CN103357433A - Carbon-nitrogen hybrid material of lamellar structure and application thereof - Google Patents
Carbon-nitrogen hybrid material of lamellar structure and application thereof Download PDFInfo
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- CN103357433A CN103357433A CN2013102681417A CN201310268141A CN103357433A CN 103357433 A CN103357433 A CN 103357433A CN 2013102681417 A CN2013102681417 A CN 2013102681417A CN 201310268141 A CN201310268141 A CN 201310268141A CN 103357433 A CN103357433 A CN 103357433A
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- 239000000463 material Substances 0.000 title claims abstract description 88
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000008187 granular material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000000440 bentonite Substances 0.000 claims abstract description 6
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229960000892 attapulgite Drugs 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 34
- YGMJSOJKDUHWCY-UHFFFAOYSA-N [C].N1C=CC=CC=C1 Chemical compound [C].N1C=CC=CC=C1 YGMJSOJKDUHWCY-UHFFFAOYSA-N 0.000 claims description 26
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 238000005119 centrifugation Methods 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 229910052622 kaolinite Inorganic materials 0.000 abstract 1
- 229910052903 pyrophyllite Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- 239000003708 ampul Substances 0.000 description 23
- 239000010453 quartz Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
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- 150000003918 triazines Chemical class 0.000 description 1
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Abstract
The invention provides a carbon-nitrogen hybrid material of a lamellar structure and an application thereof. The preparation method of the carbon-nitrogen hybrid material of lamellar structure comprises the following steps: (1) dispersing a layered template material in water, adding a carbon-nitrogen material to perform exchange adsorption, centrifugally separating, washing with water and drying to obtain granular materials, wherein the layered template material is one of the following ingredients: hectorite, bentonite, kaolinite, ammonium soapstone, fluorine soapstone, attapulgite and pyrophyllite; (2) putting the granular materials in a constant temperature region of a tubular furnace, increasing the temperature of the tubular furnace from the room temperature to 350-650 DEG C at a speed of 1-10 DEG C/min, holding the temperature to react for 2-8h to obtain a layered carbon-nitrogen compound composite material; and (3) adding hydrofluoric acid in the layered carbon-nitrogen compound composite material to remove the template material to obtain the carbon-nitrogen hybrid material of lamellar structure. Novel carbon-nitrogen hybrid material with a lamellar structure is synthesized by the preparation method of the invention for the first time, and the material is used as a catalyst to greatly improve the conversion rate of methanol dehydration reaction.
Description
(1) technical field
The present invention relates to a kind of carbon azepine formed material and application thereof of thin layer laminated structure, especially with it as the application of catalyst in Dehydration of methanol.
(2) technical background
Carbon-nitrogen material has the characteristics such as extraordinary hardness, low-density and chemical inert, thereby has caused the very big interest of scientific circles.At present, the carbon-nitrogen material of synthetic different structure has g-C
3N
4, α-C
3N
4, β-C
3N
4, cube-C
3N
4With false cube-C
3N
4Deng.β-C
3N
4, cube-C
3N
4And false cube-C
3N
4Therefore have very high hardness Deng all, their structure and characteristics is similar to diamond, is expected to replace diamond and becomes new stiff materials.But because C element and N
2Molecule all has very high thermodynamic stability, and the carbon-nitrogen material for preparing above three kinds of crystal structures is still very difficult at present.G-C
3N
4Formation mainly be by crossing the polycondensation of compound in triazine class, such as cyanamide, dicyandiamide, melamine etc.This material has the same layer structure of image-stone China ink, and interlayer contains C
3N
3Ring or C
6N
7N atom by end between the ring, ring and ring links to each other and forms the plane of one deck infinite expanding.The quite wide model of the purposes of carbon-nitrogen material can be for the preparation of the nitrogenous source of mesoporous material, metal nitride, high performance antifriction material etc.In recent years with it as a kind of novel non-metal catalyst, at cyclisation, the CO of catalysis Friedel – Crafts acylation reaction, nitrile or alkynes
2Make remarkable progress in the reactions such as activation.
