CN116196965B - Gamma-Al 2 O 3 C-N catalyst and preparation method thereof - Google Patents
Gamma-Al 2 O 3 C-N catalyst and preparation method thereof Download PDFInfo
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- CN116196965B CN116196965B CN202310454280.2A CN202310454280A CN116196965B CN 116196965 B CN116196965 B CN 116196965B CN 202310454280 A CN202310454280 A CN 202310454280A CN 116196965 B CN116196965 B CN 116196965B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 172
- 229910018072 Al 2 O 3 Inorganic materials 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 93
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 36
- 238000000137 annealing Methods 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000005121 nitriding Methods 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000007038 hydrochlorination reaction Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000013043 chemical agent Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010453 quartz Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 7
- 229940050176 methyl chloride Drugs 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002920 hazardous waste Substances 0.000 description 4
- 230000000415 inactivating effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XOOGZRUBTYCLHG-UHFFFAOYSA-N tetramethyllead Chemical compound C[Pb](C)(C)C XOOGZRUBTYCLHG-UHFFFAOYSA-N 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- OHBQPCCCRFSCAX-UHFFFAOYSA-N 1,4-Dimethoxybenzene Chemical compound COC1=CC=C(OC)C=C1 OHBQPCCCRFSCAX-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000003589 local anesthetic agent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- QYPPRTNMGCREIM-UHFFFAOYSA-M methylarsonate(1-) Chemical compound C[As](O)([O-])=O QYPPRTNMGCREIM-UHFFFAOYSA-M 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ZISSAWUMDACLOM-UHFFFAOYSA-N triptane Chemical compound CC(C)C(C)(C)C ZISSAWUMDACLOM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of methane chloride production, and particularly relates to gamma-Al 2 O 3 A catalyst for preparing C-N and its preparing process are disclosed. The gamma-Al 2 O 3 Deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol with a C-N catalyst 2 O 3 The catalyst is used as a raw material; in said gamma-Al 2 O 3 The C-N catalyst contains C-N bond and C=N bond, and the nitrogen doped carbon is uniformly distributed in gamma-Al 2 O 3 Is a surface of the substrate. The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps: (1) Preparation of gamma-Al 2 O 3 /C 1‑x : deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol 2 O 3 Annealing the catalyst in air atmosphere; (2) Preparation of gamma-Al 2 O 3 C-N: the gamma-Al obtained is then reacted with 2 O 3 /C 1‑x Nitrogen doping is carried out by adopting a nitriding agent to obtain gamma-Al 2 O 3 A C-N catalyst. The gamma-Al 2 O 3 the/C-N catalyst not only can be used as deactivated gamma-Al for dangerous waste treatment 2 O 3 The catalyst is fully utilized in a recycling way, and the obtained gamma-Al 2 O 3 The catalytic activity of the catalyst/C-N can be higher than that of the fresh gamma-Al used in the prior art 2 O 3 A catalyst.
Description
Technical Field
The invention belongs to the technical field of methane chloride production, and particularly relates to gamma-Al 2 O 3 A catalyst for preparing C-N and its preparing process are disclosed.
Background
Methyl chloride is widely used as an important methylating agent in the following fields: (1) Producing methyl cellulose, hydroquinone dimethyl ether, methyl mercaptan, arsonate and the like; (2) Preparing dichloromethane, chloroform, carbon tetrachloride, trimethylbutane, methylchlorosilane and tetramethyllead; (3) Solvents for refrigerants, blowing agents, rubbers, resins, organic compounds; (4) use as a local anesthetic or the like in medicine.
At present, the methyl chloride production adopts a methanol hydrochlorination synthesis process: placing methanol gas and hydrogen chloride gas in activated alumina (gamma-Al) 2 O 3 ) The reaction of synthesizing methyl chloride by hydrochlorination of methanol is carried out in a catalyst fixed bed reactor, the reaction temperature is 240-260 ℃, the mixed gas obtained after the reaction contains methyl chloride, water, excessive HCl, a small amount of unreacted methanol and the like, the mixed gas is subjected to a series of separation, purification and drying to obtain methyl chloride, and the methyl chloride is compressed and then sent to a subsequent system, such as methylene dichloride and the like for use.
Raw material methanol is easy to be carbonized at the reaction temperature of 240-260 ℃ in the existing production process of methane chloride, so that the adopted gamma-Al is caused 2 O 3 The pores of the catalyst are blocked, thereby affecting the catalytic performance. In addition to pore blocking caused by methanol carbonization, the formation of inactive boehmite AlO (OH) during the reaction also leads to catalyst deactivation.
Since the reaction temperature of methane chloride production is lower than that of catalytic cracking petroleum, and the molecules of raw material methanol are smaller, carbon deposition generated on the catalyst is also relatively less, and then the gamma-Al used for methane chloride production 2 O 3 The catalyst has relatively long service period and small dosage, so when the catalyst is used for producing the gamma-Al for the chloromethane 2 O 3 The catalyst is usually replaced directly by fresh gamma-Al after deactivation 2 O 3 Catalyst, and replaced deactivated gamma-Al 2 O 3 The catalyst is disposed of as hazardous waste.
However, deactivated gamma-Al produced in the production process of the para-chloromethane 2 O 3 The catalyst treatment method not only causes waste of catalyst resources, but also greatly increases production cost and hazardous waste treatment cost with the increase of time. Therefore, there is a need for an economical and environmentally friendly solution to the deactivation of gamma-Al in the production process of methyl chloride 2 O 3 Catalyst handling problems.
Disclosure of Invention
The invention provides a gamma-Al 2 O 3 C-N catalyst and preparation method thereof, gamma-Al 2 O 3 Deactivated gamma-Al in the production of chloromethane as a C-N catalyst 2 O 3 Catalyst (gamma-Al) 2 O 3 The preparation method takes/C) as the raw material, not only effectively solves the problem of inactivating gamma-Al in the production of methane chloride 2 O 3 Problems with catalyst handling, deactivated gamma-Al to be disposed of as hazardous waste 2 O 3 The catalyst is fully utilized in a recycling way, can be used for producing methane chloride again, and omits fresh gamma-Al 2 O 3 Cost of acquisition of the catalyst and the resulting gamma-Al 2 O 3 The catalytic activity of the catalyst/C-N can be higher than that of the fresh gamma-Al used in the prior art 2 O 3 The catalyst greatly improves the production efficiency of the chloromethane and brings multiple economic benefits to enterprises.
The inventors have found that if deactivated gamma-Al 2 O 3 The catalyst is used as a raw material to prepare the catalyst with activity, and the biggest difficulty is that: how to deactivate gamma-Al 2 O 3 Is the catalyst regain activity? And whether the activity of the prepared novel catalyst can reach or even exceed that of fresh gamma-Al 2 O 3 Catalytic activity of the catalyst?
The inventors have attempted to use the conventional high temperature heat treatment method, but as a result have found that not only the deactivation of the raw material gamma-Al cannot be completely recovered 2 O 3 The catalytic activity of the catalyst also greatly reduces its service life.
After a great deal of creative labor is paid, the following technical scheme is provided:
Gamma-Al 2 O 3 C-N catalyst for synthesizing deactivated gamma-Al produced in chloromethane production by hydrochlorination of methanol 2 O 3 The catalyst is used as a raw material; in said gamma-Al 2 O 3 The C-N catalyst contains C-N bond and C=N bond, and the nitrogen doped carbon is uniformly distributed in gamma-Al 2 O 3 Is a surface of the substrate.
In the present invention, the gamma-Al 2 O 3 In the nitrogen doping of the/C-N catalyst, the pyridine-N accounts for 21% -43%, the pyrrole-N accounts for 31% -47%, and the inactive graphite-N accounts for 17% -48%. It can be seen that the gamma-Al of the present invention 2 O 3 The nitrogen doping of the/C-N catalyst is based on pyridine-N and pyrrole-N.
Preferably, the gamma-Al 2 O 3 In the nitrogen doping of the/C-N catalyst, the pyridine-N accounts for 35.93 percent, the pyrrole-N accounts for 46.45 percent, and the inactive graphite-N accounts for 17.62 percent.
In the present invention, the gamma-Al 2 O 3 The specific surface area of the catalyst/C-N is 185-188sqm, and the most probable pore diameter is 9-9.5nm.
Fresh gamma-Al used for synthesizing chloromethane by hydrochlorination of methanol in the prior art 2 O 3 The catalyst is generally white Raschig ring, the external diameter is 3.95-4.05mm, the internal diameter is 1-2mm, the height is 3.9-4.1mm, the specific surface area is 190-191sqm, and the most probable pore diameter is 9.6-9.8nm. Deactivated gamma-Al produced by catalytic reaction 2 O 3 The catalyst is black Raschig ring, and besides the color change, the deactivated gamma-Al 2 O 3 The catalyst is compared with fresh gamma-Al in terms of macroscopic morphology 2 O 3 The catalyst did not change significantly. Deactivated gamma-Al 2 O 3 The specific surface area of the catalyst is 178-179sqm, and the most probable pore diameter is 8.5-8.7nm.
Above mentioned gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : hydrogen methanolDeactivated gamma-Al produced in chloromethane production 2 O 3 Annealing the catalyst in air atmosphere for 1-5 hr to obtain gamma-Al 2 O 3 /C 1-x The method comprises the steps of carrying out a first treatment on the surface of the Wherein x represents the amount of carbon deposit removed by annealing treatment, and 1-x represents the residual amount of carbon deposit after annealing treatment;
(2) Preparation of gamma-Al 2 O 3 C-N: the gamma-Al obtained in the step (1) is reacted with 2 O 3 /C 1-x Nitrogen doping is carried out by adopting a nitriding agent under the argon atmosphere to obtain gamma-Al 2 O 3 A C-N catalyst.
The preparation method of the invention synthesizes the deactivated gamma-Al generated in the production of chloromethane by the hydrochlorination of methanol 2 O 3 The catalyst is used as raw material, firstly, deactivated gamma-Al is carried out in air atmosphere 2 O 3 The catalyst is flatly paved in a muffle furnace for annealing treatment, and the removal amount and the residual amount of amorphous carbon generated by carbonization of methanol are controlled by adjusting the heat preservation time of the annealing treatment, so that a foundation is laid for forming active sites by subsequent nitrogen doping; at the same time, the inactive boehmite AlO (OH) component generated in the process of catalyzing the production of the chloromethane is decomposed again and converted into active gamma-Al 2 O 3 。
Then, the residual amorphous carbon controlled by the annealing treatment is converted into nitrogen-doped carbon by nitrogen doping with a nitriding agent, exposing more defects and active gamma-Al 2 O 3 The synergistic effect increases the catalytic activity of the catalyst. The catalyst after high temperature nitriding is recovered to porous structure, and the catalytic active site is repaired and reinforced.
In the invention, the gamma-Al 2 O 3 The annealing treatment temperature in the step (1) of the preparation method of the C-N catalyst is 500-700 ℃; the heating rate of the annealing treatment is 3-10 ℃/min, and the heat preservation time is 1-5h.
The obtained gamma-Al is controlled by regulating and controlling the heat preservation time length 2 O 3 /C 1-x Carbon content in (c). Preferably, the incubation period is 2 hours.
The annealing temperature in step (1) directly affects the gamma-Al formed 2 O 3 /C 1-x In order to better and accurately regulate the uniformity of the carbon content distribution in the catalyst, the nitrogen doping process in the step (2) is laid, and the annealing temperature is controlled to be 500-700 ℃.
Inactivating gamma-Al when annealing temperature is 400 DEG C 2 O 3 The appearance color of the catalyst is still black after the catalyst is subjected to annealing treatment and heat preservation for 2 hours, and the carbon deposit is proved to be difficult to remove at the temperature. Inactivating gamma-Al when the annealing temperature is 600 DEG C 2 O 3 The appearance color of the catalyst is changed after the catalyst is subjected to annealing treatment and heat preservation for 2 hours, and the catalyst is matched with fresh gamma-Al 2 O 3 The catalyst was slightly yellow in color compared to pure white. When the annealing temperature reaches 800 ℃, the gamma-Al is deactivated 2 O 3 The appearance color of the catalyst is not recovered to fresh gamma-Al after the catalyst is subjected to annealing treatment and heat preservation for 2 hours 2 O 3 The pure white color of the catalyst indicates that carbon deposition cannot be completely removed only by heat treatment, i.e., the catalytic activity of the catalyst cannot be completely recovered.
Preferably, the annealing treatment temperature in the step (1) is 600 ℃.
Meanwhile, the heating rate of the annealing treatment in the step (1) is not easy to be too high, if the heating rate is too high, the catalyst is easy to be heated unevenly, so that carbon is unevenly distributed in the catalyst, and the catalytic activity of the prepared catalyst is greatly influenced.
Preferably, the temperature rise rate of the annealing treatment is 5 ℃/min.
By thermogravimetric analysis, annealing at 600deg.C, maintaining for 2 hr to obtain gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 0.8wt%.
In the invention, the gamma-Al 2 O 3 In the step (2) of the preparation method of the/C-N catalyst, the nitriding agent is any one of ammonium chloride, ammonium carbonate or ammonium bicarbonate.
In the invention, the gamma-Al 2 O 3 Nitriding agent in step (2) of the preparation method of the C-N catalyst: gamma-Al 2 O 3 /C 1-x The mass ratio of (2) is 1:9-11.
Preferably, the nitridingThe preparation method comprises the following steps: gamma-Al 2 O 3 /C 1-x The mass ratio of (2) is 1:10. Placing nitriding agent at upstream of muffle furnace, and adding gamma-Al 2 O 3 /C 1-x Downstream of the muffle.
In the invention, the gamma-Al 2 O 3 The nitrogen doping temperature in the step (2) of the preparation method of the C-N catalyst is 300-500 ℃, the heating rate is 2-5 ℃/min, and the heat preservation time is 1-3h; the flow rate of argon is 10-50mL/min.
The nitrogen doping in step (2) is decomposed into NH by nitriding agent at high temperature 3 ，NH 3 With gamma-Al 2 O 3 /C 1-x The amorphous carbon in the invention reacts to finally form nitrogen doped carbon, the nitrogen doped temperature can ensure the decomposition of the nitriding agent and the gamma-Al 2 O 3 The nitrogen doping of the/C-N catalyst is mainly pyridine-N and pyrrole-N with high activity, so that the formation of inactive graphite-N is reduced as much as possible.
The heating rate in the nitrogen doping process directly influences the uniformity of nitrogen doping, and the nitrogen content is controlled by adjusting the heat preservation time of the nitrogen doping. The argon gas acts to transport NH generated by the nitriding agent 3 To gamma-Al 2 O 3 /C 1-x The surface reacts with the carbon contained in the catalyst and plays a role of protective gas, so that the flow rate of the catalyst is controlled to be 10-50mL/min.
Preferably, the temperature of nitrogen doping in the step (2) is 400 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 2 hours; argon flow was 30mL/min.
Above mentioned gamma-Al 2 O 3 C-N catalyst or gamma-Al prepared by the preparation method 2 O 3 The application of the catalyst/C-N in the catalytic production of methane chloride, wherein the conversion rate of methanol is more than or equal to 99.2%, and the selectivity of the methane chloride is more than or equal to 99.4%.
The beneficial effects of the invention are as follows: gamma-Al according to the invention 2 O 3 Deactivated gamma-Al produced in synthesizing chloromethane by hydrochlorination of methanol with C-N catalyst 2 O 3 The catalyst is prepared by taking the catalyst as the raw material, thereby not only effectively solving the problem of deactivated gamma-Al in the production of methane chloride 2 O 3 The problem of catalyst treatment is that the deactivated catalyst used as the hazardous waste treatment is fully and resource utilized, can be reused for the production of methane chloride, and omits fresh gamma-Al 2 O 3 Cost of acquisition of the catalyst, and the resulting gamma-Al 2 O 3 The catalytic activity of the catalyst/C-N is higher than that of the fresh gamma-Al used in the prior art 2 O 3 The catalyst greatly improves the production efficiency of chloromethane and brings multiple economic benefits to enterprises.
Deactivated gamma-Al in the production of chloromethane 2 O 3 Preparation of gamma-Al by using catalyst as raw material 2 O 3 The C-N catalyst is prepared by first inactivating gamma-Al in the production of chloromethane 2 O 3 The catalyst is annealed in an air atmosphere and then nitrogen doped by a nitriding agent. The method is simple and efficient, does not need other complex treatment steps, and not only converts AlO (OH) generated in the process of catalyzing the chloromethane production reaction into gamma-Al with catalytic activity at high temperature 2 O 3 Further activating by nitrogen doping process to expose more active sites and gamma-Al 2 O 3 The gamma-Al prepared by the method can produce synergistic effect to further improve the catalytic activity 2 O 3 Catalytic Activity of the/C-N catalyst compared to fresh gamma-Al 2 O 3 The catalyst is more preferable.
Drawings
FIG. 1 shows fresh gamma-Al in an embodiment of the invention 2 O 3 SEM image of the catalyst by scanning electron microscopy.
FIG. 2 shows deactivated gamma-Al produced during the hydrochlorination of methanol to synthesize chloromethane in accordance with an embodiment of the present invention 2 O 3 SEM image of the catalyst by scanning electron microscopy.
FIG. 3 shows fresh gamma-Al in an embodiment of the invention 2 O 3 Catalyst and deactivated gamma-Al 2 O 3 XRD diffraction pattern of catalyst.
FIG. 4 shows the gamma-Al obtained in example 1 of the present invention 2 O 3 /C 1-x SEM images of (a).
FIG. 5 shows the present inventionGamma-Al prepared in example 1 2 O 3 /C 1-x An XRD diffraction pattern of (C).
FIG. 6 shows the gamma-Al obtained in example 1 of the present invention 2 O 3 SEM image and elemental profile of a C-N catalyst.
FIG. 7 shows the gamma-Al obtained in example 1 of the present invention 2 O 3 XRD diffraction pattern of the C-N catalyst.
FIG. 8 shows the gamma-Al obtained in example 1 of the present invention 2 O 3 C1sXPS results for the C-N catalysts.
FIG. 9 shows the gamma-Al obtained in example 1 of the present invention 2 O 3 N1sXPS results for the C-N catalysts.
Detailed Description
The invention will now be described in more detail with reference to the drawings and examples.
The reagents, equipment and materials described in the examples below, unless otherwise indicated, are all those of the prior art and are commercially available.
The model of a thermogravimetric analyzer adopted in the 1, thermogravimetric analysis is a relaxation-resistant STA409C.
2. XPS verifies that a Siemens flight 250Xi photoelectron spectrometer is used.
3. The X-ray diffractometer used for XRD measurement was of the type Dmax-Ultima of Japanese physics.
4. The gas chromatograph used for the analysis and measurement of the gas chromatograph in experimental example 1 was Shimadzu 2010-PRO.
Example 1
The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol 2 O 3 The catalyst is flatly laid in a muffle furnace, and is annealed in the air atmosphere, the annealing temperature is controlled to be 600 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 hours; obtained by thermogravimetric analysis of the gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 0.8wt%.
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 /C 1-x Placing 10g of nitriding agent ammonium chloride at the downstream of a quartz tube of a tubular furnace, placing 10g of nitriding agent ammonium chloride at the upstream of the quartz tube of the tubular furnace, heating to 400 ℃ at a heating rate of 3 ℃/min under argon atmosphere with a gas flow of 30mL/min, and preserving heat for 2h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Fresh white raschig ring gamma-Al used in methyl chloride synthesis production by hydrochlorination of methanol 2 O 3 The catalyst had an outer diameter of 4.05mm, an inner diameter of 1.5mm, a height of 4.1mm, a specific surface area of 191sqm and a most probable pore diameter of 9.8nm.
Whereas deactivated black raschig ring gamma-Al produced in production 2 O 3 The catalyst had a specific surface area of 179sqm and a most probable pore size of 8.7nm.
The specific surface area of the gamma-Al 2O3/C-N catalyst prepared by the preparation method described in example 1 was 186sqm and the most probable pore diameter was 9.4nm.
As shown in FIG. 1, fresh gamma-Al 2 O 3 The catalyst has a relatively large number of pore structures in the interior.
As shown in FIG. 2, deactivated gamma-Al 2 O 3 The surface of the catalyst is covered with a layer of filiform carbon deposit; eventually resulting in a reduction of the specific surface area and the most probable pore size to 178 sqm,8.7nm, respectively. In addition to the pore size change, the phase of the catalyst also changes significantly.
As shown in FIG. 3, the catalyst is prepared from original gamma-Al 2 O 3 Converted to AlO (OH).
As shown in FIG. 4, by controlling the annealing temperature, the annealing temperature rise rate and the holding time, the obtained gamma-Al 2 O 3 /C 1-x The carbon in the catalyst is uniformly distributed on the surface of the catalyst, and a precondition is provided for the next nitrogen doping process.
As shown in FIG. 5, XRD results demonstrate that AlO (OH) is completely recovered to catalytically active gamma-Al after 600℃annealing 2 O 3 。
As shown in FIG. 6, it can be seen that the productγ-Al 2 O 3 The carbon and nitrogen elements in the C-N catalyst are uniformly distributed on the surface of the catalyst.
As shown in FIG. 7, the resulting gamma-Al after nitrogen doping 2 O 3 XRD diffraction pattern of the/C-N catalyst and gamma-Al obtained by annealing only 2 O 3 /C 1-x There was no significant change (shown in fig. 5).
For this reason, the results of nitrogen doping were further verified by XPS.
As shown in FIGS. 8 and 9, the results of C1s and N1s demonstrate that gamma-Al 2 O 3 The catalyst contains C-N bond and C=N bond, gamma-Al 2 O 3 The nitrogen doping of the/C-N catalyst is mainly pyridine-N and pyrrole-N, wherein the pyridine-N accounts for 35.93 percent, the pyrrole-N accounts for 46.45 percent, and the inactive graphite-N accounts for 17.62 percent. pyridine-N and pyrrole-N are rich in defects, exposing more active sites, and gamma-Al 2 O 3 After the synergistic effect, the catalytic efficiency can be effectively improved.
Example 2
The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol 2 O 3 The catalyst is flatly laid in a muffle furnace, and is annealed in the air atmosphere, the annealing temperature is controlled to be 500 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 1h; obtained by thermogravimetric analysis of the gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 1.1wt%.
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing an/C (carbon monoxide) into the downstream of a quartz tube of a tubular furnace, placing 10g of nitriding agent ammonium carbonate into the upstream of the quartz tube of the tubular furnace, heating to 400 ℃ at a heating rate of 3 ℃/min under an argon atmosphere with a gas flow of 30mL/min, and preserving heat for 2h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Example 3
The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol 2 O 3 The catalyst is flatly laid in a muffle furnace, and is annealed in the air atmosphere, the annealing temperature is controlled to be 700 ℃, the heating rate is 10 ℃/min, and the heat preservation time is 5 hours; obtained by thermogravimetric analysis of the gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 0.5wt%.
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing a nitriding agent ammonium bicarbonate 10g at the downstream of a quartz tube of a tubular furnace, heating to 400 ℃ at a heating rate of 3 ℃/min under an argon atmosphere with a gas flow of 30mL/min, and preserving heat for 2h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Example 4
The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : step (1) as in example 1;
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing an/C (carbon) into the downstream of a quartz tube of a tubular furnace, placing 10g of nitriding agent ammonium chloride into the upstream of the quartz tube of the tubular furnace, heating to 300 ℃ at a heating rate of 2 ℃/min under an argon atmosphere with a gas flow of 10mL/min, and preserving heat for 1h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Obtained by XPS verification, gamma-Al obtained in example 4 2 O 3 The pyridine-N ratio in the catalyst/C-N is 42.51%, the pyrrole-N ratio is 33.86%, and the inactive graphite-N ratio is 23.63%.
Example 5
The gamma-Al 2 O 3 A preparation method of the catalyst/C-N comprises the following steps:
(1) Manufacturing processPreparation of gamma-Al 2 O 3 /C 1-x : step (1) is the same as in example 1;
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing an/C (carbon) into the downstream of a quartz tube of a tubular furnace, placing 10g of nitriding agent ammonium chloride into the upstream of the quartz tube of the tubular furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere with a gas flow of 50mL/min, and preserving heat for 3h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Obtained by XPS verification, gamma-Al obtained in example 5 2 O 3 The pyridine-N ratio in the catalyst/C-N is 21.16%, the pyrrole-N ratio is 31.63%, and the inactive graphite-N ratio is 47.21%.
Comparative example 1
The catalyst of this comparative example was prepared by a method different from that of example 1 in that no gamma-Al was prepared 2 O 3 C-N procedure. Otherwise, the same as in example 1 was conducted.
Comparative example 2
The catalyst preparation method described in this comparative example comprises the steps of:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al in the production of chloromethane 2 O 3 The catalyst is flatly laid in a muffle furnace, and is annealed in the air atmosphere, wherein the annealing temperature is controlled to be 400 ℃, the heating rate is 5 ℃/min, and the time is 2 hours; obtained by thermogravimetric analysis of the gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 1.3wt%.
(2) Preparation of gamma-Al 2 O 3 C-N: step (2) in example 1 was repeated.
Comparative example 3
The preparation method of the catalyst in the comparative example comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al in the production of chloromethane 2 O 3 The catalyst is spread in a muffle furnace, annealed in air atmosphere, the annealing temperature is controlled to 800 ℃, and the heating rate is 5The temperature is 2 hours per minute; obtained by thermogravimetric analysis of the gamma-Al 2 O 3 /C 1-x The carbon content in (C) was 0.3wt%.
(2) Preparation of gamma-Al 2 O 3 C-N: step (2) in example 1 was repeated.
Comparative example 4
The preparation method of the catalyst in the comparative example comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : step (1) in example 1 is the same.
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing a nitriding agent ammonium bicarbonate 10g at the downstream of a quartz tube of a tubular furnace, heating to 200 ℃ at a heating rate of 5 ℃/min under an argon atmosphere with a gas flow of 20mL/min, and preserving heat for 1h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
As proved by XPS, the gamma-Al obtained in comparative example 4 is insufficient in decomposition of nitriding agent due to lower temperature 2 O 3 There is almost no nitrogen-doped carbon present in the/C-N catalyst.
Comparative example 5
The preparation method of the catalyst in the comparative example comprises the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : step (1) in example 1 is the same.
(2) Preparation of gamma-Al 2 O 3 C-N: taking 100g of gamma-Al obtained in the step (1) 2 O 3 Placing a nitriding agent ammonium bicarbonate 10g at the downstream of a quartz tube of a tubular furnace, heating to 600 ℃ at a heating rate of 10 ℃/min under an argon atmosphere with a gas flow of 40mL/min, and preserving heat for 4h to perform nitrogen doping to obtain gamma-Al 2 O 3 A C-N catalyst.
Obtained by XPS verification, gamma-Al obtained in comparative example 5 2 O 3 The pyridine-N ratio in the catalyst is 16.7%, the pyrrole-N ratio is 23.2%, and the inactive graphite-N ratio is 16.7%60.1%.
Experimental example 1
1. The purpose of the experiment is as follows: for fresh gamma-Al 2 O 3 The catalysts obtained in examples 1 to 5 and comparative examples 1 to 5 were evaluated for catalytic efficiency.
2. The experimental method comprises the following steps: the catalysts obtained above are used for catalyzing the hydrochlorination of methanol to prepare chloromethane, and the specific conditions are as follows: the ratio of methanol to hydrogen chloride is 1:1.15, the reaction temperature is controlled at 240 ℃ and the pressure is controlled at 0.2MPa. And respectively carrying out gas chromatographic analysis and determination on the mixed gas prepared by hydrochlorination using different catalysts to obtain conversion rate and selectivity data.
3. Experimental results:
the specific results are shown in Table 1.
The catalytic efficiency index of each catalyst obtained in Table 1
From the data analysis in table 1, it can be seen that: fresh gamma-Al 2 O 3 The initial methanol conversion of the catalyst is 99.41 percent, and the initial methane chloride selectivity is 99.63 percent; the methanol conversion after 200 hours was 99.22% and the methane chloride selectivity after 200 hours was 99.41%.
Gamma-Al obtained in comparative example 1 2 O 3 /C 1-x The initial methanol conversion and initial methane chloride selectivity of the catalyst were 99.13% and 99.42%, respectively, and were substantially restored to the level of fresh catalyst; the methanol conversion after 200 hours was 92.33%, and the methane chloride selectivity after 200 hours was 93.59%, which was a major decrease in catalyst life by annealing alone compared to the fresh catalyst.
Gamma-Al obtained in example 1 2 O 3 The initial methanol conversion rate and the methane chloride selectivity of the catalyst/C-N can reach 99.72 percent and 99.84 percent respectively, and the catalytic efficiency of the catalyst/C-N is even more than that of fresh gamma-Al 2 O 3 A catalyst; the methanol conversion rate after 200 hours is 99.60 percent, the chloromethane selectivity after 200 hours is 99.71 percent, and the cycle stability is also higherGood.
Claims (9)
1. Gamma-Al 2 O 3 A catalyst for synthesizing chloromethane by hydrochlorination of methanol 2 O 3 The catalyst is used as a raw material; in said gamma-Al 2 O 3 The C-N catalyst contains C-N bond and C=N bond, and the nitrogen doped carbon is uniformly distributed in gamma-Al 2 O 3 Is a surface of (2);
the gamma-Al 2 O 3 In the nitrogen doping of the/C-N catalyst, the pyridine-N accounts for 21% -43%, the pyrrole-N accounts for 31% -47%, and the inactive graphite-N accounts for 17% -48%.
2. gamma-Al according to claim 1 2 O 3 A catalyst for C-N, characterized in that the gamma-Al 2 O 3 In the nitrogen doping of the/C-N catalyst, the pyridine-N accounts for 35.93 percent, the pyrrole-N accounts for 46.45 percent, and the inactive graphite-N accounts for 17.62 percent.
3. gamma-Al according to claim 1 2 O 3 A catalyst for C-N, characterized in that the gamma-Al 2 O 3 The specific surface area of the catalyst/C-N is 185-188sqm, and the most probable pore diameter is 9-9.5nm.
4. A gamma-Al according to any one of claims 1 to 3 2 O 3 The preparation method of the catalyst/C-N is characterized by comprising the following steps:
(1) Preparation of gamma-Al 2 O 3 /C 1-x : deactivated gamma-Al produced in the production of chloromethane by hydrochlorination of methanol 2 O 3 Annealing the catalyst in air atmosphere for 1-5 hr to obtain gamma-Al 2 O 3 /C 1-x The method comprises the steps of carrying out a first treatment on the surface of the Wherein x represents the amount of carbon deposit removed by annealing treatment, and 1-x represents the residual amount of carbon deposit after annealing treatment;
(2) Preparation of gamma-Al 2 O 3 C-N: the gamma-Al obtained in the step (1) is reacted with 2 O 3 /C 1-x Nitrogen under argon atmosphereNitrogen doping is carried out by the chemical agent to obtain gamma-Al 2 O 3 a/C-N catalyst;
wherein the temperature of nitrogen doping is 300-500 ℃.
5. gamma-Al according to claim 4 2 O 3 The preparation method of the/C-N catalyst is characterized in that the annealing treatment temperature in the step (1) is 500-700 ℃; the heating rate of the annealing treatment is 3-10 ℃/min.
6. gamma-Al according to claim 4 2 O 3 The preparation method of the catalyst/C-N is characterized in that the nitriding agent in the step (2) is any one of ammonium chloride, ammonium carbonate or ammonium bicarbonate.
7. gamma-Al according to claim 4 2 O 3 A process for preparing a C-N catalyst, characterized in that in step (2) the nitriding agent: gamma-Al 2 O 3 /C 1-x The mass ratio of (2) is 1:9-11.
8. gamma-Al according to claim 4 2 O 3 The preparation method of the catalyst/C-N is characterized in that the heating rate of nitrogen doping in the step (2) is 2-5 ℃/min, and the heat preservation time is 1-3h; the flow rate of argon is 10-50mL/min.
9. A gamma-Al according to any one of claims 1-3 2 O 3 A C-N catalyst or gamma-Al prepared by the process of any one of claims 4 to 8 2 O 3 The application of the catalyst/C-N in the catalytic production of methane chloride is characterized in that the conversion rate of methanol is more than or equal to 99.2%, and the selectivity of the methane chloride is more than or equal to 99.4%.
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