CN114433224B - A kind of composite catalyst and its preparation method and application - Google Patents
A kind of composite catalyst and its preparation method and application Download PDFInfo
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- CN114433224B CN114433224B CN202011193859.0A CN202011193859A CN114433224B CN 114433224 B CN114433224 B CN 114433224B CN 202011193859 A CN202011193859 A CN 202011193859A CN 114433224 B CN114433224 B CN 114433224B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- 239000002086 nanomaterial Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims description 46
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 230000003647 oxidation Effects 0.000 claims description 20
- 150000001721 carbon Chemical class 0.000 claims description 17
- 150000001924 cycloalkanes Chemical class 0.000 claims description 16
- -1 amine compounds Chemical class 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229910003472 fullerene Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002113 nanodiamond Substances 0.000 claims description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- 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
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明涉及一种复合催化剂及其制备方法和应用，该方法包括：使碳纳米材料与含有模板剂的分子筛混合得到混合物，对混合物进行分段焙烧处理；分段焙烧处理包括依次进行的第一焙烧处理和第二焙烧处理。本发明的方法制备得到的复合催化剂在烷烃的选择性氧化反应中具有优异的反应性能。The invention relates to a composite catalyst and its preparation method and application. The method comprises: mixing a carbon nanomaterial with a molecular sieve containing a template agent to obtain a mixture, and performing staged roasting on the mixture; the staged roasting process includes the first Roasting treatment and second roasting treatment. The composite catalyst prepared by the method of the invention has excellent reaction performance in the selective oxidation reaction of alkanes.
Description
技术领域technical field
本发明涉及一种复合催化剂及其制备方法和应用。The invention relates to a composite catalyst and its preparation method and application.
背景技术Background technique
碳纳米材料与普通纳米材料类似，它在光学、电学、磁性等方面也具有量子尺寸效应、小尺寸效应和宏观量子隧道效应等特殊性质。2004年通过电泳法净化单层碳纳米管时发现的尺寸小于10nm的细小碳纳米颗粒首次被命名为碳点，它是一种新型的小尺寸碳纳米材料。相比于有机染料和传统的半导体量子点，碳点除了具有良好的水溶性，高稳定性，低毒性和良好的生物相容性，还具有独特的光学和电学特性。所以，碳点的性质与应用的研究得到了人们越来越多的关注，可应用于能源问题、环境保护、光伏器件等相关领域。绿色催化氧化材料如钛硅分子筛是上世纪八十年代初开始开发的，其不但具有钛的催化氧化作用，而且还具有择形作用和优良的稳定性。由于在有机物的氧化反应中，可采用无污染的低浓度过氧化氢作为氧化剂，避免了氧化过程工艺复杂和污染环境的问题，具有传统氧化体系无可比拟的节能、经济和环境友好等优点，并具有良好的反应选择性，因此具有极大的工业应用前景。但目前其合成方法的重复性和稳定性以及成本等方面不是十分理想。所以，改进相应合成改性方法是材料开发的关键。Similar to ordinary nanomaterials, carbon nanomaterials also have special properties such as quantum size effects, small size effects, and macroscopic quantum tunneling effects in terms of optics, electricity, and magnetism. In 2004, the fine carbon nanoparticles with a size less than 10nm discovered during the purification of single-walled carbon nanotubes by electrophoresis were named carbon dots for the first time, which is a new type of small-sized carbon nanomaterial. Compared with organic dyes and traditional semiconductor quantum dots, carbon dots have unique optical and electrical properties in addition to good water solubility, high stability, low toxicity and good biocompatibility. Therefore, the research on the properties and applications of carbon dots has received more and more attention, and can be applied to energy issues, environmental protection, photovoltaic devices and other related fields. Green catalytic oxidation materials such as titanium-silicon molecular sieves were developed in the early 1980s. They not only have the catalytic oxidation of titanium, but also have shape selectivity and excellent stability. Because in the oxidation reaction of organic matter, non-polluting low-concentration hydrogen peroxide can be used as the oxidant, which avoids the problems of complex oxidation process and environmental pollution, and has the incomparable advantages of energy saving, economy and environmental friendliness in traditional oxidation systems. And it has good reaction selectivity, so it has great industrial application prospect. However, the repeatability, stability and cost of the synthesis method are not very ideal. Therefore, improving the corresponding synthesis and modification methods is the key to material development.
发明内容Contents of the invention
本发明的目的是提供一种复合催化剂及其制备方法和应用，该方法制备得到的复合催化剂在烷烃的选择性氧化反应中具有优异的反应性能。The object of the present invention is to provide a composite catalyst and its preparation method and application. The composite catalyst prepared by the method has excellent reaction performance in the selective oxidation reaction of alkanes.