The synthetic method of graphite-structure carbon-nitrogen material mainly contains two kinds of the hot method of non-solvent and solvent-thermal methods, and the hot method of non-solvent mainly is to generate graphite-structure carbon-nitrogen material (as shown in table 1) by polymerization in the thermal decomposition processes about 500 ℃ such as cyanamide, dicyandiamide, melamine; 2,5,8-triamido-3-triazine (Miller amine) is the important intermediate that forms the graphite-structure carboritride, can get g-C by its further polycondensation
3N
4Material.(the Jurgens B such as Jurgens, Irran E, Senker J, et al.Melem (2,5,8-triamino-tri-s-triazine), an important intermediate during condensation of melamine rings to graphitic carbon nitride:Synthesis, structure determination by X-ray powder diffractometry, solid-state NMR, and theoretical studies[J] .Journal of the American Chemical Society, 2003,125 (34): 10288-10300.) pass through melamine (C
3N
3(NH
2)
3), dicyandiamide (H
4C
2N
4), hydrazoic acid ammonium (NH
4[N (CN)
2]) or cyanamide (H
2CN
2) etc. the polycondensation of compound, obtained intermediate Miller amine, and thought that this intermediate has layer structure, every one deck is the C by the plane
6N
7(NH
2)
3Molecular composition links by hydrogen bond between the molecule, and to have recorded interlamellar spacing be 0.327nm, and when temperature was elevated to 580 ℃, Miller amine can form the g-C that interlamellar spacing is 0.340nm
3N
4Material.(the Guo Q X such as Guo, Yang Q, Yi C Q, et al.Synthesis of carbon nitrides with graphite-like or onion-like lamellar structures via a solvent-free route at low temperatures[J] .Carbon, 2005,43 (7): 1386-1391.) adopt cyanuric chloride (C
3N
3Cl
3) and NaNH
2Or K or NaN
3Be nitrogenous source, place autoclave and be heated to respectively 220 ℃, 300 ℃, 380 ℃, the result has obtained bi-material.The first is to be heated to 220 ℃ C
3N
3Cl
3With NaNH
2Mixture and be heated to 300 ℃ C
3N
3Cl
3Obtained respectively the CN of graphite-structure with the K mixture
1.20And CN
0.96, interplanar distance is respectively 0.328nm and 0.320nm, contains C between the aspect
3N
3Ring; When (N/C〉1) time, link to each other by nitrogen-atoms between the triazine ring; When (N/C ≈ 1), link to each other by carbon-carbon bond between the triazine ring.Another kind is to be heated to 380 ℃ C
3N
3Cl
3With NaN
3Mixture has obtained the less CN of nitrogen content
0.25Material, interplanar distance are 0.341nm; Because formed the lamella microcellular structure as onion, this material has higher interplanar distance.(the Vinu A such as Vinu, Ariga K, Mori T, et al.Preparation and characterization of well-ordered hexagonal mesoporous carbon nitride.Advanced Materials, 2005,17 (13): 1648-1652.) take SBA-15 as template, ethylenediamine (CH
2)
2(NH
2)
2With CCl
4Be raw material, first under 90 ℃ of return stirrings, react 6h, again under nitrogen protection in 600 ℃ of reaction 5h, obtain the aperture and be about 4.0nm, the thick 4.52nm of hole wall, surface area be 505m
2g
-1, pore volume is 0.55cm
3g
-1And has the extraordinary mesoporous carbon nitrogen material that is hexagonal array.Recently, they replace SBA-15 as template with SBA-16, react 6h first under 90 ℃ of return stirrings, again under nitrogen protection in 600 ℃ of reaction 5h, prepared the aperture and be about 3.45nm, the thick 2.91nm of hole wall, surface area be 810m
2g
-1, pore volume is 0.81cm
3g
-1, the cage diameter is 10.83nm and the mesoporous carbon nitrogen material with three-dimensional basket structure.(the Liu L such as Liu, Ma D, Zheng H, et al.Synthesis and characterization of microporous carbon nitride[J] .Microporous and Mesoporous Materials, 2008,110 (2-3): 216-222.) use HZSM-5 instead as template, under identical condition, obtained the aperture and be
Surface area is 408m
2g
-1, pore volume is 0.17cm
3g
-1Carbon-nitrogen material.
