温和的优势，但是糠醛化学性质活泼、不易保存，同时在糠醛胺化反应中糠胺选择性通常较低，且所用催化剂易因积碳失活。
糠醇作为糠醛的羰基加氢衍生物，化学性质更为稳定，并且可通过玉米芯、秸秆及甘蔗渣等农林副产品获得，是重要的绿色生物质基平台分子。因此，以糠醇取代糠醛来进行还原胺化反应制备糠胺，具有非常大的吸引力。然而，目前由糠醇通过胺化反应高选择性地制备糠胺的报道还非常少；其中，Liu等以雷尼镍为催化剂进行糠醇选择胺化反应；在180℃和0.35MPa氨气压力下，反应60h后糠醇的转化率仅为24％，糠胺选择性为92.5％，而过度加氢产物四氢糠胺的选择性则为7.5％(LiuY,Zhou K,Shu H,et al.Switchable synthesisoffurfurylamineandtetrahydrofurfurylamine from furfuryl alcohol overnickel[J].CatalysisScience&Technology,2017,7,4129-4135)；除了催化活性和选择性不尽理想，该方法所使用的催化剂雷尼镍还存在稳定性差等问题，在第二次循环使用时催化剂活性下降约32％。此外，Kita等报道以Ru-MgO/TiO2作为催化剂，在110℃下，反应20h后糠醇转化率大于99％，糠胺选择性达94％(Yusuke Kita,MidoriKuwabara,SatoshiYamadera,Keigo Kamata,Michikazu Hara.Effects ofrutheniumhydride species onprimary amine synthesis by direct amination of alcohols over aheterogeneousRu catalyst.Chemical Science,2020,11,9884-9890)；这里需要指出的是，虽然该研究获得了较高的糠胺收率，但贵金属Ru的高昂成本限制了其应用空间。综上所述，针对糠醇选择性还原胺化制备糠胺的方法，目前还尚缺乏兼具高活性、高选择性和高稳定性的廉价金属催化剂，这是发展该绿色新过程的技术瓶颈之一。
发明内容
针对上述现有技术存在的不足之处，本发明的目的在于提供一种耐失活镍基催化剂催化选择性还原胺化制备糠胺的方法。
为了达成上述目的，本发明的解决方案是：
1.一种耐失活镍基催化剂上选择性制备糠胺的方法，其特征在于：具体包括以下步骤：
(1)镍基催化剂的制备：将0.29g硝酸镍与2.0425g氯化铝混合后在空气中600℃煅烧4h，然后将所得混合物在氢气中进行还原，还原温度为400℃，还原时间为3h；将制得的催化剂记为Ni@Al2O3；
(2)催化糠醇胺化反应：将步骤(1)中制得的Ni@Al2O3催化剂0.40g放入高压磁力搅拌反应釜中，然后再将0.20g糠醇与20mL四氢呋喃混合后投入至反应釜中，往反应釜中充入H2吹扫除去釜中空气，再充入0.5MPa的NH3；设置反应温度为180℃，转速为600r/min，反应时间为8h。
本发明的设计原理如下：
本发明所提供的耐失活镍基催化剂上选择性制备糠胺的反应机理为：首先通过简单的煅烧法制备出比表面积大且具有介孔孔道的镍基催化剂(Ni@Al2O3)。具体说来，本发明所提供的方法利用原位合成方法将活性金属镍包裹在具有介孔结构的三氧化二铝中，这样可以有效提高活性金属镍的稳定性和抗积碳能力。此外，利用镍与三氧化二铝载体的紧密接触不仅可以实现三氧化二铝的弱酸性位点与金属镍的协同作用，还可以调节氨气和糠胺在金属镍表面的吸附强度，进而促进糠醇的胺化速率及抑制产物糠胺过度加氢为四氢糠胺等副产物，从而提高了催化剂的活性和选择性。
本发明的有益效果：
(1)本发明所提供的耐失活镍基催化剂上选择性制备糠胺的方法成功实现了在较短反应时间和较少催化剂用量的条件下，利用廉价金属催化剂得到较高的糠胺收率。
(2)本发明所提供的耐失活镍基催化剂上选择性制备糠胺的方法由于所用催化剂具有较优异的稳定性，在实际应用中可有效地降低糠醇胺化制备糠胺的生产成本。
(3)本发明所提供的耐失活镍基催化剂上选择性制备糠胺的方法还具有原料简单易得及制备过程简易的优点，能进一步降低糠醇胺化制备糠胺催化剂的生产成本。
(4)本发明所提供的耐失活镍基催化剂上选择性制备糠胺的方法所选用的非均相催化剂Ni@Al2O3为固体催化剂且具有磁性，这便于催化剂的回收利用。
附图说明
图1为催化剂Ni@Al2O3在连续6次循环反应中的稳定性测试图。
具体实施方式
下面进一步结合附图和实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，示例中具体的质量、反应时间和温度、工艺参数等也仅是合适范围中的一个示例，本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。实施例中未注明具体技术或条件者，均为按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市场购买的常规产品。
实施例1
耐失活镍基催化剂上选择性制备糠胺的步骤如下：
(1)镍基催化剂的制备：将0.29g硝酸镍与2.0425g氯化铝混合后在空气中600℃煅烧4h，然后将所得混合物在氢气中进行还原，还原温度为400℃，还原时间为3h；将制得的催化剂记为Ni@Al2O3-1；对该催化剂进行氮气物理吸附表征，氮气等温吸脱附曲线为典型的Ⅳ型等温线曲线，说明该催化剂均具有介孔结构；氮气等温吸脱的结果可测得催化剂的孔径为5.6nm，比表面积为409.8cm2/g。采用N2O氧化-H2程序升温还原方法(参考文献：(Tada S,YokoyamaM,Kikuchi R,et al.N2O pulse titration of Ni/α-Al2O3 catalysts:a newtechnique applicable to nickel surface-area determination of nickel-basedcatalysts[J].The Journal of Physical Chemistry,2013,117(28):14652-14658.))来测定催化剂表面暴露的金属Ni含量，根据得到的氢气消耗量可以算出Ni的分散度(dp)为17.1％。再根据以下公式可以算得Ni的粒径(D)为5.9nm。