为了实现上述目的，本发明第一方面提供一种制备复合催化剂的方法，该方法包括：使碳纳米材料与含有模板剂的分子筛混合得到混合物，对所述混合物进行分段焙烧处理；In order to achieve the above object, the first aspect of the present invention provides a method for preparing a composite catalyst, the method comprising: mixing a carbon nanomaterial with a molecular sieve containing a template to obtain a mixture, and performing a staged roasting process on the mixture;
所述分段焙烧处理至少包括依次进行的第一焙烧处理和第二焙烧处理；The staged calcination treatment includes at least a first calcination treatment and a second calcination treatment carried out in sequence;
所述第一焙烧处理的条件包括：在密闭环境下，使所述混合物从初始温度升温至终点温度，所述初始温度为0～80℃，所述终点温度为300～600℃，升温速率为0.1～5℃/min，所述第一焙烧处理的总时间为1～12小时；The conditions of the first roasting treatment include: heating the mixture from the initial temperature to the terminal temperature in a closed environment, the initial temperature is 0-80°C, the terminal temperature is 300-600°C, and the heating rate is 0.1-5°C/min, the total time of the first roasting treatment is 1-12 hours;
所述第二焙烧处理的条件包括：在开放环境下，温度为300～600℃，时间为1～12小时。The conditions of the second calcination treatment include: in an open environment, the temperature is 300-600° C., and the time is 1-12 hours.
可选地，所述第一焙烧处理的总时间与所述第二焙烧处理的时间之和为2～24小时。Optionally, the sum of the total time of the first calcination treatment and the time of the second calcination treatment is 2 to 24 hours.
可选地，所述第一焙烧处理的终点温度与所述第二焙烧处理的温度相同。Optionally, the end point temperature of the first calcination treatment is the same as the temperature of the second calcination treatment.
可选地，所述碳纳米材料与含有模板剂的分子筛的用量重量比为1：(1～100)，优选为1：(5～20)；Optionally, the weight ratio of the carbon nanomaterial to the molecular sieve containing the template is 1:(1-100), preferably 1:(5-20);
以所述含有模板剂的分子筛的总重量为基准，所述模板剂的含量为2～20重量％，所述含有模板剂的分子筛的平均粒径为50～500nm。Based on the total weight of the molecular sieve containing the template agent, the content of the template agent is 2-20% by weight, and the average particle diameter of the molecular sieve containing the template agent is 50-500nm.
可选地，所述模板剂选自季胺碱类化合物、脂肪胺类化合物和醇胺类化合物中的一种或几种；Optionally, the template agent is selected from one or more of quaternary ammonium base compounds, fatty amine compounds and alcohol amine compounds;
所述季胺碱类化合物选自四乙基氢氧化铵、四丙基氢氧化铵或四丁基氢氧化铵，或者为它们中的两者或三者的组合；The quaternary ammonium base compound is selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide, or a combination of two or three of them;
所述脂肪胺类化合物选自乙胺、正丁胺、丁二胺或己二胺，或者为它们中的两者或三者的组合；The fatty amine compound is selected from ethylamine, n-butylamine, butylenediamine or hexamethylenediamine, or a combination of two or three of them;
所述醇胺类化合物单乙醇胺、二乙醇胺或三乙醇胺，或者为它们中的两者或三者的组合。The alcohol amine compound is monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of them.
可选地，所述碳纳米材料包括碳纳米管、石墨烯、富勒烯、纳米石墨、纳米金刚石和活性炭中的一种或几种；Optionally, the carbon nanomaterials include one or more of carbon nanotubes, graphene, fullerenes, nano-graphite, nano-diamonds and activated carbon;
所述含有模板剂的分子筛中的分子筛选自TS-1、TS-2、Ti-MCM-22、Ti-MCM-41、Ti-SBA-15和Ti-ZSM-48中的一种或几种。The molecular sieve in the molecular sieve containing the template agent is selected from one or more of TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15 and Ti-ZSM-48 .
本发明第二方面提供一种本发明第一方面提供的方法制备得到的复合催化剂。The second aspect of the present invention provides a composite catalyst prepared by the method provided in the first aspect of the present invention.
可选地，所述复合催化剂含有改性分子筛和改性碳纳米材料，所述改性分子筛的含量40-99重量％，所述改性分子筛的硅钛摩尔比为15-50，所述改性碳纳米材料中氮含量为0.01-5重量％。Optionally, the composite catalyst contains modified molecular sieves and modified carbon nanomaterials, the content of the modified molecular sieves is 40-99% by weight, the silicon-titanium molar ratio of the modified molecular sieves is 15-50, and the modified The content of nitrogen in the permanent carbon nanometer material is 0.01-5% by weight.
本发明第三方面提供一种本发明第二方面提供的复合催化剂在环烷烃的选择性氧化中的应用。The third aspect of the present invention provides an application of the composite catalyst provided in the second aspect of the present invention in the selective oxidation of naphthenes.