Table 1 non-solvent hot preparation graphite-structure carbon-nitrogen material
And solvent-thermal method two mainly is take benzene or hydrazine as solvent, generates graphite-structure carbon-nitrogen material (as shown in table 2) about the vessel in heating to 200 of the sealing take cyanuric chloride as raw material～400 ℃.The solvent heat preparation is compared with above method, has two advantages: (1) temperature conditions in solvent becomes relatively gentle, so that nitrogen is difficult for running off; (2) solid-liquid phase interface or by solvation the species surface more be conducive to the generation of reacting.Because melamine has C
3N
3Skeleton is used as reaction raw materials so be considered at first.That adopt the earliest that solvent-thermal method prepares carboritride is people (the Montigaud H such as Montigaud, Tanguy B, Demazeau G, et al.Graphitic form of C3N4through the solvothermal route[J] .Comptes Rendus De L Academie Des Sciences Serie li Fascicule B-Mecanique Physique Chimie Astronomie, 1997,325 (4): 229-234.), they are take ethyl-2-isopropylamine as solvent, the polycondensation under 140MPa pressure and 250 ℃ of temperature of mixture by melamine and cyanuric chloride obtains the carboritride of graphite-structure, but this material crystallinity is very poor, the mol ratio of carbon nitrogen is C/N=0.78, and very unstable, Montigaud etc. think that the factors of instability are because contain too many hydrogen atom in the material.Recently, (the Li C such as Li, Yang X G, Yang B J, et al.Synthesis and characterization of nitrogen-rich graphitic carbon nitride[J] .Materials Chemistry and Physics, 2007,103 (2-3): 427-432.) with same reactant (melamine and cyanuric chloride), take benzene as solvent, in the situation that Ni exists under 400 ℃ temperature and spontaneous pressure, polycondensation has obtained being of a size of the carboritride spheroid of the stable graphite-structure of 10～40nm hollow, and the mol ratio of carbon nitrogen is C/N=0.625.Li etc. have been the contrast experiment in the situation that does not have Ni, and the carboritride that the result obtains is soluble in organic solvent, think that the carboritride that obtains this moment is oligomer.So think that the adding of Ni has promoted the further polymerization of reactant, also so that products therefrom has special structure; In addition, with (Zhang Z, Leinenweber K, Bauer M, et al.High-pressure bulk synthesis of crystalline C such as Zhang
6N
9H
3HCl:A novel C
3N
4Graphitic derivative[J] .Journal of the American Chemical Society, 2001,123 (32): (pressure: 1～1.5GPa is compared in experiment 7788-7796.); Temperature: 500～550 ℃), the adding of Ni is also so that the gentleness that reaction condition becomes many.They are also with hydrazine (NH
2NH
2) be solvent, having studied at pressure is that 3GPa, temperature are 800～850 ℃ of lower melamine polycondensation reactions, has obtained consisting of C
3N
3.36O
0.14H
1.24The carboritride of graphite-structure, and this material has preferably crystallinity.
