CN108160095A - A kind of preparation method and application of the catalyst without mercury of acetylene hydrochlorination reaction - Google Patents
A kind of preparation method and application of the catalyst without mercury of acetylene hydrochlorination reaction Download PDFInfo
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- CN108160095A CN108160095A CN201711367823.8A CN201711367823A CN108160095A CN 108160095 A CN108160095 A CN 108160095A CN 201711367823 A CN201711367823 A CN 201711367823A CN 108160095 A CN108160095 A CN 108160095A
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- 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
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- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
The present invention relates to a kind of catalyst preparation technologies, more particularly to catalyst without mercury and preparation method of the acetylene hydrochlorination reaction without metallic element.The catalyst mixes carbon nanotube including nitrogen（NCNT）And carbonitride（C3N4）, the NCNT accounts for 0wt%~20wt% of catalyst gross mass, and the carbonitride accounts for 80wt%~100wt% of catalyst gross mass, NCNT and C in the catalyst3N4It is alternate to form close heterojunction structure.Metallic element is free of in the catalyst of the present invention, raw material for it is simple, be easy to get, cheap rich in C, N material, prepare the catalyst performance stabilised of gained, and catalytic activity and selectivity are higher, the catalyst is to can replace high toxicity mercury catalyst, and other are rich in the catalyst without mercury of metallic element, are applied to acetylene hydrochlorination industrial processes.
Description
Technical field
The invention belongs to preparing chloroethylene by acetylene hydrochlorination catalyst and its technology of preparing and applications, are more particularly to used for
The mercury-free of acetylene hydrochlorination reaction and the catalyst without mercury without metallic element and its application.
Background technology
It is main that vinyl chloride monomer is still prepared using calcium carbide-acetylene process route due to the national conditions of the few oil of the more coals of China, it should
Process, as catalyst, is synthesized using mercury chloride/activated carbon catalyst using fixed bed reactors.Whole world PVC productions in 2013
It measures as 50.9 Mta-1, China accounts for 41%.As global maximum PVC producing countries, mercury catalyst is largely used, but due to fixation
Bed reactor heat transfer is slower, easily forms the heat spot that temperature is more than 200 DEG C, accelerates the loss of volatile mercury in catalyst, according to
Estimation production 1.0tPVC, consumes about 1.02-1.41Kg mercury catalysts (HgCl2Content:10-12wt%), and the HgCl more than 25%2
It is discharged into environment, is not recycled.With the deterioration of environment, to the limited of the threat of human health and mercury resource
Property, United Nations Environment Programme has passed through the international convention for being intended to that mercury emissions are controlled and reduced in global range《Minamata pact》.
The catalyst without mercury used at present is mostly metal-based catalyst, however the preparation energy consumption of catalyst is higher, loss of active component
Rapidly, catalyst inactivation is fast, and commercial Application difficulty is larger.The present invention proposes that a kind of activity is higher, and manufacturing cost is low, stability
The good catalyst without mercury and preparation method without metallic element.
Invention content
The object of the present invention is to provide a kind of catalyst without mercury of acetylene hydrochlorination reaction（NCNT/C3N4）, the catalyst
It is the C that layered mesoporous structure is loaded to by NCNT3N4On be combined, the catalyst activity is higher, and manufacturing cost is low, stability
Well and without metallic element.
In order to achieve the above object, the present invention uses following technical scheme：According to NCNT and C3N4Percentage, will be a certain amount of
The NCNT of the activation and C of activation3N4It is dispersed in the mixed solution of 20ml ethyl alcohol and 30ml concentrated hydrochloric acids, in 70 DEG C of constant temperature, stirring is anti-
Answer 4h.
The catalyst without mercury（NCNT/C3N4）Preparation method is：
1）, prepare Fe-Ni layered metal hydroxides：By a certain amount of Mg (NO3)2∙6H2O,Al(NO3)3∙9H2O,Fe(NO3)3
∙9H2O,Ni(NO3)2∙6H2O, which is dissolved in respectively in 100mL distilled water, is made into mixing salt solution（C(Mg):C(Al):C(Fe:)C(Ni)
=1:1:1:2,C(Mg)+C(Al)+C(Fe:)+C(Ni)=2molL-1）, take NaOH and Na2CO3It is dissolved in 100mL distilled water, so
Above-mentioned alkaline solution is poured into mixing salt solution afterwards, is stirred evenly, is put into reaction kettle, 200 DEG C keep the temperature for 24 hours, after cooling, from
The heart, washing, 70 DEG C of vacuum drying 8h；
2）, prepare and activation NCNT：5gFe-Ni layered metal hydroxides are catalyst precursor, and ethylene is as carbon source, acetonitrile
As nitrogen source, argon gas and hydrogen calcine 4h by chemical vapor deposition method in 750 DEG C, obtain NCNT as protection gas；
3）, prepare and activation C3N4：Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is
Reactant, self-assembling reaction generates meso-g-C in ethanol solution under certain temperature3N4。
4）, by 0wt%~20wt% activation NCNT and 80wt%~100wt% activation C3N4Be dispersed in 20ml ethyl alcohol and
In the mixed solution of 30ml concentrated hydrochloric acids；In 70 DEG C of constant temperature, 4h is stirred to react to get catalyst without mercury（NCNT/C3N4）.