可选地，所述环烷烃的选择性催化氧化的方法包括：使环烷烃与所述的复合催化剂接触进行氧化反应；Optionally, the method for the selective catalytic oxidation of cycloalkane comprises: contacting cycloalkane with the composite catalyst for oxidation reaction;
所述环烷烃与所述复合催化剂用量的重量比为100：(0.1～20)，所述氧化反应的条件包括：温度为80～200℃，时间为1～24小时。The weight ratio of the cycloalkane to the composite catalyst is 100:(0.1-20), and the conditions of the oxidation reaction include: the temperature is 80-200° C., and the time is 1-24 hours.
通过上述技术方案，本发明的方法制备得到的复合催化剂在环烷烃的选择性氧化中具有优异的反应性能。Through the above technical scheme, the composite catalyst prepared by the method of the present invention has excellent reaction performance in the selective oxidation of naphthenes.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present invention will be described in detail in the following detailed description.
具体实施方式Detailed ways
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
本发明第一方面提供一种制备复合催化剂的方法，该方法包括：使碳纳米材料与含有模板剂的分子筛混合得到混合物，对混合物进行分段焙烧处理；The first aspect of the present invention provides a method for preparing a composite catalyst, the method comprising: mixing a carbon nanomaterial with a molecular sieve containing a template to obtain a mixture, and performing staged roasting on the mixture;
分段焙烧处理至少包括依次进行的第一焙烧处理和第二焙烧处理；The staged calcination treatment includes at least the first calcination treatment and the second calcination treatment carried out in sequence;
第一焙烧处理的条件包括：在密闭环境下，使混合物从初始温度升温至终点温度，其中，初始温度为0～80℃，终点温度为300～600℃，升温速率为0.1～5℃/min，第一焙烧处理的总时间为1～12小时；The conditions of the first roasting treatment include: heating the mixture from the initial temperature to the final temperature in a closed environment, wherein the initial temperature is 0-80°C, the final temperature is 300-600°C, and the heating rate is 0.1-5°C/min , the total time for the first roasting treatment is 1 to 12 hours;
第二焙烧处理的条件包括：在开放环境下，温度为300～600℃，时间为1～12小时。The conditions of the second roasting treatment include: in an open environment, the temperature is 300-600° C., and the time is 1-12 hours.
其中，依次进行的第一焙烧处理和第二焙烧处理是指将碳纳米材料与含有模板剂的分子筛混合得到混合物进行第一焙烧处理后，将第一焙烧处理得到的产物再进行第二焙烧处理。本发明的方法中以碳纳米材料与含有模板剂的分子筛混合物为原料，采用分步焙烧的过程，能够制备得到对烷烃的氧化具有良好选择性的复合催化剂。Wherein, the first calcination treatment and the second calcination treatment carried out sequentially refer to mixing the carbon nanomaterial with the molecular sieve containing the template agent to obtain the mixture and then performing the first calcination treatment, and then subjecting the product obtained from the first calcination treatment to the second calcination treatment. . In the method of the invention, the composite catalyst with good selectivity for the oxidation of alkane can be prepared by using the carbon nanometer material and the molecular sieve mixture containing the template agent as raw materials and adopting a step-by-step roasting process.
在一种优选的具体实施方式中，第一焙烧处理的条件包括：在密闭环境下，使混合物从初始温度升温至终点温度，其中，初始温度为20～60℃，终点温度为350～550℃，升温速率为0.5～2℃/min，第一焙烧处理的总时间为2～12小时；第二焙烧处理的条件包括：在开放环境下，温度为350～550℃，时间为1～6小时。In a preferred embodiment, the conditions of the first calcination treatment include: heating the mixture from the initial temperature to the final temperature in a closed environment, wherein the initial temperature is 20-60°C, and the final temperature is 350-550°C , the heating rate is 0.5-2°C/min, the total time of the first roasting treatment is 2-12 hours; the conditions of the second roasting treatment include: in an open environment, the temperature is 350-550°C, and the time is 1-6 hours .
根据本发明，密闭环境指的是焙烧处理时的焙烧设备中放置待焙烧物的空间与外界无气体交换；开放环境指的是焙烧处理时的焙烧设备中放置待焙烧物的空间与外界存在气体交换。According to the present invention, the closed environment refers to the space where the object to be roasted is placed in the roasting equipment during the roasting process and there is no gas exchange with the outside world; the open environment refers to the space where the object to be roasted is placed in the roasting equipment during the roasting process. exchange.
根据本发明，第一焙烧处理开始前，焙烧气氛为空气、贫氧气氛或惰性气体气氛；第二焙烧处理的焙烧气氛始终为空气或贫氧气氛。According to the present invention, before the first calcination treatment starts, the calcination atmosphere is air, an oxygen-poor atmosphere or an inert gas atmosphere; the calcination atmosphere of the second calcination treatment is always air or an oxygen-depleted atmosphere.
根据本发明，第一焙烧处理的总时间与第二焙烧处理的时间之和可以在较大范围内变化，例如可以为3～20小时。在一种具体实施方式中，第一焙烧处理的总时间为2～10小时，第二焙烧处理的时间为1～10小时。根据本发明，第一焙烧处理和第二焙烧处理可以在具有程序升温功能的马弗炉中进行。According to the present invention, the sum of the total time of the first calcination treatment and the time of the second calcination treatment can vary within a wide range, for example, it can be 3-20 hours. In a specific embodiment, the total time of the first calcination treatment is 2-10 hours, and the time of the second calcination treatment is 1-10 hours. According to the present invention, the first calcination treatment and the second calcination treatment can be carried out in a muffle furnace with a temperature programming function.