Table 2 solvent heat prepares carbon-nitrogen material
Carbon-nitrogen material is as novel catalyst, at cyclisation (such as table 4), the CO of Friedel – Crafts acylation reaction (such as table 3), nitrile or alkynes
2Shown good catalytic activity in activation numerous reactions such as (such as table 5).In these a few class reactions, what really play catalytic action is the carbon-nitrogen material of meso-hole structure, carbon nitrogen is made meso-hole structure changed its surperficial form, has increased surface area, just so that carbon nitrogen has had catalytic activity, and yet there are no the research report for the stratiform carbon-nitrogen nano-material of similar graphite film.Therefore, the carbon azepine formed material of the synthetic thin layer laminated structure of this experimental study, and with in its application dehydration of alcohols reaction.
The mesoporous g-C of table 3
3N
4Be the Friedel – Crafts acylation reaction of the different electrophilic reagents of substrate at 150 ℃ of lower catalysis benzene
The mesoporous g-C of table 4
3N
4The cyclisation result
The mesoporous g-C of table 5
3N
4Catalysis CO
2Reaction result with benzene
| CO 2The source | Reactant | Reaction time/h | Conversion ratio (%) | Product |
| NaHCO 3(200mg) | |
20 | 46 | Phenol (100%) |
| NaHCO 3(100mg) | |
20 | 100 | Phenol (100%) |
| NaHCO 3(400mg) | |
20 | 100 | Phenol (100%) |
| CO 2(10bar) | Benzene | 12 | 20 | Phenol (65%), biphenyl (35%) |
| CO 2(3bar) | Benzene | 24 | 13 | Phenol (29%), biphenyl (71%) |
(3) summary of the invention
First purpose of the present invention is to provide a kind of carbon azepine formed material, and this carbon azepine formed material has the thin layer laminated structure.
Second purpose of the present invention is with the catalyst of described carbon azepine formed material as Dehydration of methanol.
The below does technical scheme of the present invention and specifies.
The invention provides a kind of carbon azepine formed material, its preparation method comprises the steps:
(1) the stratiform mould material is scattered in the water, adds carbon-nitrogen material and carry out exchange adsorption, finish by centrifugation, washing, drying and obtain granular materials; It is one of following that described stratiform mould material is selected from: hectorite, bentonite, kaolin, ammonium soaps stone, fluorine saponite, attapulgite, pyrophillite; It is one of following that described carbon-nitrogen material is selected from: cyanamide, dicyandiamide, melamine, hydrazoic acid ammonium, cyanuric chloride, ethylenediamine;
(2) granular materials carries out the vacuum seal calcination process, temperature is warming up to 350～650 ℃ by room temperature with the speed of 1～10 ℃/min, and insulation reaction 2～8h, then naturally cool to room temperature, obtain carbonitride layer shape compound composite material through vacuum drying, cooling, grinding again;
(3) in carbonitride layer shape compound composite material, add hydrofluoric acid, in ice-water bath, place centrifugation behind 1～5h, again with NaOH solution and concentrated hydrochloric acid successively cyclic washing until faint yellow solid occurs for extremely, wash with water to pH=7, the gained solid obtains carbon azepine formed material through vacuum drying, cooling, grinding again.
In the described step (1), the mass ratio that feeds intake of stratiform mould material and carbon-nitrogen material is 1:1～10, is preferably 1:1～3.
In the described step (1), described exchange adsorption carries out 10～60min under stirring condition.
In the described step (1), described baking temperature is 50～110 ℃, and be 5～20 hours drying time.
In the described step (2), described vacuum seal roasting can be carried out in tube furnace, for example granular materials is put into little quartz ampoule, and entangles with large quartz ampoule, vacuumizes processing, quartz ampoule is placed the flat-temperature zone of tube furnace again.The described vacuum drying temperature of step (2) is 50～100 ℃, and the vacuum drying time is 3～8 hours.
In the described step (3), add the hydrofluoric acid dissolution mould material, its addition is so that can fully dissolve mould material and get final product.
In the described step (3), described vacuum drying temperature is 50～100 ℃, and the vacuum drying time is 5～15 hours.
The present invention also provides described carbon azepine formed material as the application of catalyst in Dehydration of methanol.