Utilize 5%NCNT/95% C3N4Catalyzing acetylene hydrogen chloride synthesizing ethylene, by 0.3g C3N4It is put into quartz ampoule, in
180 DEG C, 12sccmHCl activation 15min, in C2H2With HCl flow-rate ratio Q (C2H2/HCl)=1:1.3, gas hourly space velocity
180h-1, 180 DEG C of hour reaction 120min of temperature, conversion of alkyne 12%, selective acetylene 97%.
In above-mentioned preparation method, step 2）It is middle that obtained head product is dispersed in 8.0molL-112h in HCl is centrifuged,
Water washing is distilled, by obtained substance redisperse to 8.0molL-112h in HCl is centrifuged, and distills water washing；It then will production
Object is distributed to 6.0molL-1In HF solution, 1h is stirred, detaches, be filtered, washed, 70 DEG C of dry 12h；
In above-mentioned preparation method, step 2）Middle NCNT activation methods are：A certain amount of NCNT is dispersed in 10molL-1HNO3Solution
In, handle 8h in 0 DEG C of water bath with thermostatic control；
In above-mentioned preparation method, step 3）Middle synthesis C3N4Reaction temperature for 230 DEG C, reaction time 48h；
In above-mentioned preparation method, the NCNT and the C of activation that preferably activate3N4Dosage be respectively 15wt% and 85wt%；
Beneficial effects of the present invention are：Not mercurous and other metallic elements in the catalyst of the present invention, catalyst is by cheap and easy to get
C, N element composition, the cost for reducing catalyst of high degree, the catalyst stability of preparation is good, and catalytic activity is high, choosing
Selecting property is high, which can replace high toxicity mercury catalyst and other catalyst without mercury containing metallic element, be applied to second
In the production engineering of alkynes preparing vinyl chloride by hydrochlorination.
Specific embodiment
With reference to example, the present invention is described in more detail, but protection scope of the present invention is not limited only to these implementations
Example.
Embodiment 1
Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is reactant, in 230 DEG C of ethyl alcohol
Self-assembling reaction 48h in solution generates meso-g-C3N4。
Utilize C3N4Catalyzing acetylene hydrogen chloride synthesizing ethylene, by 0.3gC3N4It is put into quartz ampoule, in 180 DEG C,
12sccmHCl activates 15min, in C2H2With HCl flow-rate ratio Q (C2H2/HCl)=1:1.3, gas hourly space velocity 180h-1, temperature
180 DEG C of hour reaction 120min of degree, conversion of alkyne 0%, selective acetylene 0%.
Embodiment 2
5gFe-Ni layered metal hydroxides are catalyst precursor, and ethylene is as carbon source, and acetonitrile is as nitrogen source, argon gas and hydrogen
Gas calcines 4h by chemical vapor deposition method in 750 DEG C, obtains NCNT, the head product product that will be obtained divides as protection gas
It is dispersed in 8.0molL-112h in HCl is centrifuged, and water washing is distilled, by obtained substance redisperse to 8.0molL-1In HCl
12h is centrifuged, and distills water washing；Then product is distributed to 6.0molL-1In HF solution, 1h is stirred, detaches, filter, wash
It washs, 70 DEG C of dry 12h；A certain amount of NCNT is dispersed in 10molL-1HNO38h is handled in solution, in 0 DEG C of water bath with thermostatic control to obtain
The NCNT of activation.
Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is reactant, in 230 DEG C
Self-assembling reaction 48h in ethanol solution generates meso-g-C3N4。
According to CNT and C3N4Percentage for 5wt% and 95wt%, by the NCNT and C of a certain amount of activation3N4It is dispersed in 20ml
In ethyl alcohol and 30ml concentrated hydrochloric acid solutions, in 70 DEG C of constant temperature, it is stirred to react 4h.
Utilize 5%NCNT/95% C3N4Catalyzing acetylene hydrogen chloride synthesizing ethylene, by 0.3g C3N4It is put into quartz ampoule, in
180 DEG C, 12sccmHCl activation 15min, in C2H2With HCl flow-rate ratio Q (C2H2/HCl)=1:1.3, gas hourly space velocity
180h-1, 180 DEG C of hour reaction 120min of temperature, conversion of alkyne 12%, selective acetylene 97%.