在一种优选的具体实施方式中，第一焙烧处理的终点温度与第二焙烧处理的起始温度相同，使得操作更为简便，只需改变体系内气氛氛围即可，且有利于制备得到具有更优的选择性氧化特性的复合催化剂。In a preferred embodiment, the end point temperature of the first calcination treatment is the same as the start temperature of the second calcination treatment, which makes the operation easier, only needs to change the atmosphere in the system, and is conducive to the preparation of Composite catalyst with better selective oxidation characteristics.
根据本发明，碳纳米材料与含有模板剂的分子筛的用量重量比可以在较大范围内变化，例如可以为1：(1～100)，优选为1：(5～20)；以含有模板剂的分子筛的总重量为基准，模板剂的含量可以为2～20重量％。According to the present invention, the weight ratio of carbon nanomaterials to molecular sieves containing templates can be changed in a wide range, for example, it can be 1: (1-100), preferably 1: (5-20); Based on the total weight of the molecular sieve, the content of the template agent can be 2-20% by weight.
根据本发明，模板剂可以选自季胺碱类化合物、脂肪胺类化合物和醇胺类化合物中的一种或几种。According to the present invention, the templating agent can be selected from one or more of quaternary ammonium base compounds, fatty amine compounds and alcohol amine compounds.
在一种实施方式中，季铵碱类化合物的分子通式可以为(R1)4NOH，其中，R1可以选自C1-C4的直链烷基和C3-C4的支链烷基的至少一种，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基或甲基烯丙基。优选地，季胺碱类化合物选自四乙基氢氧化铵、四丙基氢氧化铵或四丁基氢氧化铵，或者为它们中的两者或三者的组合。In one embodiment, the general molecular formula of the quaternary ammonium base compound can be (R 1 ) 4 NOH, wherein, R 1 can be selected from C 1 -C 4 straight chain alkyl and C 3 -C 4 branched At least one of alkanyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or methallyl. Preferably, the quaternary ammonium base compound is selected from tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide, or a combination of two or three of them.
脂肪胺类化合物的分子通式可以为R2(NH2)n，其中，R2可以为C1-C6的直链烷基和C3-C6的支链烷基的至少一种，例如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基或正己基，R2也可以为C1-C6的亚烷基，例如亚甲基、亚乙基、亚正丙基、亚正丁基或亚正己基，n为1或2的整数。优选地，脂肪胺类化合物选自乙胺、正丁胺、丁二胺或己二胺，或者为它们中的两者或三者的组合；The general molecular formula of the fatty amine compound may be R 2 (NH 2 ) n , wherein R 2 may be at least one of C 1 -C 6 straight-chain alkyl and C 3 -C 6 branched-chain alkyl, Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, R can also be C 1 -C 6 Alkyl, such as methylene, ethylene, n-propylene, n-butylene or n-hexylene, n is an integer of 1 or 2. Preferably, the fatty amine compound is selected from ethylamine, n-butylamine, butylenediamine or hexamethylenediamine, or a combination of two or three of them;
醇胺类化合物的分子通式可以为(HOR3)mNH(3-m)，其中，R3可以为C1-C4的烷基，m为1、2或3的整数。优选地，醇胺类化合物单乙醇胺、二乙醇胺或三乙醇胺，或者为它们中的两者或三者的组合。The general molecular formula of the alcohol amine compound may be (HOR 3 ) m NH (3-m) , wherein, R 3 may be a C 1 -C 4 alkyl group, and m is an integer of 1, 2 or 3. Preferably, the alcohol amine compound is monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of them.
根据本发明，含有模板剂的分子筛的平均粒径可以在较大的范围内变化，例如可以为50～500nm。According to the present invention, the average particle diameter of the molecular sieve containing the template agent can be changed within a relatively large range, for example, it can be 50-500 nm.
根据本发明，碳纳米材料为本领域的技术人员所熟知的，对其具体种类不做限制，优选为碳纳米管、石墨烯、富勒烯、纳米石墨、纳米金刚石和活性炭中的一种或几种，更优选为碳纳米管，进一步优选为多壁碳纳米管；含有模板剂的分子筛的实例包括但不限于钛硅分子筛，钛硅分子筛也为本领域的技术人员所熟知的，例如可以为TS-1、TS-2、Ti-MCM-22、Ti-MCM-41、Ti-SBA-15和Ti-ZSM-48中的一种或几种。碳纳米材料和含有模板剂的分子筛可以由商购或自行制备得到。二者的制备方法为本领域的技术人员所熟知的，在此不再赘述。According to the present invention, carbon nanomaterials are well known to those skilled in the art, and its specific type is not limited, and is preferably one or more of carbon nanotubes, graphene, fullerenes, nano-graphite, nano-diamonds and activated carbon. Several, more preferably carbon nanotubes, further preferably multi-walled carbon nanotubes; examples of molecular sieves containing templates include but are not limited to titanium-silicon molecular sieves, titanium-silicon molecular sieves are also well known to those skilled in the art, for example, One or more of TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15 and Ti-ZSM-48. Carbon nanomaterials and molecular sieves containing templates can be purchased commercially or prepared by ourselves. The preparation methods of the two are well known to those skilled in the art and will not be repeated here.