Compared with prior art, beneficial effect of the present invention is: the present invention has synthesized the New Type of Carbon azepine formed material that lamellar structure has flake structure first, can significantly improve the conversion ratio of Dehydration of methanol as catalyst with this material.
(4) description of drawings
Fig. 1 is the XRD figure of the thin layer sheet carbon azepine formed material (B) that makes of the carbonitride layer shape compound composite material (A) that makes of embodiment 1 and embodiment 2, among the figure at the 27.68 ° stronger crystal face diffraction maximum assorted nitrogen aromatic ring system d corresponding to conjugation
002The crystal face diffraction, the diffraction maximum of 2 θ=12.83 ° appearance, this is owing to the layered planar structure of class graphite.
Fig. 2 is the FT-IR spectrogram of the thin layer sheet carbon azepine formed material (B) that makes of the carbonitride layer shape compound composite material (A) that makes of embodiment 1 and embodiment 2, among the figure at 1253cm
-1And 1418cm
-1Locate that extremely strong INFRARED ABSORPTION belongs to secondary C on the aromatic ring and the C-N stretching vibration between the tertiary amine N absorbs; 1458cm
-1The place strong absworption peak be in succession on the triazine ring NH and
The C-N stretching vibration of group absorbs; 1632cm
-1The place then belongs to the absorption of vibrations of the C=N on the triazine ring; 1578cm
-1And 3414cm
-1The absorption at place belongs to the absorption of vibrations of N-H; 1320cm
-1Locate stronger absworption peak owing to sp
3The absorption of vibrations of the C-C key of hydridization; 886cm
-1The place then is because sp
2The graphite regions of hydridization.
Fig. 3 is the SEM figure of the thin layer sheet carbon azepine formed material (B) that makes of the carbonitride layer shape compound composite material (A) that makes of embodiment 1 and embodiment 2.
Fig. 4 is the TEM figure of the thin layer sheet carbon azepine formed material (B) that makes of the carbonitride layer shape compound composite material (A) that makes of embodiment 1 and embodiment 2.
(5) specific embodiment
The below is described further technical scheme of the present invention with specific embodiment, but protection scope of the present invention is not limited to this:
Take by weighing 2.00g cyanamide crystal, put into little quartz ampoule, and entangle gravelstone English pipe with large quartz ampoule, vacuumize processing, again quartz ampoule is put into tube furnace together, quartz ampoule remains on the flat-temperature zone of tube furnace substantially, and tube furnace is warming up to 550 ℃ with 4 ℃/min from room temperature, and maintenance 4h, naturally cool to room temperature, get the faint yellow solid powder, in 70 ℃ of vacuum drying 4h, then cool off, grind, obtain flaxen carbonitride layer shape compound composite material pressed powder.Its X-ray diffraction as shown in Figure 1.Its infrared spectrum as shown in Figure 2.Its ESEM pattern as shown in Figure 3.Its transmission electron microscope pattern as shown in Figure 4.
The catalytic performance test of the material that embodiment 1 makes is carried out at the gas-solid bed reaction device take Dehydration of methanol as probe reaction.Take absolute methanol as reaction raw materials, charging rate is controlled to be 0.13ml/min.Take by weighing approximately the 0.5g catalyst reaction tube of packing into and carry out performance test.Carburettor temperature in the course of reaction (TC1), pipeline holding temperature (TC2), reactor heating-up temperature (TC3), clack box heating-up temperature (TC5), chromatogram pipeline holding temperature (TC8), reactor inlet pressure (PT1) and gas circuit 1 nitrogen feed (FL1) are controlled to be respectively 100 ℃, 100 ℃, 200 ℃, 100 ℃, 100 ℃, self-generated pressure and 30ml/min.Product is detected by gas-chromatography Kechuang GC900A, high-purity N
2Do carrier gas, 100 ℃ of hydrogen flame detector temperature, 100 ℃ of vaporizer temperature, 100 ℃ of post case temperature adopt area normalization method to carry out quantitative analysis.The result shows, the material that embodiment 1 makes is in Dehydration of methanol, and the conversion ratio of methyl alcohol is 5.3%, and dimethyl ether is selective 100%, yield of dimethyl ether 5.3%.