D(nm)＝(1.0092)/dp
(2)催化糠醇胺化反应：将步骤(1)中制得的Ni@Al2O3-1催化剂0.40g放入高压磁力搅拌反应釜中，然后再将0.20g糠醇与20mL四氢呋喃混合后投入至反应釜中，往反应釜中充入H2吹扫除去釜中空气，再充入0.5MPa的NH3。设置反应温度为180℃，转速为600r/min，反应时间为8h。反应结束后，等高压反应釜自然冷却至室温后，加入内标物1，4-二氧六环0.15g后混合均匀，取2mL溶液用于气相色谱的定量检测分析；计算后得到糠醇的转化率为31.7％，糠胺的选择性为99.9％。
实施例2
耐失活镍基催化剂上选择性制备糠胺的步骤如下：
(1)镍基催化剂的制备步骤同实施例1；
(2)催化糠醇胺化反应步骤参考实施例1，不同之处在于将溶剂四氢呋喃换为甲苯；反应结果如下：糠醇的转化率为23.8％，糠胺的选择性为99.9％。
实施例3-8
对镍基催化剂进行稳定性实验测试，步骤如下：
镍基催化剂的制备步骤和催化糠醇胺化反应步骤均同实施例1。反应结束后对催化剂进行回收：将釜中混合物取出添加乙醇后放入离心管，离心后倒掉上层清液；将离心得到的催化剂放入烘箱烘干后，放入管式气氛炉中在50mL/min氢气气氛下还原。将还原后的催化剂再次用于催化糠醇胺化制备糠胺反应，反应条件与实施例1相同。重复上述步骤6次。得到的糠胺收率如图1所示，可以看出：随着反应次数的增加，催化剂的活性保持不变(转化率保持在25％左右)，并且保持高糠胺选择性(99％)。从图1中的数据还可看出本发明所用的催化剂Ni@Al2O3-1具有高稳定性，不易失活。
Claims (1)
1.一种耐失活镍基催化剂上选择性制备糠胺的方法，其特征在于：具体包括以下步骤：
（1）镍基催化剂的制备：将0.29 g硝酸镍与2.0425 g氯化铝混合后在空气中600 ℃煅烧4 h，然后将所得混合物在氢气中进行还原，还原温度为400 ℃，还原时间为3 h；将制得的催化剂记为Ni@Al2O3；
（2）催化糠醇胺化反应：将步骤（1）中制得的Ni@Al2O3催化剂0.40g放入高压磁力搅拌反应釜中，然后再将0.20 g糠醇与20mL四氢呋喃混合后投入至反应釜中，往反应釜中充入H2吹扫除去釜中空气，再充入0.5MPa的NH3；设置反应温度为180℃，转速为600 r/min，反应时间为8h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210499544.1A CN114805259B (zh) | 2022-05-09 | 2022-05-09 | 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210499544.1A CN114805259B (zh) | 2022-05-09 | 2022-05-09 | 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805259A CN114805259A (zh) | 2022-07-29 |
| CN114805259B true CN114805259B (zh) | 2024-01-12 |
Family
ID=82513705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210499544.1A Active CN114805259B (zh) | 2022-05-09 | 2022-05-09 | 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805259B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116217525A (zh) * | 2023-03-21 | 2023-06-06 | 厦门大学 | 一种生物质基醛酮化合物还原胺化制备有机胺的方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203108A (zh) * | 2008-08-10 | 2011-09-28 | 耶达研究与发展有限公司 | 用于从醇和氨制备胺的方法 |
| CN107245066A (zh) * | 2017-06-26 | 2017-10-13 | 浙江大学 | 一种选择性制备糠胺或四氢糠胺的方法 |
| WO2020103006A1 (en) * | 2018-11-21 | 2020-05-28 | Rhodia Operations | Process for preparing primary amines from alcohols |
| CN113522294A (zh) * | 2021-08-11 | 2021-10-22 | 中国科学院青岛生物能源与过程研究所 | 一种Ni基催化剂及其制备方法与在还原胺化中的应用 |
-
2022
- 2022-05-09 CN CN202210499544.1A patent/CN114805259B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102203108A (zh) * | 2008-08-10 | 2011-09-28 | 耶达研究与发展有限公司 | 用于从醇和氨制备胺的方法 |