本发明第二方面提供一种本发明第一方面提供的方法制备得到的复合催化剂。本发明的复合催化剂尤其适用于无溶剂条件下直接进行环烷烃的选择性氧化反应，对。The second aspect of the present invention provides a composite catalyst prepared by the method provided in the first aspect of the present invention. The composite catalyst of the present invention is especially suitable for the selective oxidation reaction of naphthenes directly under solvent-free conditions.
根据本发明，复合催化剂含有改性分子筛和改性碳纳米材料，其中改性分子筛含量40-99重量％，改性分子筛的硅钛摩尔比为15-50，改性碳纳米材料中氮含量为0.01-5重量％。According to the present invention, the composite catalyst contains modified molecular sieves and modified carbon nanomaterials, wherein the modified molecular sieve content is 40-99% by weight, the silicon-titanium molar ratio of the modified molecular sieves is 15-50, and the nitrogen content in the modified carbon nanomaterials is 0.01-5% by weight.
本发明第三方面提供一种本发明第二方面制备得到的复合催化剂在环烷烃的选择性催化氧化中的应用，复合催化剂作为环烷烃选择性氧化催化剂。The third aspect of the present invention provides an application of the composite catalyst prepared in the second aspect of the present invention in the selective catalytic oxidation of naphthenes, and the composite catalyst is used as a catalyst for the selective oxidation of naphthenes.
根据本发明，环烷烃的选择性催化氧化的方法可以包括：使环烷烃与复合催化剂和氧化剂接触进行氧化反应，对反应体系内环烷烃与氧化剂的用量的重量比没有特别限定，可以在较大范围内变化，只要能实现环烷烃的氧化即可；环烷烃与复合催化剂用量的重量比可以在较大的范围内变化如100：(0.1～20)，优选为100：(1～10)，氧化反应的条件可以包括：温度为80～200℃，时间为1～24小时；优选温度为100～160℃，时间为2～12小时。According to the present invention, the method for the selective catalytic oxidation of cycloalkane can comprise: making cycloalkane contact with composite catalyst and oxidizing agent to carry out oxidation reaction, there is no special limitation to the weight ratio of the amount of cycloalkane and oxidizing agent in the reaction system, it can be larger Change within the range, as long as the oxidation of cycloalkane can be realized; the weight ratio of cycloalkane and composite catalyst consumption can be changed in a large range such as 100: (0.1～20), preferably 100: (1～10), Conditions of the oxidation reaction may include: the temperature is 80-200° C., and the time is 1-24 hours; preferably, the temperature is 100-160° C., and the time is 2-12 hours.
根据本发明，环烷烃为环己烷、环戊烷及其卤代或烷基衍生物，氧化剂为氧气或空气。对于加料方式无特别限定，在一种优选的具体实施方式中，环烷烃可以一次性加入，氧化剂可以持续通入。According to the present invention, cycloalkane is cyclohexane, cyclopentane and their halogenated or alkyl derivatives, and the oxidizing agent is oxygen or air. There is no particular limitation on the feeding method. In a preferred embodiment, the cycloalkane can be added at one time, and the oxidizing agent can be fed continuously.
下面通过实施例来进一步说明本发明，但是本发明并不因此而受到任何限制。The present invention will be further illustrated below by way of examples, but the present invention is not limited thereto.
所用多壁碳纳米管商购自国药集团化学试剂有限公司(CNT，平均管径为20nm，长度5μm，灰分小于0.1重量％)。The multi-walled carbon nanotubes used were commercially purchased from Sinopharm Chemical Reagent Co., Ltd. (CNT, with an average diameter of 20 nm, a length of 5 μm, and an ash content of less than 0.1 wt%).
所用的含模板剂钛硅分子筛(TS-1)是按现有技术Zeolites，1992，Vol.12第943～950页中所描述的方法制备出的分子筛样品。The used template-containing titanium-silicon molecular sieve (TS-1) is a molecular sieve sample prepared according to the method described in the prior art Zeolites, 1992, Vol.12 pages 943-950.