Embodiment 2
Take by weighing 2.00g bentonite (being purchased from Chang'an Renheng Chemical Co., Ltd.), add again approximately 100ml distilled water, behind the magnetic agitation 10min, add the 2.0g cyanamide and carry out exchange adsorption, under magnetic agitation, mix, carry out centrifugation after stirring 30min, wash 3 times after, in surface plate, at 70 ℃ of lower dry 12h, after grinding, gained white solid particle packs.
Take by weighing the above-mentioned granular materials of 1.00g and put into little quartz ampoule, and entangle with large quartz ampoule, vacuumize processing, again quartz ampoule is put into tube furnace together, quartz ampoule remains on the flat-temperature zone of tube furnace substantially, tube furnace is warming up to 550 ℃ with 4 ℃/min from room temperature, and keeps 4h, naturally cools to room temperature, can get the gray solid powder, be 70 ℃ of lower vacuum drying 4h, then cool off, grind, gained gray solid powder is carbonitride layer shape compound composite material.
Take by weighing 1.00g gray solid powder carbon nitrogen layer shape compound composite material, the hydrofluoric acid 25ml of adding 36%, centrifugation behind the placement 3h in 0 ℃ of ice-water bath, again with the NaOH solution of 2mol/L and concentrated hydrochloric acid successively cyclic washing 5-6 time until faint yellow solid occurs for extremely, again with distillation washing 2-3 time to the pH=7, the gained faint yellow solid in 70 ℃ of vacuum drying 8h, is then cooled off, grinds, and flaxen solid is thin layer sheet carbon azepine formed material.Its X-ray diffraction as shown in Figure 1.Its infrared spectrum as shown in Figure 2.Its ESEM pattern as shown in Figure 3.Its transmission electron microscope pattern as shown in Figure 4.The catalytic performance of material is tested according to the method for embodiment 1, and the result shows, in Dehydration of methanol, the conversion ratio of methyl alcohol is 23.9%, and dimethyl ether is selective 100%, yield of dimethyl ether 23.9%.
Embodiment 3
Take by weighing 2.00g ammonium soaps stone (being purchased from Jiahe, Ninghai County chemical industry Co., Ltd), add again approximately 100ml distilled water, behind the magnetic agitation 10min, add the 2.0g cyanamide and carry out exchange adsorption, under magnetic agitation, mix, carry out centrifugation after stirring 30min, wash 3 times after, in surface plate, at 70 ℃ of lower dry 12h, after grinding, gained white solid particle packs.Take by weighing the above-mentioned granular materials of 1.00g and put into little quartz ampoule, and entangle with large quartz ampoule, vacuumize processing, again quartz ampoule is put into tube furnace together, quartz ampoule remains on the flat-temperature zone of tube furnace substantially, tube furnace is warming up to 550 ℃ with 4 ℃/min from room temperature, and keeps 4h, naturally cools to room temperature, can get the gray solid powder, be 70 ℃ of lower vacuum drying 4h, then cool off, grind, gained gray solid powder is carbonitride layer shape compound composite material.Take by weighing 1.00g gray solid powder carbon nitrogen layer shape compound composite material, the hydrofluoric acid 25ml of adding 36%, centrifugation behind the placement 3h in 0 ℃ of ice-water bath, again with the NaOH solution of 2mol/L and concentrated hydrochloric acid successively cyclic washing 5-6 time until faint yellow solid occurs for extremely, again with distillation washing 2-3 time to the pH=7, the gained faint yellow solid in 70 ℃ of vacuum drying 8h, is then cooled off, grinds, and flaxen solid is thin layer sheet carbon azepine formed material.The catalytic performance of material is tested according to the method for embodiment 1, and the result shows, material is in Dehydration of methanol, and the conversion ratio of methyl alcohol is 27.6%, and dimethyl ether is selective 100%, yield of dimethyl ether 27.6%.
Embodiment 4
Take by weighing the 2.00g bentonite, add again approximately 100ml distilled water, behind the magnetic agitation 10min, add the 2.0g cyanamide and carry out exchange adsorption, under magnetic agitation, mix, carry out centrifugation after stirring 30min, wash 3 times after, in surface plate, at 70 ℃ of lower dry 12h, after grinding, gained white solid particle packs.Take by weighing the above-mentioned granular materials of 1.00g and put into little quartz ampoule, and entangle with large quartz ampoule, vacuumize processing, again quartz ampoule is put into tube furnace together, quartz ampoule remains on the flat-temperature zone of tube furnace substantially, tube furnace is warming up to 650 ℃ with 5 ℃/min from room temperature, and keeps 4h, naturally cools to room temperature, can get the gray solid powder, be 70 ℃ of lower vacuum drying 4h, then cool off, grind, gained gray solid powder is carbonitride layer shape compound composite material.Take by weighing 1.00g gray solid powder carbon nitrogen layer shape compound composite material, the hydrofluoric acid 25ml of adding 36%, centrifugation behind the placement 3h in 0 ℃ of ice-water bath, again with the NaOH solution of 2mol/L and concentrated hydrochloric acid successively cyclic washing 5-6 time until faint yellow solid occurs for extremely, again with distillation washing 2-3 time to the pH=7, the gained faint yellow solid in 70 ℃ of vacuum drying 8h, is then cooled off, grinds, and flaxen solid is thin layer sheet carbon azepine formed material.The catalytic performance of material is tested according to the method for embodiment 1, and the result shows, material is in Dehydration of methanol, and the conversion ratio of methyl alcohol is 21.7%, and dimethyl ether is selective 100%, yield of dimethyl ether 21.7%.
Embodiment 5
Take by weighing the 2.00g bentonite, add again approximately 100ml distilled water, behind the magnetic agitation 10min, add the 4.0g cyanamide and carry out exchange adsorption, under magnetic agitation, mix, carry out centrifugation after stirring 30min, wash 3 times after, in surface plate, at 70 ℃ of lower dry 12h, after grinding, gained white solid particle packs.Take by weighing the above-mentioned granular materials of 1.00g and put into little quartz ampoule, and entangle with large quartz ampoule, vacuumize processing, again quartz ampoule is put into tube furnace together, quartz ampoule remains on the flat-temperature zone of tube furnace substantially, tube furnace is warming up to 450 ℃ with 3 ℃/min from room temperature, and keeps 4h, naturally cools to room temperature, can get the gray solid powder, be 70 ℃ of lower vacuum drying 4h, then cool off, grind, gained gray solid powder is carbonitride layer shape compound composite material.Take by weighing 1.00g gray solid powder carbon nitrogen layer shape compound composite material, the hydrofluoric acid 25ml of adding 36%, centrifugation behind the placement 3h in 0 ℃ of ice-water bath, again with the NaOH solution of 2mol/L and concentrated hydrochloric acid cyclic washing 5-6 time until faint yellow solid occurs for extremely, again with distillation washing 2-3 time to the pH=7, the gained faint yellow solid in 70 ℃ of vacuum drying 8h, is then cooled off, grinds, and flaxen solid is thin layer sheet carbon-nitrogen nano-material.The catalytic performance of material is tested according to the method for embodiment 1, and the result shows, material is in Dehydration of methanol, and the conversion ratio of methyl alcohol is 26.6%, and dimethyl ether is selective 100%, yield of dimethyl ether 26.6%.
Claims (8)
1. carbon azepine formed material, its preparation method comprises the steps:
(1) the stratiform mould material is scattered in the water, adds carbon-nitrogen material and carry out exchange adsorption, finish by centrifugation, washing, drying and obtain granular materials; It is one of following that described stratiform mould material is selected from: hectorite, bentonite, kaolin, ammonium soaps stone, fluorine saponite, attapulgite, pyrophillite; It is one of following that described carbon-nitrogen material is selected from: cyanamide, dicyandiamide, melamine, hydrazoic acid ammonium, cyanuric chloride, ethylenediamine;
(2) granular materials carries out the vacuum seal calcination process, temperature is warming up to 350～650 ℃ by room temperature with the speed of 1～10 ℃/min, and insulation reaction 2～8h, then naturally cool to room temperature, obtain carbonitride layer shape compound composite material through vacuum drying, cooling, grinding again;
(3) in carbonitride layer shape compound composite material, add hydrofluoric acid, in ice-water bath, place centrifugation behind 1～5h, again with NaOH solution and concentrated hydrochloric acid successively cyclic washing until faint yellow solid occurs for extremely, wash with water to pH=7, the gained solid obtains carbon azepine formed material through vacuum drying, cooling, grinding again.
2. carbon azepine formed material as claimed in claim 1, it is characterized in that: the mass ratio that feeds intake of stratiform mould material and carbon-nitrogen material is 1:1～10.
3. carbon azepine formed material as claimed in claim 1, it is characterized in that: the mass ratio that feeds intake of stratiform mould material and carbon-nitrogen material is 1:1～3.
4. such as the described carbon azepine of one of claim 1～3 formed material, it is characterized in that: in the described step (1), described exchange adsorption is to carry out 10～60min under stirring condition.
5. such as the described carbon azepine of one of claim 1～3 formed material, it is characterized in that: in the described step (1), described baking temperature is 50～110 ℃, and be 5～20 hours drying time.
6. such as the described carbon azepine of one of claim 1～3 formed material, it is characterized in that: in the described step (2), described vacuum drying temperature is 50～100 ℃, and the vacuum drying time is 3～8 hours.
7. such as the described carbon azepine of one of claim 1～3 formed material, it is characterized in that: in the described step (3), described vacuum drying temperature is 50～100 ℃, and the vacuum drying time is 5～15 hours.
8. carbon azepine formed material as claimed in claim 1 is as the application of catalyst in Dehydration of methanol.
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| CN104772043A (en) * | 2015-04-07 | 2015-07-15 | 天津大学 | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane |
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| CN111111737A (en) * | 2020-01-03 | 2020-05-08 | 山西大学 | Nitrogen-doped layered carbon catalyst for catalyzing ethylbenzene oxidation and preparation method thereof |
| CN111261837A (en) * | 2020-03-27 | 2020-06-09 | 中南大学 | Cathode material of pentafluoromagnesium aluminum/nitrogen carbon-doped lithium sulfur battery and preparation method thereof |
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| CN104588063A (en) * | 2015-01-09 | 2015-05-06 | 常州大学 | Attapulgite/graphite phase carbon nitride composite material and preparation method thereof |
| CN104772043A (en) * | 2015-04-07 | 2015-07-15 | 天津大学 | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane |
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| CN111111737A (en) * | 2020-01-03 | 2020-05-08 | 山西大学 | Nitrogen-doped layered carbon catalyst for catalyzing ethylbenzene oxidation and preparation method thereof |
| CN111261837A (en) * | 2020-03-27 | 2020-06-09 | 中南大学 | Cathode material of pentafluoromagnesium aluminum/nitrogen carbon-doped lithium sulfur battery and preparation method thereof |
| CN111261837B (en) * | 2020-03-27 | 2022-02-15 | 中南大学 | Cathode material of pentafluoromagnesium aluminum/nitrogen carbon-doped lithium sulfur battery and preparation method thereof |
| CN114308101A (en) * | 2021-12-22 | 2022-04-12 | 华南理工大学 | Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof |
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