| CN107245066A (zh) * | 2017-06-26 | 2017-10-13 | 浙江大学 | 一种选择性制备糠胺或四氢糠胺的方法 |
| WO2020103006A1 (en) * | 2018-11-21 | 2020-05-28 | Rhodia Operations | Process for preparing primary amines from alcohols |
| CN113522294A (zh) * | 2021-08-11 | 2021-10-22 | 中国科学院青岛生物能源与过程研究所 | 一种Ni基催化剂及其制备方法与在还原胺化中的应用 |
Non-Patent Citations (1)
| Title |
|---|
| "Direct Amination of Biomass-based Furfuryl Alcohol and 5-(Aminomethyl)-2-furanmethanol with NH3 over Hydrotalcite-derived Nickel Catalysts via the Hydrogenborrowing Strategy";Kuo Zhou et al;ChemCatChem;第13卷(第8期);第2074–2085页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805259A (zh) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kano et al. | Organocatalytic asymmetric synthesis of propargylamines with two adjacent stereocenters: mannich-type reactions of in situ generated C-alkynyl imines with β-keto esters. | |
| CN112661653B (zh) | 一种环状（烷基）（氨基）卡宾铬络合物催化还原硝基化合物制备胺的方法 | |
| CN102728386B (zh) | 一种Pd-Ni/Al2O3催化剂及其制备方法和用途 | |
| CN114805259B (zh) | 一种耐失活镍基催化剂上糠醇选择性胺化制备糠胺的方法 | |
| CN104387340B (zh) | 一种制备n‑甲基哌嗪及其催化剂的方法 | |
| CN108273507B (zh) | 一种催化加氢还原腈类化合物的方法 | |
| Gao et al. | Direct construction of chiral quaternary dihydropyranones through highly enantioselective organocatalytic hetero-Diels–Alder reactions of olefinic azlactones | |
| CN113880822B (zh) | 一种手性含亚胺喹啉噁唑啉类化合物及其金属络合物以及制备方法和应用 | |
| CN108129426B (zh) | 一种2,5-二氰基呋喃催化加氢合成2,5-二甲胺基呋喃的方法 | |
| WO2019200778A1 (zh) | 一种用于合成气制吡啶碱的催化剂及制备方法和应用 | |
| CN109622031B (zh) | 2-羟基膦酰基乙酸锆的制备方法及其在糠醇合成中的应用 | |
| CN101456790A (zh) | 一种通过镍催化芳基硼酸对醛的加成反应制备二芳基醇的方法 | |
| WO2020034058A1 (en) | PROCESS FOR REDUCTIVE AMINATION OF α,β-UNSATURATED CARBONYL COMPOUND | |
| WO2020034062A1 (en) | Process for the reductive amination of a carbonyl compound | |
| CN114870881A (zh) | 一种海藻衍生缺陷碳材料负载镍催化剂及应用 | |
| WO2022028176A1 (zh) | 顺式烯烃异构化为反式烯烃的方法 | |
| CN113304747B (zh) | 用于制备2-甲基吡啶的催化剂、制备方法和用其制备2-甲基吡啶的方法 | |
| RU2614420C1 (ru) | Катализатор и способ осуществления реакции Фишера-Тропша с его использованием | |
| CN111217750B (zh) | 一种己内酰胺的制备方法 | |
| CN111253230B (zh) | 一种水相催化5-羟甲基糠醛加氢制备3-羟甲基环戊酮的方法 | |
| TW201127786A (en) | Process and catalyst | |
| CN109433214A (zh) | 一种Ni/Zn多孔碳负载型催化剂及其在苯环催化加氢中的应用 | |
| CN112961130B (zh) | 二维MoS2催化剂在催化马来酸酐选择性加氢制备丁二酸酐中的应用 | |
| CN116459857B (zh) | 一种高选择性催化剂Co/NS800及其制备方法和在非均相体系中选择性加氢对氯硝基苯的方法 | |
| CN114656442B (zh) | 一种由5-羟甲基糠酸制备己内酯的方法 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |