CN112705186B - 2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof - Google Patents
2, 5-dichlorotoluene isomerization catalyst, preparation method and application thereof Download PDFInfo
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- CN112705186B CN112705186B CN201911019197.2A CN201911019197A CN112705186B CN 112705186 B CN112705186 B CN 112705186B CN 201911019197 A CN201911019197 A CN 201911019197A CN 112705186 B CN112705186 B CN 112705186B
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- dichlorotoluene
- catalyst
- heteroatom
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- KFAKZJUYBOYVKA-UHFFFAOYSA-N 1,4-dichloro-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1Cl KFAKZJUYBOYVKA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 37
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 31
- DMEDNTFWIHCBRK-UHFFFAOYSA-N 1,3-dichloro-2-methylbenzene Chemical compound CC1=C(Cl)C=CC=C1Cl DMEDNTFWIHCBRK-UHFFFAOYSA-N 0.000 claims abstract description 20
- RYMMNSVHOKXTNN-UHFFFAOYSA-N 1,3-dichloro-5-methyl-benzene Natural products CC1=CC(Cl)=CC(Cl)=C1 RYMMNSVHOKXTNN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001721 carbon Chemical class 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
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- 235000013162 Cocos nucifera Nutrition 0.000 claims description 8
- 244000060011 Cocos nucifera Species 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
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- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 11
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- 238000003756 stirring Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
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- UZPZYFDULMKDMB-UHFFFAOYSA-N 1,2-dichloro-3,4-dimethylbenzene Chemical group CC1=CC=C(Cl)C(Cl)=C1C UZPZYFDULMKDMB-UHFFFAOYSA-N 0.000 description 2
- WYUIWKFIFOJVKW-UHFFFAOYSA-N 1,2-dichloro-4-methylbenzene Chemical class CC1=CC=C(Cl)C(Cl)=C1 WYUIWKFIFOJVKW-UHFFFAOYSA-N 0.000 description 2
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 2
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
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- GWLKCPXYBLCEKC-UHFFFAOYSA-N 1,2-dichloro-3-methylbenzene Chemical class CC1=CC=CC(Cl)=C1Cl GWLKCPXYBLCEKC-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 1
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical compound NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 description 1
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 description 1
- KGKGSIUWJCAFPX-UHFFFAOYSA-N 2,6-dichlorothiobenzamide Chemical compound NC(=S)C1=C(Cl)C=CC=C1Cl KGKGSIUWJCAFPX-UHFFFAOYSA-N 0.000 description 1
- NGBMMSDIZNGAOK-UHFFFAOYSA-N 2h-triazolo[4,5-d]pyrimidine-5-sulfonamide Chemical compound NS(=O)(=O)C1=NC=C2NN=NC2=N1 NGBMMSDIZNGAOK-UHFFFAOYSA-N 0.000 description 1
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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Abstract
The invention relates to a 2, 5-dichlorotoluene isomerization catalyst, a preparation method and application thereof, wherein the catalyst comprises the following components: the heteroatom source is used for doping a modified carbon source as a catalyst for 2, 5-dichlorotoluene isomerization, and the content of the heteroatom is 0.1-20wt% based on the weight of the doped 2, 5-dichlorotoluene isomerization catalyst. The 2, 5-dichlorotoluene isomerization catalyst prepared by the method has developed pore channels, has a micropore specific surface area not less than 60% of the total specific surface area of the catalyst, and is beneficial to improving the selectivity of 2, 6-dichlorotoluene.
Description
Technical Field
The invention belongs to the field of preparation of fine chemical raw materials, and particularly relates to a 2, 5-dichlorotoluene isomerization catalyst, a preparation method and application thereof.
Background
2, 6-dichlorotoluene is an important fine chemical intermediate applied to the fields of medicine, pigment dye, agrochemical product production and the like. After chlorination and hydrolysis of the side chain methyl, 2, 6-dichlorobenzaldehyde can be prepared, which is a raw material for further preparing the bleaching blue B and the 2, 6-dichlorobenzaldehyde oxime. 2, 6-dichlorobenzene can be obtained by direct oxidation of 2, 6-dichlorotoluene by methyl, and then is subjected to acylation, hydroxylation and CO removal 2 The 2, 6-dichloroaniline can be used for further preparing triazolopyrimidine sulfonamide herbicides TP and the like, and the medicine can be used for synthesizing drugs such as dichlorometacin and the like. The methyl side chain of 2, 6-dichlorotoluene can also react with NH under the action of ammonia oxidation catalyst 3 And air to generate 2, 6-dichlorobenzonitrile in one step, the compound can be directly used as herbicide (dixypyr), and can be further used for synthesizing herbicide (Chlorthi-amid), fluorine-containing acyl urea pesticide and the like.
From the above, 2, 6-dichlorotoluene is a substituted aromatic hydrocarbon with wide application and large usage amount, and along with the continuous increase of the demands of the fields of medicine, agriculture, textile, additives and the like on organic fine chemicals in China, the preparation process of 2, 6-dichlorotoluene also needs to be continuously updated to meet the demands of the products in China, so that the research on the preparation of 2, 6-dichlorotoluene has important practical significance and remarkable economic significance.
The existing preparation methods of the 2, 6-dichlorotoluene mainly comprise an o/p-nitrotoluene method, an o/p-toluenesulfonyl chloride method, a p-tert-butyltoluene chlorination method, a toluene/o-chlorotoluene chlorination method and the like, wherein the toluene/o-chlorotoluene chlorination method is the most simple and convenient in preparation process, less in emission, lower in cost and relatively higher in atom utilization rate. However, a considerable part of 2, 5-dichlorotoluene is generated in the chlorination process of toluene/o-chlorotoluene, and the byproduct has low utilization value and needs to be subjected to isomerization treatment to be converted into 2, 6-dichlorotoluene. The isomerization of the 2, 5-dichlorotoluene is realized by a gas phase isomerization reaction method, which has important significance for improving the production level of fine chemicals in China, meeting the social demands and realizing the high-value utilization of organic raw materials.
In the literature and patent reports, the isomerization reaction of 2, 5-dichlorotoluene mainly uses zeolite molecular sieve or Al 2 O 3 Mainly, the H-type molecular sieve or the metal Ag ion modified zeolite molecular sieve has better 2, 5-dichlorotoluene isomerization performance, but the catalytic materials have certain problems: al (Al) 2 O 3 As a catalyst, the catalyst is considered to be weak in acidity and poor in selectivity, and acid mist is found to be easy to generate in practical application, equipment is corroded, and the environment and human health are harmed; the zeolite molecular sieve is used as a catalytic material with developed micropore channels, has larger specific surface area, strong shape selectivity and more ideal acid distribution, but the acidity of the zeolite molecular sieve is still too high, and part of strong acid sites are easy to cause carbon deposition deactivation, so that the part of acid sites are required to be eliminated by post-treatment to avoid. In addition, the zeolite molecular sieve catalyst has larger micropore content difference along with different framework structures, so that the pore structure and acidity of the zeolite molecular sieve catalyst are in a place needing to be balanced. The zeolite molecular sieve is also complicated in preparation process, aluminum source, silicon source and the like are required to be mixed in a certain proportion under corresponding conditions to prepare synthetic gel, then crystallization is carried out, the synthesized Na-type zeolite also needs to be subjected to ammonium exchange and roasting to obtain H-type zeolite, more steps and conditions are controlled, unstable factors are easy to generate, the addition of an organic template agent is also involved in the synthesis process of a part of zeolite, and the template agent is required to be removed after crystallization is finished, so that the cost is obviously increased. Finally, the zeolite preparation process, the modification process and the like also involve the use of a large amount of water, and the sewage discharge is more, which affects the application of the zeolite molecular sieve, so that further optimization space still exists. The carbon-based material has developed pore canal, stable property and environmental protectionThe method has the advantages of wide sources, low application cost and the like, can realize the doping of various atoms in the carbon-based material by a simple treatment means, and can generate remarkable acidity, reactivity and electron transfer property improvement through doping, so that the method can generate the capability of catalyzing a series of reactions including chemical catalysis, electrocatalytic and the like. After the atomic doping is realized, the carbon-based material can also be a solid acid material with larger specific surface area/micropore specific surface area, so that the carbon-based material has certain isomerization performance and larger application potential.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the 2, 5-dichlorotoluene isomerization catalyst and the preparation method and application thereof, and the catalyst has the advantages of wide raw material sources, simple and convenient preparation, developed pore channels, better reaction performance and low cost.
In order to solve the technical problems, the first aspect of the invention provides a 2, 5-dichlorotoluene isomerization catalyst, which comprises the following components:
heteroatoms and carbon sources, wherein the content of heteroatoms is 0.1 to 20% by weight, preferably 0.5 to 5% by weight, based on the weight of the catalyst.
According to some embodiments of the invention, the catalyst has a particle size of 10 to 40 mesh.
According to some embodiments of the invention, the specific surface area of the catalyst is 700-1200 m 2 ·g -1 Preferably 750 to 1000m 2 ·g -1 。
According to some embodiments of the invention, the catalyst has a micropore specific surface area of 500 to 1100m 2 ·g -1 Preferably 550 to 900m 2 ·g -1 。
According to some embodiments of the invention, the micropore specific surface area is not less than 60%, preferably not less than 72% of the total specific surface area of the catalyst.
According to some embodiments of the invention, the heteroatom is one or more of group IIIA, group VA and group VIA.
According to some embodiments of the invention, the heteroatom is selected from at least one of B, al, N, P.
According to some embodiments of the invention, the carbon source is selected from one or more of coal-based activated carbon, graphene oxide, carbon nanotubes, coconut shell activated carbon, bamboo charcoal.
According to some embodiments of the invention, the catalyst prepared according to the invention is a 2, 5-dichlorotoluene isomerization catalyst.
The second aspect of the invention provides a method for preparing a 2, 5-dichlorotoluene isomerization catalyst, comprising the following steps:
1) Treating a carbon source with alkali liquor to obtain a pretreated modified carbon source;
2) Providing a heteroatom source solution, and then carrying out contact treatment on the pretreated modified carbon source and the heteroatom source solution to obtain a 2, 5-dichlorotoluene isomerization catalyst precursor;
3) And carrying out heat treatment on the 2, 5-dichlorotoluene isomerization catalyst precursor to obtain the 2, 5-dichlorotoluene isomerization catalyst.
According to some embodiments of the invention, the heteroatom source is one or more of an oxide, acid, ammonium salt, hydroxide, nitrate and halide in group IIIA, VA, VIA, preferably one or more of an oxide, acid and ammonium salt selected from B, al, N, P.
According to some embodiments of the invention, the heteroatom source comprises one or more of boric acid, diboron trioxide, boron powder, trimethyl borate, tributyl borate, aluminum isopropoxide, trimethylaluminum, aluminum hydroxide, pyridine, pyrrole, cyanamide, melamine, benzamide, acrylamide, phosphoric acid, diammonium phosphate, monoammonium phosphate, and phosphorus pentachloride.
According to some embodiments of the invention, in step 1), the concentration of the lye is 1 to 4 mol.L -1 Preferably 1 to 2 mol.L -1 。
According to some embodiments of the invention, in step 1), the mass ratio of lye to carbon source is 1-10, preferably 2.5-5.
According to some embodiments of the invention, in step 1), the treatment temperature is 60-100 ℃ and the treatment time is 1-8 hours.
According to some embodiments of the invention, in step 1), the alkaline solution is preferably an aqueous NaOH or KOH solution.
According to some embodiments of the invention, in step 1), the means of treating the carbon source with lye preferably comprises soaking, filtering, washing and drying.
According to some embodiments of the invention, in step 1), the alkaline solution is treated, filtered and washed to a ph=7 of the filtrate.
According to some embodiments of the invention, in step 1), the carbon source is dried in a constant temperature forced air drying oven at 110 ℃ for 2 to 8 hours after the pH is adjusted, to obtain the pretreated modified carbon source.
According to some embodiments of the invention, in step 2), the 2, 5-dichlorotoluene isomerization catalyst precursor may be prepared by an isovolumetric impregnation/overdose/hydrothermal treatment/rotary evaporation method after the pretreated modified carbon source is added to the heteroatom source solution.
According to some embodiments of the invention, in step 2), the heteroatom source solution has a heteroatom source content of 1 to 20 wt-%, preferably 2 to 10 wt-%.
According to some embodiments of the invention, in step 2), the heteroatom source solution comprises 1 to 20wt%, preferably 0.5 to 4wt% of the carbon source.
According to some embodiments of the invention, in step 2), the contact treatment temperature is 80-220 ℃, and the contact treatment time is 2-8 hours.
According to some embodiments of the invention, in step 2), drying is preferably performed after the contacting treatment, more preferably at a drying temperature of 80-110 ℃ for a drying time of 4-8 hours.
According to some embodiments of the invention, in step 3), the heat treatment is performed in an atmosphere of an inert gas selected from Ar, ne and N 2 One or more of the following.
According to some embodiments of the invention, in step 3), the heat treatment is performed at a temperature of 550 to 900 ℃ for a treatment time of 0.5 to 8 hours.
According to some embodiments of the invention, in step 3), the heat treatment is preferably carried out in a tube reactor.
In a third aspect, the invention provides a method for preparing 2, 6-dichlorotoluene by isomerizing 2, 5-dichlorotoluene, comprising the following steps:
the catalyst according to the first aspect of the present invention or the catalyst prepared by the preparation method according to the second aspect of the present invention is contacted with 2, 5-dichlorotoluene in an inert gas atmosphere to react, thereby producing 2, 6-dichlorotoluene.
According to some embodiments of the present invention, a 2, 5-dichlorotoluene isomerization catalyst is placed in a constant temperature fixed bed tubular reactor equipped with a pre-heat vaporizer and contacted with 2, 5-dichlorotoluene to effect a reaction.
According to some embodiments of the present invention, the 2, 5-dichlorotoluene isomerization catalyst particles are placed in a constant temperature section of a constant temperature fixed bed tubular reactor equipped with a pre-heated vaporizer and connected to an inert carrier gas, a liquid phase feed line for the reaction feed 2, 5-dichlorotoluene, and the other sections of the reaction tube are filled with quartz sand. After the reaction product flows out of the reaction tube, it is condensed and collected with circulating cooling water and analyzed by gas chromatography.
According to some embodiments of the invention, the inert gas is selected from Ar, ne and N 2 One or more of the following.
According to some embodiments of the invention, the flow rate of 2, 5-dichlorotoluene is 10-80 mL-min -1 。
According to some embodiments of the invention, the liquid hourly space velocity is 0.2 to 1.0h -1 。
According to some embodiments of the invention, the reaction pressure is 0.1MPa to 2MPa and the reaction temperature is 300 ℃ to 420 ℃.
According to some embodiments of the invention, liquid hourly space velocity = feedstock volumetric flow rate/packed catalyst volume.
According to some embodiments of the invention, preferred reaction preference conditions are: reaction temperature of 360 ℃, N 2 The flow rate is 20 mL/min -1 Liquid hourly space velocity of 0.44h -1 Under the condition, the conversion rate of the 2, 5-dichlorotoluene can reach 44.6 percent, and the selectivity of the 2, 6-dichlorotoluene can reach 32.2 percent.
The invention has the beneficial effects that:
1. the invention uses the 2, 5-dichlorotoluene doped isomerization catalyst for catalyzing the 2, 5-dichlorotoluene to prepare the 2, 6-dichlorotoluene for the first time, and the catalyst has the advantages of simple preparation method, wide carbon source and low cost.
2. The 2, 5-dichlorotoluene isomerization catalyst prepared by the method has developed pore channels, has a micropore specific surface area not less than 60% of the total specific surface area of the catalyst, and is beneficial to improving the selectivity of 2, 6-dichlorotoluene.
Drawings
FIG. 1 is a NH view of the 2, 5-dichlorotoluene isomerization catalyst prepared in examples 1-6 3 -TPD characterization results.
FIG. 2 is an XRD characterization of the 2, 5-dichlorotoluene isomerization catalyst prepared in examples 1-2.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
The preparation of the B-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) Adding the pretreated modified carbon source into a solution consisting of 1.25 g boric acid and 23.75 ml distilled water, wherein the solution is treated with H 3 BO 3 The mass percentage is 5wt%. After fully mixing, the obtained solid-liquid mixture is filled into an autoclave with a polytetrafluoroethylene lining, is heated at 180 ℃ for 6 hours, is filtered and washed, and is dried at 110 ℃ for 4 hours to obtain a precursor of the B-doped 2, 5-dichlorotoluene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 Is heated to 700 ℃ and is treated at the temperature for 6 hours to obtain the B doping2, 5-dichlorotoluene isomerization catalyst.
Example 2
The preparation of the B-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) Adding the pretreated modified carbon source into a solution consisting of 2.5 g boric acid and 22.5 ml distilled water, wherein the solution is prepared by using H 3 BO 3 The mass percentage is 10wt%. After fully mixing, the obtained solid-liquid mixture is filled into an autoclave with a polytetrafluoroethylene lining, is heated at 180 ℃ for 6 hours, is filtered and washed, and is dried at 110 ℃ for 4 hours to obtain a precursor of the B-doped 2, 5-dichlorotoluene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 And the temperature is raised to 700 ℃ and the catalyst is treated for 6 hours at the temperature to obtain the B doped 2, 5-dichlorotoluene isomerization catalyst.
Example 3
The preparation of the P-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) 10 g of the pretreated modified carbon source was added to a solution of 2.5 g of phosphoric acid and 22.5 ml of distilled water, which solution was prepared according to H 3 PO 4 The mass percentage is 10wt%. After fully mixing, the obtained solid-liquid mixture is put into an autoclave with polytetrafluoroethylene lining, heated at 180 ℃ for 6 hours, filtered and washed, dried at 110 ℃ for 4 hours, and the P-doped 2, 5-dichloro methyl is obtainedA precursor to a benzene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 And the temperature is raised to 700 ℃ and the catalyst is treated for 6 hours at the temperature to obtain the B doped 2, 5-dichlorotoluene isomerization catalyst.
Example 4
The preparation of the Al-doped 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) Dropwise adding 10 g of pretreated modified carbon source into a mixed sol consisting of 0.75 g of aluminum isopropoxide and 12.5 ml of distilled water (calculated according to the mass percent of the final Al accounting for 1% of the total solid acid), fully mixing, continuously evaporating water in an open beaker under the conditions of room temperature and magnetic stirring, and drying the mixture at 110 ℃ for 4 hours to obtain a precursor of the Al-doped 2, 5-dichlorotoluene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 And the temperature is raised to 750 ℃ and the reaction is carried out for 6 hours at the temperature to obtain the Al doped 2, 5-dichlorotoluene isomerization catalyst.
Example 5
N, B doped 2, 5-dichlorotoluene isomerization catalyst preparation comprising the steps of:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) Dropwise adding 10 g of a pretreated modified carbon source into a solution which takes 0.48 g of pyrrole, 0.59 g of boric acid and 14 g of absolute ethyl alcohol as solvents, fully mixing, standing at room temperature until the ethanol is completely evaporated, and then heating and drying at 80 ℃ for 2 hours to obtain a precursor of the N, B doped 2, 5-dichlorotoluene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 Is heated to 750 ℃ and treated at this temperature for 6 hours to give N, B doped 2, 5-dichlorotoluene isomerization catalyst.
Example 6
P, B doped 2, 5-dichlorotoluene isomerization catalyst preparation comprising the steps of:
1) Adding 10 g of coconut shell activated carbon into a solution which consists of 2 g of NaOH and 23 ml of distilled water and has the temperature of 80 ℃, fully stirring for 4 hours, filtering, washing, and drying at 110 ℃ for 4 hours to obtain a pretreated modified carbon source;
2) 10 g of the pretreated modified carbon source was added dropwise to a solution of 2.5 g of boric acid, 2.5 g of phosphoric acid, 20ml of distilled water, which solution was prepared according to H 3 BO 3 H and H 3 PO 4 The mass percent is 10 percent by weight. After fully mixing, the obtained solid-liquid mixture is put into an autoclave with a polytetrafluoroethylene lining, heated at 180 ℃ for 6 hours, filtered and washed, and dried at 110 ℃ for 4 hours to obtain a precursor of B, P doped 2, 5-dichlorotoluene isomerization catalyst;
3) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 Is heated to 700 ℃ and treated at that temperature for 6 hours to obtain N, B doped 2, 5-dichlorotoluene isomerization catalyst.
NH doped 2, 5-dichlorotoluene isomerization catalysts prepared in examples 1-6 3 The TPD characterization result is shown in figure 1, and the samples generate obvious acid difference due to the doping elements and the preparation method. Wherein the acid strength of the B doped sample is lower than that of the P doped sample, and the total acid content of the Al doped sample is the lowest. Fig. 2 shows XRD characterization results of representative examples 1 and 2, wherein the broad diffraction peaks corresponding to the (002) and (100) crystal planes of graphite structures are mainly 23 ° and 42 ° except for the boron carbide diffraction peak between 2θ=30 to 40° in example 2. Other samples were identical to example 1 except for example 2 in the position of the XRD diffraction peak out.
Comparative example 1
The preparation of the B-doped nano carbon particle solid acid catalyst comprises the following steps:
1) Taking 10 g of nano carbon particles, adding a solution which takes 0.2 g of boric acid and 15 g of absolute ethyl alcohol as solvents, fully mixing, standing at room temperature until the ethyl alcohol is completely evaporated, and then heating and drying at 80 ℃ for 2 hours to obtain a precursor of the B-doped nano carbon particle solid acid catalyst.
2) Putting the precursor into a quartz boat, putting the quartz boat into a tube furnace communicated with Ar atmosphere, and controlling the flow rate to be 60 mL/min -1 In Ar protective atmosphere environment of (2) in the following temperature of 2 ℃ min -1 And (3) heating to 750 ℃, and treating at the temperature for 6 hours to obtain the B-doped nano carbon particle solid acid catalyst.
Comparative example 2
The preparation of the HZSM-5 molecular sieve, and the synthesis of the HZSM-5 molecular sieve is carried out based on a hydrothermal crystallization method reported in literature, and comprises the following specific steps:
1) Putting 10.0 g of deionized water into a beaker, placing a magnet, opening a magnetic stirrer, and adding 1.6 g of sodium metaaluminate and 3.3 g of sodium hydroxide under stirring to prepare a mixed solution;
2) 58.2 g of SiO was taken 2 Adding 30% by weight of silica sol into the solution prepared in the step (1) under stirring, and stirring for 1.5 hours to uniformly mix the sol;
3) Adding 3.9 g of tetrapropylammonium hydroxide solution into the mixed sol prepared in the step (2), and continuously stirring for 1.5 hours after the addition is finished;
4) Transferring the synthetic gel into a crystallization kettle, standing at 170 ℃ for 28 hours for hydrothermal crystallization, cooling the obtained product, and carrying out suction filtration, washing and drying at 110 ℃ to obtain the ZSM-5 molecular sieve containing the template agent;
5) The ZSM-5 molecular sieve containing the template agent is heated to 550 ℃ at the heating rate of 4 ℃/min, and the template agent is removed by roasting at 550 ℃ for 4 hours, so as to obtain the NaZSM-5 molecular sieve;
6) The NH of the obtained NaZSM-5 molecular sieve is 1mol/L 4 Molecular sieve in Cl solution, NH 4 The mass ratio of Cl solution is 1:10, and the ion exchange is continuously carried out for 3 times under the condition that the treatment temperature is 80 ℃ to obtain NH 4 ZSM-5 molecular sieve;
7) NH obtained 4 The ZSM-5 molecular sieve is heated to 480 ℃ at the heating rate of 4 ℃/min and kept at 480 ℃ for 4 hours, so as to obtain the HZSM-5 molecular sieve;
8) After tabletting, HZSM-5 molecular sieve is crushed and sieved to 40-60 mesh granules, and the granules are used as a catalyst for the isomerization reaction of 2, 5-dichlorotoluene.
The results of characterization of the pore structures and elemental analysis of examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
Table 1 pore structure and heteroatom content characterization results for doped 2, 5-dichlorotoluene isomerization catalysts prepared in different ways
* HZSM-5 molecular sieve is composed of Si, al and SiO elements only 2 /Al 2 O 3 ＝30
As can be seen from Table 1, the catalysts prepared in examples 1 to 6 had a ratio of micropore specific surface area to catalyst total specific surface area of 72.34 to 81.63%.
Examples 7 to 14
Taking the catalysts prepared in examples 1 to 6 and comparative examples 1 to 2 as examples, the reaction temperature was 360℃and N 2 The flow rate is 20 mL/min -1 Liquid hourly space velocity of 0.44h -1 The gas phase isomerization reaction of 2, 5-dichlorotoluene is carried out under the condition of (1), the influence of a preparation method and doping elements on isomerization performance is examined, and the reaction results are shown in table 2:
TABLE 2 preparation of doped 2, 5-dichlorotoluene isomerization catalysts by different means evaluation results of 2, 5-dichlorotoluene isomerization reaction Performance
*2,6-DCT, 2,4-DCT, 3,4-DCT, 2,3-DCT represent isomers of dichlorotoluene, 2, 6-dichlorotoluene, 2, 4-dichlorotoluene, 3, 4-dichlorotoluene, 2, 3-dichlorotoluene, respectively; DCX represents dichloroxylenes; DCB represents dichlorobenzene; CB represents chlorobenzene, and is similar to the following.
As can be seen from Table 2, the B-doped 2, 5-dichlorotoluene isomerization catalyst had good 2, 5-dichlorotoluene isomerization reaction performance at a B-doped level of 0.97% by weight.
Example 15
This example illustrates the B-doped 2, 5-dichlorotoluene isomerization catalyst prepared in example 2, at N 2 The flow rate is 20 mL/min -1 Liquid hourly space velocity of 0.44h -1 The gas phase isomerization reaction of 2, 5-dichlorotoluene is carried out under the condition of (1), the influence of temperature on isomerization performance is examined, and the reaction evaluation results are shown in table 3:
TABLE 3 influence of reaction temperature on 2, 5-dichlorotoluene isomerization reaction Performance by doped 2, 5-dichlorotoluene isomerization catalyst
As can be seen from table 3, the conversion rate was lower before 350 ℃ with increasing reaction temperature, and the reaction conversion rate and the selectivity of 2, 6-dichlorotoluene were continuously improved with increasing reaction temperature; the conversion rate is not greatly increased after the reaction temperature is further increased to 370 ℃, but the selectivity of the 2, 6-dichlorotoluene is obviously reduced, so that the reaction temperature of 350 ℃ is the reaction temperature most suitable for the gas-phase isomerization of the 2, 5-dichlorotoluene in the comprehensive view.
Example 16
This example illustrates the B-doped 2, 5-dichlorotoluene isomerization catalyst prepared in example 2, at N 2 The flow rate is 20 mL/min -1 The gas phase isomerization reaction of 2, 5-dichlorotoluene is carried out at the reaction temperature of 360 ℃, the influence of the liquid space velocity on the isomerization performance is examined, and the reaction evaluation results are shown in table 4:
TABLE 4 influence of reaction temperature on the performance of doped 2, 5-dichlorotoluene isomerization catalysts in 2, 5-dichlorotoluene isomerization reactions
As can be seen from table 4, the reaction conversion gradually decreased with increasing liquid hourly space velocity, but at low liquid hourly space velocity, the selectivity of side reaction products, particularly dichloroxylenes and the like, was significantly increased, indicating that disproportionation reaction more favorable for methyl transfer occurs at lower liquid hourly space velocity, which is detrimental to isomerization reaction. At higher liquid hourly space velocity, the reaction conversion rate and the selectivity of the 2, 6-dichlorotoluene isomer also obviously decrease due to insufficient residence time of the 2, 5-dichlorotoluene molecules of the raw material, thus 0.44h -1 Is a more proper liquid hourly space velocity condition.
It should be noted that the above examples are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (15)
1. A preparation method of 2, 6-dichlorotoluene comprises the following steps:
in inert atmosphere, contacting 2, 5-dichlorotoluene isomerization catalyst with 2, 5-dichlorotoluene to react and produce 2, 6-dichlorotoluene;
the 2, 5-dichlorotoluene isomerization catalyst comprises the following components: heteroatom and carbon source, wherein, the content of the heteroatom is 0.1-20wt% based on the weight of the catalyst;
the preparation method of the 2, 5-dichlorotoluene isomerization catalyst comprises the following steps:
1) Treating a carbon source with alkali liquor to obtain a pretreated modified carbon source;
2) Providing a heteroatom source solution, and then carrying out contact treatment on the pretreated modified carbon source and the heteroatom source solution to obtain a 2, 5-dichlorotoluene isomerization catalyst precursor;
3) Carrying out heat treatment on a 2, 5-dichlorotoluene isomerization catalyst precursor to obtain a 2, 5-dichlorotoluene isomerization catalyst;
the hetero atom is one or more of IIIA group and VA group.
2. The method of claim 1, wherein the inert atmosphere is selected from the group consisting of N 2 One or more of Ne and Ar, the flow rate of 2, 5-dichlorotoluene is 10-80 mL-min -1 Liquid hourly space velocity of 0.2-1.0 h -1 The reaction pressure is 0.1-2 MPa, and the reaction temperature is 300-420 ℃.
3. The process according to claim 1 or 2, wherein the heteroatom content is from 0.5 to 5wt% based on the weight of the catalyst;
and/or, the treating the carbon source with the lye includes soaking, filtering, washing and drying.
4. The method according to claim 1 or 2, wherein the specific surface area of the catalyst is 700-1200 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Micropores of catalystSpecific surface area of 500-1100 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The micropore specific surface area is not less than 60% of the total specific surface area of the catalyst.
5. The method according to claim 4, wherein the specific surface area of the catalyst is 750-1000 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The micropore specific surface area of the catalyst is 550-900 m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The micropore specific surface area is not less than 72% of the total specific surface area of the catalyst.
6. The method according to claim 1 or 2, wherein the heteroatom is selected from at least one of B, al, N and P.
7. The method of claim 1 or 2, wherein the carbon source is selected from one or more of coal-based activated carbon, graphene oxide, carbon nanotubes, coconut shell activated carbon, and bamboo charcoal.
8. The method of claim 1 or 2, wherein the heteroatom source is one or more of oxides, acids, ammonium salts, hydroxides, nitrates, and halides in groups IIIA, VA.
9. The method of claim 8, wherein the heteroatom source is selected from one or more of an oxide, an acid, and an ammonium salt of B, al, N, P.
10. The method of claim 1 or 2, wherein the heteroatom source is selected from one or more of boric acid, diboron trioxide, boron powder, trimethyl borate, tributyl borate, aluminum isopropoxide, trimethylaluminum, aluminum hydroxide, pyridine, pyrrole, cyanamide, melamine, benzamide, acrylamide, phosphoric acid, diammonium hydrogen phosphate, monoammonium dihydrogen phosphate, and phosphorus pentachloride.
11. The method according to claim 1 or 2, wherein in step 1), the concentration of the lye is 1 to 4 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The treatment temperature is 60-100 ℃, and the treatment time is 1-8 hours.
12. The method according to claim 11, wherein in step 1), the concentration of the alkali solution is 1 to 2 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the alkali liquor is NaOH or KOH aqueous solution; and/or the mass ratio of the alkali liquor to the carbon source is 1-10.
13. The method according to claim 12, wherein in the step 1), the mass ratio of the alkali solution to the carbon source is 2.5-5.
14. The method according to claim 1 or 2, wherein in step 2), the heteroatom source solution has a heteroatom source content of 1 to 20wt%; and/or the total amount of the heteroatom source solution accounts for 1-20wt% of the carbon source; and/or the contact temperature is 80-220 ℃, and/or the contact treatment time is 2-8 hours,
and/or drying after the contacting treatment;
in the step 3), the heat treatment is carried out in an inert atmosphere, the temperature of the heat treatment is 550-900 ℃, and the treatment time is 0.5-8 h.
15. The method according to claim 14, wherein in step 2), the content of the heteroatom source in the heteroatom source solution is 2-10wt%; and/or the total amount of the heteroatom source solution accounts for 0.5-4wt% of the carbon source;
and/or drying at 80-110 ℃ for 4-8 hours;
and/or the inert atmosphere in the step 3) is selected from Ar, ne and N 2 One or more of the following.
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