CN109622016A - A kind of method of preparation and use of the nitrogen-doped carbon material for acetylene hydrochlorination reaction - Google Patents
A kind of method of preparation and use of the nitrogen-doped carbon material for acetylene hydrochlorination reaction Download PDFInfo
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- CN109622016A CN109622016A CN201811591751.XA CN201811591751A CN109622016A CN 109622016 A CN109622016 A CN 109622016A CN 201811591751 A CN201811591751 A CN 201811591751A CN 109622016 A CN109622016 A CN 109622016A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 53
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 37
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 34
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 33
- 239000004640 Melamine resin Substances 0.000 claims abstract description 32
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 16
- 239000005011 phenolic resin Substances 0.000 claims abstract description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 93
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 76
- 238000010438 heat treatment Methods 0.000 claims description 66
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 238000012423 maintenance Methods 0.000 claims description 41
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 235000019270 ammonium chloride Nutrition 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 230000000717 retained effect Effects 0.000 claims description 22
- 238000011049 filling Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229960003511 macrogol Drugs 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004451 qualitative analysis Methods 0.000 claims description 3
- 238000004445 quantitative analysis Methods 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- OOSUHIIJYDMCCW-UHFFFAOYSA-N cyanamide;formaldehyde Chemical compound O=C.NC#N OOSUHIIJYDMCCW-UHFFFAOYSA-N 0.000 claims 1
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 23
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000007711 solidification Methods 0.000 abstract description 6
- 230000008023 solidification Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003643 water by type Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 2
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 2
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 2
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- -1 phenolic aldehyde Chemical class 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Abstract
The present invention proposes the preparation method and its application method of a kind of nitrogen-doped carbon material for the reaction of fixed bed acetylene hydrochlorination, belongs to material synthesis technology.The industrially melamine resin that has been commercialized can be used in this method and phenolic resin is precursor, and temperature-programmed calcination obtains nitrogen-doped carbon catalyst by solidification and under an inert atmosphere.The catalyst is applied in the reaction of fixed bed preparing chloroethylene by acetylene hydrochlorination, there is certain catalytic activity and selectivity.
Description
Technical field
The present invention propose it is a kind of for fixed bed acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method and its make
With method, belong to material synthesis technology.The melamine resin being industrially commercialized and phenolic aldehyde tree can be used in this method
Rouge is precursor, and by solidification and under an inert atmosphere temperature-programmed calcination obtains nitrogen-doped carbon catalyst.By the catalyst
In reaction applied to fixed bed preparing chloroethylene by acetylene hydrochlorination, there is certain catalytic activity and selectivity.
Background technique
Polyvinyl chloride (PVC) is one of most popular thermoplastic resin.This resin can be made into hard tough products,
It is with a wide range of applications, including pipeline and accessory, door and window and clad plate.Vinyl chloride monomer (VCM) is for producing PVC
Monomer.According to the energy resource structure of China, the key industry route for producing VCM is the acetylene hydrochlorination based on carbide.Currently,
The reaction relies primarily on HgCl2Catalyst.But the loss of mercury brings to human health and environment and seriously threatens.Therefore, carry out and use
It is of great significance in the research of the catalyst without mercury of acetylene hydrochlorination.
Currently, the report about catalyst without mercury is mainly some metal chlorides, including Bi3+, Pt2+, Pd2+Deng all having
There is preferable activity, wherein the Au-based catalyst of Huctings et al. report is the optimum catalyst of acetylene hydrochlorination reaction, but
It is that Au-based catalyst is easy inactivation in the reaction, and the cost of gold is very high, limits the further genralrlization of the catalyst.In recent years
Come, domestic numerous studies mechanism studies have shown that nitrogen-doped carbon material for there is preferable catalysis in acetylene hydrochlorination reaction
Property.For example, the Dai Bin of university, Shihezi of Xinjiang teaches et al. and to report g-C3N4/ AC catalyst has in acetylene hydrochlorination reaction
Preferable catalytic activity；SiC the@C-N and h-BN of the packet letter and academician of Dalian chemistry and physics Institute et al. research preparation are urged
Agent also shows excellent catalytic performance in the reaction.But the preparation step of above-mentioned catalyst is cumbersome, and condition requires more severe
It carves, is unfavorable for mass production.
Summary of the invention
It is an object of the invention to propose it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation and its make
With method, this method introduces process using melamine resin liquid as raw material, without complicated nitrogen, in conjunction with pore-foaming agent
It uses, the nitrogen-doped carbon catalyst with certain specific surface area is obtained by solidification, carbonization and activation, is reacted in acetylene hydrochlorination
In have preferable catalytic activity and selectivity.
The specific technical solution of the present invention is as described below:
A kind of scheme 1: preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that including following step
It is rapid:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, be added 20-60 nm's that resin liquid mass fraction is 3-10%
One or more of silica or aluminium oxide, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time is obtained
Sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is placed in 36-48 h of agitator treating in the beaker for filling HF solution, etches away the titanium dioxide retained in sample
Silicon or aluminium oxide are dried after being then washed with deionized water to neutrality to get nitrogen-doped carbon material is arrived, and wherein HF dosage is addition two
10-20 times of silica or alumina molar amount.
Scheme 2: it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method, it is characterised in that including with
Lower step:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
One or more of silica or aluminium oxide of 20-60 nm of mixed resin liquid mass fraction 3-10% is added in ionized water,
Precuring is heated at 80-110 DEG C, 0.5-1 h of pre-cure time obtains sample A, wherein liquid phenolic resin and melamine
The mass ratio of formaldehyde resin liquid is 0.1-1；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is placed in 36-48 h of agitator treating in the beaker for filling HF solution, etches away the titanium dioxide retained in sample
Silicon or aluminium oxide are dried after being then washed with deionized water to neutrality to get nitrogen-doped carbon material is arrived, and wherein HF dosage is addition two
10-20 times of silica or alumina molar amount.
Scheme 3: it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method, it is characterised in that including with
Lower step:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, sodium chloride, the carbonic acid of resin liquid mass fraction 3-10% be added
One or more of sodium or ammonium carbonate, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time obtains sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, sodium carbonate or carbonic acid
Sample is filtered dry after separating to get nitrogen-doped carbon material is arrived later by ammonium.
Scheme 4: it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method, it is characterised in that including with
Lower step:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
One or more of sodium chloride, sodium carbonate or the ammonium carbonate of mixed resin liquid mass fraction 3-10% is added, 80-in ionized water
Precuring is heated at 110 DEG C, 0.5-1 h of pre-cure time obtains sample A, wherein liquid phenolic resin and melamino-formaldehyde tree
The mass ratio of rouge liquid is 0.1-1；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, sodium carbonate or carbonic acid
Sample is filtered dry after separating to get nitrogen-doped carbon material is arrived later by ammonium.
Scheme 5: it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method, it is characterised in that including with
Lower step:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, the polyethylene glycol of resin liquid mass fraction 20-50% be added
400, one of macrogol or polyvinyl butyral or several, heat precuring at 80-110 DEG C, when precuring
Between 0.5-1 h, obtain sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then with the heating rate of 1-5 DEG C/min be raised to 500-900 DEG C of maintenance at least 3 h to get
To nitrogen-doped carbon material, wherein inert atmosphere is He, N2, one of Ar.
Scheme 6: it is a kind of for acetylene hydrochlorination reaction nitrogen-doped carbon material preparation method, it is characterised in that including with
Lower step:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
Ionized water is added in polyethylene glycol 400, macrogol or the polyvinyl butyral of mixed resin liquid mass fraction 20-50%
One or more, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time obtains sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one of Ar；
4) sample C is mixed with potassium hydroxide powder, mixture is transferred in tube furnace after being fully ground, in the lazy of flowing
Property gas atmosphere under, 180-200 DEG C and constant temperature at least 1 h are warming up to the heating rate of 5-10 DEG C/min, then with 1-5 DEG C
The heating rate of/min is warming up to 450-1200 DEG C and is activated at least 2 h, naturally cold under inert atmosphere purging later
But to room temperature, sample D is obtained, wherein the mass ratio of sample C and potassium hydroxide is 0.5-3；
5) sample D is sufficiently washed to neutrality with excessive deionized water, sample is filtered dry after separating to get arriving later
Nitrogen-doped carbon material.
A kind of scheme 7: nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that appoint in operational version 1-6
Preparation method described in one is made.
Scheme 8: a kind of application method of nitrogen-doped carbon catalyst described in scheme 7, feature specifically includes the following steps:
1) it takes nitrogen-doped carbon material to be placed in fixed bed reactors, 160-260 DEG C and perseverance is warming up under the inert gas of flowing
Temperature at least 1 h, wherein the volume space velocity of inert gas is 15-45 h-1；
2) inert gas is closed, is switched to the hydrogen chloride gas of flowing, and constant temperature at least 1 h, wherein the volume space velocity of hydrogen chloride
For 15-45 h-1；
3) it is passed through acetylene gas, acetylene volume space velocity is 15-45 h-1, the molar ratio of hydrogen chloride and acetylene is 1.05-1.3:1；
4) use temperature range of nitrogen-doped carbon catalyst is 160-260 DEG C；
5) qualitative and quantitative analysis is carried out to the gas after reaction using gas-chromatography.
The present invention has following significant innovation compared with the prior art:
The present invention obtains the nitrogen with certain specific surface area by solidification, pore, roasting and activating process using resin liquid as raw material
Doped carbon material catalyst, compared with existing catalyst, which has the advantages that environmental-friendly free of contamination, and raw material
Use can industrial resin liquid, be free of any metallic element, raw material is sufficient, cheap.In nitrogen-doped carbon material
In preparation process, without being introduced back into nitrogen source, simple process is easy to operate.Acetylene hydrochlorination reaction in can show compared with
Good activity and selectivity is expected to alleviate the pollution problem of mercury metal and the expensive problem of noble metal to a certain extent.
Detailed description of the invention
Fig. 1: the SEM figure of nitrogen-doped carbon material prepared by embodiment 2.
Fig. 2: the SEM figure of nitrogen-doped carbon material prepared by embodiment 8.
Specific embodiment
To better illustrate this patent, following embodiment is now listed.Following embodiment is to keep industry personnels more detailed
The thin understanding present invention or content according to the present invention make some nonessential modifications and adaptations.But the scope of the present invention
It is not restricted by the embodiments.Protection scope of the present invention proposes in the dependent claims.
Embodiment 1
1) 10 g melamine resin liquid are weighed, 0.05 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 0.5 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
Product A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material catalyst CAT-1 is arrived, wherein HF dosage is addition two
10 times of silica mole.
Embodiment 2
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 0.5 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
Product A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-2 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 3
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-3 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 4
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the aluminium oxide of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-4 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 5
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 100 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-5 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 6
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 10 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-6 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 7
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 500 DEG C of 3 h of maintenance are raised to the heating rate of 3 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-7 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 8
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-8 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 9
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added the silica of 1 g, 20-60 nm, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample
A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 4 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-9 is arrived, wherein HF dosage is that silica is added
10 times of mole.
Embodiment 10
1) 10 g melamine resin liquid are weighed, then weigh 5 g liquid phenolic resins, mixes, is added under stirring
0.15 g ammonium chloride adds 15 g deionized waters, and the silica of 1.5 g, 20-60 nm is added, and heats at 90 DEG C pre-
Solidification, 0.5 h of pre-cure time obtain sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-10 is arrived, wherein HF dosage is that titanium dioxide is added
10 times of silicon mole.
Embodiment 11
1) 10 g melamine resin liquid are weighed, then weigh 3 g liquid phenolic resins, mixes, is added under stirring
0.13 g ammonium chloride adds 13 g deionized waters, and the silica of 1.3 g, 20-60 nm is added, and heats at 90 DEG C pre-
Solidification, 0.5 h of pre-cure time obtain sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is placed in 48 h of agitator treating in the beaker for filling HF solution, etches away the silica retained in sample,
Then it is dried after being washed with deionized water to neutrality to get nitrogen-doped carbon material C AT-11 is arrived, wherein HF dosage is that titanium dioxide is added
10 times of silicon mole.
Embodiment 12
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added 1 g sodium chloride, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, later filters sample
It is dried after separation to get nitrogen-doped carbon material C AT-12 is arrived.
Embodiment 13
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g go from
Sub- water is added 0.5 g sodium chloride, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, later filters sample
It is dried after separation to get nitrogen-doped carbon material C AT-13 is arrived.
Embodiment 14
1) 10 g melamine resin liquid are weighed, then weigh 5 g liquid phenolic resins, mixes, is added under stirring
0.15 g ammonium chloride, adds 15 g deionized waters, and 1.5 g sodium chloride are added, and heats precuring at 90 DEG C, when precuring
Between 0.5 h, obtain sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, later filters sample
It is dried after separation to get nitrogen-doped carbon material C AT-14 is arrived.
Embodiment 15
1) 10 g melamine resin liquid are weighed, 0.1 g ammonium chloride is added under stirring, add 10 g deionizations
Water is added 3 g polyethylene glycol 400s, precuring is heated at 90 DEG C, 0.5 h of pre-cure time obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains nitrogen-doped carbon material C AT-15；
Embodiment 16
1) 10 g melamine resin liquid are weighed, then weigh 5 g liquid phenolic resins, mixes, is added under stirring
0.15 g ammonium chloride adds 15 g deionized waters, and 3 g polyethylene glycol 400s are added, precuring, precuring are heated at 90 DEG C
0.5 h of time, obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is mixed with potassium hydroxide powder, mixture is transferred in tube furnace after being fully ground, in the N of flowing2
Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to the heating rate of 5 DEG C/min, then heat up with the heating rate of 5 DEG C/min
It carries out being activated 2 h to 600 DEG C, the cooled to room temperature under inert atmosphere purging, obtains sample D, wherein sample later
The mass ratio of C and potassium hydroxide is 1:1；
5) sample D is sufficiently washed to neutrality with excessive deionized water, sample is filtered dry after separating to get arriving later
Nitrogen-doped carbon material C AT-16.
Embodiment 17
1) 10 g melamine resin liquid are weighed, then weigh 5 g liquid phenolic resins, mixes, is added under stirring
0.15 g ammonium chloride adds 15 g deionized waters, and 3 g polyethylene glycol 400s are added, precuring, precuring are heated at 90 DEG C
0.5 h of time, obtains sample A；
2) sample A is placed in 120 DEG C of baking ovens and is solidified, 5 h of curing time obtains sample B；
3) sample B is placed in tube furnace, N2Atmosphere is roasted, and is first raised to 300 DEG C of dimensions with the heating rate of 5 DEG C/min
1 h is held, then 700 DEG C of 3 h of maintenance are raised to the heating rate of 5 DEG C/min, obtains sample C；
4) sample C is mixed with potassium hydroxide powder, mixture is transferred in tube furnace after being fully ground, in the N of flowing2
Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to the heating rate of 5 DEG C/min, then heat up with the heating rate of 5 DEG C/min
It carries out being activated 2 h to 800 DEG C, the cooled to room temperature under inert atmosphere purging, obtains sample D, wherein sample later
The mass ratio of C and potassium hydroxide is 1:1；
5) sample D is sufficiently washed to neutrality with excessive deionized water, sample is filtered dry after separating to get arriving later
Nitrogen-doped carbon material C AT-17.
The evaluation procedure and condition of catalyst are as follows:
1) it takes 1 mL catalyst to be placed in fixed bed reactors, 220 DEG C are warming up under the inert gas of flowing and maintain 1
H, wherein the volume space velocity of inert gas is 45 h-1；
2) inert gas is closed after, is switched to the hydrogen chloride gas of flowing, and maintain 1 h, wherein the volume space velocity of hydrogen chloride
For 45 h-1；
3) it is passed through acetylene gas, acetylene volume space velocity is 30 h-1, the molar ratio of hydrogen chloride and acetylene is 1.2:1.
Qualitative and quantitative analysis is carried out to the gas after reaction using gas-chromatography.It is primary every 0.5 h sampling, and use gas
Analysis of hplc product composition, with react 2 h point carry out sampling analysis, the conversion of alkyne of different nitrogen-doped carbon catalyst and
It is as shown in the table for vinyl chloride selectivity correlation data:
| Catalyst number | Conversion of alkyne (%) | Vinyl chloride selectivity (%) |
| CAT-1 | 56.8 | 98.8 |
| CAT-2 | 57.3 | 98.7 |
| CAT-3 | 65.4 | 98.5 |
| CAT-4 | 62.7 | 99.2 |
| CAT-5 | 64.8 | 98.7 |
| CAT-6 | 63.2 | 99.3 |
| CAT-7 | 67.3 | 98.5 |
| CAT-8 | 94.2 | 99.1 |
| CAT-9 | 92.7 | 98.4 |
| CAT-10 | 96.7 | 98.9 |
| CAT-11 | 95.8 | 97.9 |
| CAT-12 | 92.9 | 98.5 |
| CAT-13 | 91.8 | 98.6 |
| CAT-14 | 95.1 | 98.3 |
| CAT-15 | 93.2 | 97.9 |
| CAT-16 | 85.6 | 99.2 |
| CAT-17 | 84.7 | 98.9 |
Claims (8)
1. a kind of preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that the following steps are included:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, the two of 20-60 nm of resin liquid mass fraction 3-10% be added
One or more of silica or nano aluminium oxide, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time is obtained
To sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is placed in 36-48 h of agitator treating in the beaker for filling HF solution, etches away the titanium dioxide retained in sample
Silicon or nano aluminium oxide are dried after being then washed with deionized water to neutrality to get target product is arrived, and wherein HF dosage is addition two
10-20 times of silica or nano aluminium oxide mole.
2. a kind of preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that the following steps are included:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
Ionized water, be added 20-60 nm of mixed resin liquid mass fraction 3-10% silica or one of nano aluminium oxide or
It is several, precuring is heated at 80-110 DEG C, 0.5-1 h of pre-cure time obtains sample A, wherein liquid phenolic resin and trimerization
The mass ratio of cyanamide formaldehyde resin liquid is 0.1-1；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is placed in 36-48 h of agitator treating in the beaker for filling HF solution, etches away the titanium dioxide retained in sample
Silicon or nano aluminium oxide are dried after being then washed with deionized water to neutrality to get target product is arrived, and wherein HF dosage is addition two
10-20 times of silica or nano aluminium oxide mole.
3. a kind of preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that the following steps are included:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, sodium chloride, the carbonic acid of resin liquid mass fraction 3-10% be added
One or more of sodium or ammonium carbonate, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time obtains sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, sodium carbonate or carbonic acid
Sample is filtered dry after separating to get target product is arrived later by ammonium.
4. a kind of preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that the following steps are included:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
One or more of sodium chloride, sodium carbonate or the ammonium carbonate of mixed resin liquid mass fraction 3-10% is added, 80-in ionized water
Precuring is heated at 110 DEG C, 0.5-1 h of pre-cure time obtains sample A, wherein liquid phenolic resin and melamino-formaldehyde tree
The mass ratio of rouge liquid is 0.1-1；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one or more of Ar；
4) sample C is sufficiently washed with excessive deionized water to remove the sodium chloride retained in sample, sodium carbonate or carbonic acid
Sample is filtered dry after separating to get target product is arrived later by ammonium.
5. a kind of preparation method for the nitrogen-doped carbon material that can be used for acetylene hydrochlorination reaction, it is characterised in that including following step
It is rapid:
1) resin liquid mass fraction 0.5-1% is added in the melamine resin liquid for weighing certain mass under stirring
Ammonium chloride, add the deionized water of one times of resin liquid quality, the polyethylene glycol of resin liquid mass fraction 20-50% be added
400, one of macrogol or polyvinyl butyral or several, heat precuring at 80-110 DEG C, when precuring
Between 0.5-1 h, obtain sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then with the heating rate of 1-5 DEG C/min be raised to 500-900 DEG C of maintenance at least 3 h to get
To nitrogen-doped carbon material, wherein inert atmosphere is He, N2, one of Ar.
6. a kind of preparation method of the nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that the following steps are included:
1) it carries out liquid phenolic resin and melamine resin liquid to be mixed to get mixing by a certain percentage under stirring
Then resin liquid is added the ammonium chloride of mixed resin liquid mass fraction 0.5-1%, adds going for one times of mixed resin liquid quality
Ionized water is added in polyethylene glycol 400, macrogol or the polyvinyl butyral of mixed resin liquid mass fraction 20-50%
One or more, heat precuring at 80-110 DEG C, and 0.5-1 h of pre-cure time obtains sample A；
2) sample A is placed in 120-125 DEG C of baking ovens and is solidified, 4-6 h of curing time obtains sample B；
3) sample B is placed in tube furnace, passes to inert atmosphere and is roasted, be first raised to the heating rate of 5-10 DEG C/min
300-400 DEG C of maintenance at least 1 h, then 500-900 DEG C of maintenance at least 3 h are raised to the heating rate of 1-5 DEG C/min, it obtains
Sample C, wherein inert atmosphere is He, N2, one of Ar；
4) sample C is mixed with potassium hydroxide powder, mixture is transferred in tube furnace after being fully ground, in the lazy of flowing
Property gas atmosphere under, 180-200 DEG C and constant temperature at least 1 h are warming up to the heating rate of 5 ~ 10 DEG C/min, then with 1-5 DEG C/
The heating rate of min is warming up to 450-1200 DEG C and is activated at least 2 h, naturally cold under inert atmosphere purging later
But to room temperature, sample D is obtained, wherein the mass ratio of sample C and potassium hydroxide is 0.5-3；
5) sample D is sufficiently washed to neutrality with excessive deionized water, sample is filtered dry after separating to get arriving later
Nitrogen-doped carbon material.
7. a kind of nitrogen-doped carbon material for acetylene hydrochlorination reaction, it is characterised in that use any one of claim 1-6
The preparation method is made.
8. a kind of application method of nitrogen-doped carbon material as claimed in claim 7, it is characterised in that specifically includes the following steps:
1) nitrogen-doped carbon material is placed in fixed bed reactors, 160-260 DEG C is warming up under the inert gas of flowing simultaneously
Constant temperature at least 1 h, wherein the volume space velocity of inert gas is 15-45 h–1；
2) inert gas is closed, is switched to the hydrogen chloride gas of flowing, and constant temperature at least 1 h, wherein the volume space velocity of hydrogen chloride
For 15-45 h–1；
3) it is passed through acetylene gas, acetylene volume space velocity is 15-45 h–1, the molar ratio of hydrogen chloride and acetylene is 1.05-1.3:1；
4) use temperature range of nitrogen-doped carbon material is 160-260 DEG C；
5) qualitative and quantitative analysis is carried out to the gas after reaction using gas-chromatography.
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| CN111346662A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst |
| CN111346663A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Amino resin modified nitrogen-doped activated carbon catalyst and preparation method and application thereof |
| CN111359649A (en) * | 2020-04-16 | 2020-07-03 | 郑州大学 | One-step method for preparing shell-based nitrogen-doped activated carbon catalyst, product and application |
| CN112657524A (en) * | 2019-10-15 | 2021-04-16 | 新疆大学 | Non-mercury catalyst for preparing vinyl chloride by hydrochlorinating acetylene and preparation and use methods thereof |
| CN116196965A (en) * | 2023-04-25 | 2023-06-02 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
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| CN111346662A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst |
| CN111346663A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Amino resin modified nitrogen-doped activated carbon catalyst and preparation method and application thereof |
| CN111359649A (en) * | 2020-04-16 | 2020-07-03 | 郑州大学 | One-step method for preparing shell-based nitrogen-doped activated carbon catalyst, product and application |
| CN111346662B (en) * | 2020-04-16 | 2023-03-31 | 郑州大学 | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst |
| CN111346663B (en) * | 2020-04-16 | 2023-06-27 | 郑州大学 | Amino resin modified nitrogen-doped active carbon catalyst and preparation method and application thereof |
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