具体制备方法如下：将22.5克正硅酸四乙酯与7.0克四丙基氢氧化铵(25重量％的水溶液)混合，并加入50克蒸馏水进一步混合均匀，在剧烈搅拌下缓慢地加入由1.1克钛酸四丁酯与5.0克无水异丙醇所组成的溶液，将所得混合物在75℃下搅拌3小时，得到胶体。将此胶体放入不锈钢反应釜，在170℃的温度下恒温放置3天，得到晶化产物的混合物；将此混合物过滤、用水洗涤，并于110℃干燥60分钟，得产物含模板剂的钛硅分子筛(TS-1)，其模板剂的含量为14重量％，平均粒径为220nm。The specific preparation method is as follows: 22.5 grams of tetraethyl orthosilicate and 7.0 grams of tetrapropylammonium hydroxide (25% by weight aqueous solution) are mixed, and 50 grams of distilled water are added to further mix uniformly, and slowly add the mixture made of 1.1 grams under vigorous stirring. 1 g of tetrabutyl titanate and 5.0 g of anhydrous isopropanol, and the resulting mixture was stirred at 75° C. for 3 hours to obtain a colloid. Put the colloid into a stainless steel reaction kettle, and place it at a constant temperature of 170°C for 3 days to obtain a mixture of crystallized products; filter the mixture, wash with water, and dry at 110°C for 60 minutes to obtain the product titanium containing template Silica molecular sieve (TS-1), the content of the template agent is 14% by weight, and the average particle diameter is 220nm.
复合催化剂的改性分子筛含量以及改性分子筛的硅钛摩尔含量比采用X射线荧光光谱分析(XRF)测量得到，改性碳纳米材料中氮含量用X射线光电子能谱(XPS)测量得到。The modified molecular sieve content of the composite catalyst and the silicon-titanium molar content ratio of the modified molecular sieve were measured by X-ray fluorescence spectroscopy (XRF), and the nitrogen content in the modified carbon nanomaterial was measured by X-ray photoelectron spectroscopy (XPS).
采用气相色谱方法分析烷烃选择性氧化产物的组成，在此基础上分别采用以下公式来计算环己烷转化率、环己酮选择性以及环己醇选择性选择性：Gas chromatography was used to analyze the composition of alkane selective oxidation products. On this basis, the following formulas were used to calculate the conversion rate of cyclohexane, the selectivity of cyclohexanone and the selectivity of cyclohexanol:
环己烷转化率＝[(加入的环己烷的摩尔量－未反应的环己烷的摩尔量)/加入的环己烷的摩尔量]×100％；Cyclohexane conversion rate=[(molar quantity of cyclohexane added-molar quantity of unreacted cyclohexane)/molar quantity of cyclohexane added]×100%;
环己酮选择性＝[反应生成的环己酮的摩尔量/(加入的环己烷的摩尔量－未反应的环己烷的摩尔量)]×100％；Cyclohexanone selectivity=[the molar amount of cyclohexanone generated by the reaction/(the molar amount of added cyclohexane-the molar amount of unreacted cyclohexane)]×100%;
环己醇选择性＝[反应生成的环己醇的摩尔量/(加入的环己烷的摩尔量－未反应的环己烷的摩尔量)]×100％。Cyclohexanol selectivity=[the molar amount of cyclohexanol produced by the reaction/(the molar amount of added cyclohexane-the molar amount of unreacted cyclohexane)]×100%.
实施例1Example 1
将CNT和含模板剂的钛硅分子筛(TS-1)按重量比1：10混合均匀后放入坩埚内(坩埚加盖密封)，然后转入马弗炉内关闭马弗炉门后开始第一焙烧处理，第一焙烧处理的初始温度为20℃，终点温度为400℃，升温速率为2℃/min，焙烧总时间为4.5h；第一焙烧处理结束后打开坩埚盖在400℃下进行第二焙烧处理2.5h，冷却取出，得到复合催化剂A。经检测，复合催化剂A中改性分子筛含量88重量％，改性分子筛的硅钛摩尔比为24，改性碳纳米材料中氮含量为0.17重量％。Mix CNT and titanium-silicon molecular sieve (TS-1) containing template agent evenly at a weight ratio of 1:10, put them into the crucible (the crucible is covered and sealed), and then transfer to the muffle furnace and close the muffle furnace door to start the first step. First roasting treatment, the initial temperature of the first roasting treatment is 20°C, the end point temperature is 400°C, the heating rate is 2°C/min, and the total roasting time is 4.5h; after the first roasting treatment, open the crucible lid and proceed at 400°C The second calcination treatment was performed for 2.5 hours, and the composite catalyst A was obtained after being cooled and taken out. After testing, the modified molecular sieve content in the composite catalyst A is 88% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 24, and the nitrogen content in the modified carbon nanomaterial is 0.17% by weight.
实施例2Example 2
将CNT和TS-1按重量比1：1混合均匀后放入坩埚内(坩埚加盖密封)，然后转入马弗炉内关闭马弗炉门后开始第一焙烧处理，第一焙烧处理的初始温度为60℃，终点温度为500℃，升温速率为4℃/min，焙烧时间为3.5h；第一焙烧处理结束后打开坩埚盖在500℃下进行第二焙烧处理0.5h，冷却取出，得到复合催化剂B。经检测，复合催化剂B中改性分子筛含量43重量％，改性分子筛的硅钛摩尔比为26，改性碳纳米材料中氮含量为0.03重量％。Mix CNT and TS-1 evenly at a weight ratio of 1:1 and put them into the crucible (the crucible is covered and sealed), then transfer to the muffle furnace and close the muffle furnace door to start the first roasting process. The initial temperature is 60°C, the end point temperature is 500°C, the heating rate is 4°C/min, and the roasting time is 3.5h; after the first roasting treatment, open the crucible lid and perform the second roasting treatment at 500°C for 0.5h, and then take it out after cooling. Composite catalyst B is obtained. After testing, the modified molecular sieve content in the composite catalyst B is 43% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 26, and the nitrogen content in the modified carbon nanomaterial is 0.03% by weight.
实施例3Example 3
将CNT和TS-1按重量比为1：50混合均匀后放入坩埚内(坩埚加盖密封)，然后转入马弗炉内关闭马弗炉门后开始第一焙烧处理，第一焙烧处理的初始温度为30℃，终点温度为350℃，升温速率1℃/min，焙烧时间为8h；第一焙烧处理结束后打开坩埚盖在350℃下进行第二焙烧处理6h，冷却取出，得到复合催化剂C。经检测，复合催化剂C中改性分子筛含量97重量％，改性分子筛的硅钛摩尔比为23，改性碳纳米材料中氮含量为4.4重量％。Mix CNT and TS-1 evenly at a weight ratio of 1:50 and put them into the crucible (the crucible is covered and sealed), then transfer to the muffle furnace and close the muffle furnace door to start the first roasting process, the first roasting process The initial temperature is 30°C, the end point temperature is 350°C, the heating rate is 1°C/min, and the roasting time is 8h; after the first roasting treatment, the crucible lid is opened and the second roasting treatment is carried out at 350°C for 6h, and then cooled and taken out to obtain a composite Catalyst C. After testing, the modified molecular sieve content in the composite catalyst C is 97% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 23, and the nitrogen content in the modified carbon nanomaterial is 4.4% by weight.
实施例4Example 4
采用与实施例1相同的方法制备复合催化剂D，不同之处仅在于，第二焙烧处理的温度为350℃。经检测，复合催化剂D中改性分子筛含量89重量％，改性分子筛的硅钛摩尔比为27，改性碳纳米材料中氮含量为0.19重量％。Composite catalyst D was prepared by the same method as in Example 1, except that the temperature of the second calcination treatment was 350°C. After testing, the content of the modified molecular sieve in the composite catalyst D is 89% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 27, and the nitrogen content in the modified carbon nanomaterial is 0.19% by weight.
实施例5Example 5
采用与实施例1相同的方法制备复合催化剂E，不同之处仅在于，第一焙烧处理的初始温度为20℃，终点温度为400℃，升温速率为2℃/min，焙烧时间为10h；第一焙烧处理结束后打开坩埚盖在400℃下进行第二焙烧处理12h。经检测，复合催化剂E中改性分子筛含量85重量％，改性分子筛的硅钛摩尔比为28，改性碳纳米材料中氮含量为0.14重量％。Composite catalyst E was prepared in the same manner as in Example 1, the difference being that the initial temperature of the first calcination treatment was 20°C, the end point temperature was 400°C, the heating rate was 2°C/min, and the calcination time was 10h; After the first calcination treatment, open the crucible lid and carry out the second calcination treatment at 400° C. for 12 hours. After testing, the modified molecular sieve content in the composite catalyst E is 85% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 28, and the nitrogen content in the modified carbon nanomaterial is 0.14% by weight.
实施例6Example 6
采用与实施例1相同的方法制备复合催化剂F，不同之处仅在于，CNT和TS-1用量的重量比为1：25。经检测，复合催化剂F中改性分子筛含量93重量％，改性分子筛的硅钛摩尔比为22，改性碳纳米材料中氮含量为0.06重量％。Composite catalyst F was prepared by the same method as in Example 1, except that the weight ratio of CNT and TS-1 was 1:25. After testing, the modified molecular sieve content in the composite catalyst F is 93% by weight, the silicon-titanium molar ratio of the modified molecular sieve is 22, and the nitrogen content in the modified carbon nanomaterial is 0.06% by weight.
对比例1Comparative example 1
将含模板剂的钛硅分子筛(TS-1)在500℃下焙烧8小时，得到不含模板剂的钛硅分子筛。在马弗炉内，氮气气氛下将CNT和不含模板剂的钛硅分子筛按重量比1：10混合均匀后放入坩埚内(坩埚加盖密封)，然后转入马弗炉内关闭马弗炉门后从20℃以2℃/min的升温速率升温到400℃焙烧4.5h后，打开坩埚盖在400℃下焙烧2.5h，冷却取出，得到对比的复合催化剂a。经检测，催化剂a中钛硅分子筛含量91重量％，钛硅分子筛的硅钛摩尔比为25，改性碳纳米材料不含氮。The titanium-silicon molecular sieve (TS-1) containing the template was calcined at 500°C for 8 hours to obtain the titanium-silicon molecular sieve without the template. In the muffle furnace, under the nitrogen atmosphere, mix the CNT and the titanium silicon molecular sieve without the template agent in a weight ratio of 1:10, put it into the crucible (the crucible is covered and sealed), and then transfer to the muffle furnace to close the muffle After the furnace door was raised from 20°C at a rate of 2°C/min to 400°C for 4.5 hours, the lid of the crucible was opened and fired at 400°C for 2.5 hours, then cooled and taken out to obtain comparative composite catalyst a. After testing, the content of the titanium-silicon molecular sieve in the catalyst a is 91% by weight, the silicon-titanium molar ratio of the titanium-silicon molecular sieve is 25, and the modified carbon nanomaterial does not contain nitrogen.
对比例2Comparative example 2
通过物理机械混合使CNT和含模板剂的钛硅分子筛(TS-1)按重量比1：10混合均匀，得到对比的复合催化剂b。经检测，催化剂b中钛硅分子筛含量78重量％，钛硅分子筛的硅钛摩尔比为26，改性碳纳米材料不含氮。By physical and mechanical mixing, the CNT and the titanium-silicon molecular sieve (TS-1) containing the template were uniformly mixed at a weight ratio of 1:10 to obtain the comparative composite catalyst b. After testing, the content of titanium-silicon molecular sieve in the catalyst b is 78% by weight, the molar ratio of silicon to titanium of the titanium-silicon molecular sieve is 26, and the modified carbon nanomaterial does not contain nitrogen.
对比例3Comparative example 3
采用与实施例1相同的方法制备对比的复合催化剂c，不同之处仅在于，只进行第一焙烧处理，不进行第二焙烧处理。经检测，催化剂c中钛硅分子筛含量85重量％，钛硅分子筛的硅钛摩尔比为26，改性碳纳米材料中氮含量为1.24重量％。Comparable composite catalyst c was prepared by the same method as in Example 1, the only difference being that only the first calcination treatment was carried out, and the second calcination treatment was not carried out. After testing, the content of titanium-silicon molecular sieve in the catalyst c is 85% by weight, the molar ratio of silicon to titanium of the titanium-silicon molecular sieve is 26, and the nitrogen content in the modified carbon nanomaterial is 1.24% by weight.
对比例4Comparative example 4
采用与实施例1相同的方法制备对比的复合催化剂d，不同之处仅在于，只进行第二焙烧处理，不进行第一焙烧处理。经检测，催化剂d中钛硅分子筛含量89重量％，钛硅分子筛的硅钛摩尔比为29，改性碳纳米材料中氮含量为0重量％。Comparable composite catalyst d was prepared by the same method as in Example 1, the only difference being that only the second calcination treatment was carried out, and the first calcination treatment was not carried out. After testing, the titanium-silicon molecular sieve content in the catalyst d is 89% by weight, the silicon-titanium molar ratio of the titanium-silicon molecular sieve is 29, and the nitrogen content in the modified carbon nanomaterial is 0% by weight.
对比例5Comparative example 5
采用与实施例1相同的方法制备对比的复合催化剂e，不同之处仅在于，进行第一焙烧处理时，坩埚不加盖密封。经检测，催化剂e中钛硅分子筛含量81重量％，钛硅分子筛的硅钛摩尔比为25，改性碳纳米材料中氮含量为0重量％。The comparative composite catalyst e was prepared in the same manner as in Example 1, except that the crucible was not covered and sealed during the first calcination treatment. After testing, the content of titanium-silicon molecular sieve in the catalyst e is 81% by weight, the molar ratio of silicon to titanium of the titanium-silicon molecular sieve is 25, and the nitrogen content in the modified carbon nanomaterial is 0% by weight.
测试实施例Test Example
无溶剂条件下，环己烷的选择性催化氧化。Selective catalytic oxidation of cyclohexane under solvent-free conditions.
分别将250mg实施例以及对比例制备的复合催化剂和25mL环己烷加入到具有水冷凝器的50mL高压反应釜中，无其他溶剂。之后在温和条件下(130℃，氧气作为氧化剂，持续通入氧气至压力维持在2.0MPa)搅拌该混合物反应5小时后，通过离心和过滤分离催化剂后，分析氧化产物组成。250mg of the composite catalysts prepared in Examples and Comparative Examples and 25mL of cyclohexane were added to a 50mL autoclave with a water condenser, without other solvents. Afterwards, the mixture was stirred and reacted for 5 hours under mild conditions (130° C., oxygen was used as an oxidant, and the pressure was maintained at 2.0 MPa). After the catalyst was separated by centrifugation and filtration, the composition of the oxidation product was analyzed.
表1Table 1
本发明的方法制备得到的复合催化剂对无溶剂下环烷烃的选择性氧化具有良好的催化性能。The composite catalyst prepared by the method of the invention has good catalytic performance for the selective oxidation of cycloalkane under no solvent.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.
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