Embodiment 3
5gFe-Ni layered metal hydroxides are catalyst precursor, and ethylene is as carbon source, and acetonitrile is as nitrogen source, argon gas and hydrogen
Gas calcines 4h by chemical vapor deposition method in 750 DEG C, obtains NCNT, the head product product that will be obtained divides as protection gas
It is dispersed in 8.0molL-112h in HCl is centrifuged, and water washing is distilled, by obtained substance redisperse to 8.0molL-1In HCl
12h is centrifuged, and distills water washing；Then product is distributed to 6.0molL-1In HF solution, 1h is stirred, detaches, filter, wash
It washs, 70 DEG C of dry 12h；A certain amount of NCNT is dispersed in 10molL-18h is handled in HNO3 solution, in 0 DEG C of water bath with thermostatic control to obtain
The NCNT of activation.
Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is reactant, in 230 DEG C
Self-assembling reaction 48h in ethanol solution generates meso-g-C3N4。
According to CNT and C3N4Percentage for 15wt% and 85wt%, by the NCNT and C of a certain amount of activation3N4It is dispersed in 20ml
In ethyl alcohol and 30ml concentrated hydrochloric acid solutions, in 70 DEG C of constant temperature, it is stirred to react 4h.
Utilize 15%NCNT/85% C3N4Catalyzing acetylene hydrogen chloride synthesizing ethylene, by 0.3g C3N4It is put into quartz ampoule, in
180 DEG C, 12sccmHCl activation 15min, in C2H2With HCl flow-rate ratio Q (C2H2/HCl)=1:1.3, gas hourly space velocity
180h-1, 180 DEG C of hour reaction 120min of temperature, conversion of alkyne 61%, selective acetylene 97%.
Embodiment 4
5gFe-Ni layered metal hydroxides are catalyst precursor, and ethylene is as carbon source, and acetonitrile is as nitrogen source, argon gas and hydrogen
Gas calcines 4h by chemical vapor deposition method in 750 DEG C, obtains NCNT, the head product product that will be obtained divides as protection gas
It is dispersed in 8.0molL-112h in HCl is centrifuged, and water washing is distilled, by obtained substance redisperse to 8.0molL-1In HCl
12h is centrifuged, and distills water washing.Then product is distributed to 6.0molL-1In HF solution, 1h is stirred, detaches, filter, wash
It washs, 70 DEG C of dry 12h；A certain amount of NCNT is dispersed in 10molL-1HNO38h is handled in solution, in 0 DEG C of water bath with thermostatic control to obtain
The NCNT of activation.
Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is reactant, in 230 DEG C
Self-assembling reaction 48h in ethanol solution generates meso-g-C3N4。
According to CNT and C3N4Percentage for 20wt% and 80wt%, by the NCNT and C of a certain amount of activation3N4It is dispersed in 20ml
In ethyl alcohol and 30ml concentrated hydrochloric acid solutions, in 70 DEG C of constant temperature, it is stirred to react 4h.
Utilize 20%NCNT/80% C3N4Catalyzing acetylene hydrogen chloride synthesizing ethylene, by 0.3gC3N4It is put into quartz ampoule, in
180 DEG C, 12sccmHCl activation 15min, in C2H2With HCl flow-rate ratio Q (C2H2/HCl)=1:1.3, gas hourly space velocity
180h-1, 180 DEG C of hour reaction 120min of temperature, conversion of alkyne 42%, selective acetylene 97%.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (6)
1. the preparation method of the catalyst without mercury of a kind of acetylene hydrochlorination reaction, which is characterized in that preparation method is：
1）, prepare Fe-Ni layered metal hydroxides：By a certain amount of Mg (NO3)2∙6H2O,Al(NO3)3∙9H2O,Fe(NO3)3∙
9H2O,Ni(NO3)2∙6H2O, which is dissolved in respectively in 100mL distilled water, is made into mixing salt solution（C(Mg):C(Al):C(Fe:)C(Ni)=
1:1:1:2,C(Mg)+C(Al)+C(Fe:)+C(Ni)=2molL-1）, take NaOH and Na2CO3It is dissolved in 100mL distilled water, then
Above-mentioned alkaline solution to be poured into mixing salt solution, is stirred evenly, is put into reaction kettle, 200 DEG C of heat preservations for 24 hours, after cooling, centrifuge,
Washing, 70 DEG C of vacuum drying 8h；
2）, prepare and activation NCNT：5gFe-Ni layered metal hydroxides are catalyst precursor, and ethylene is as carbon source, acetonitrile
As nitrogen source, argon gas and hydrogen calcine 4h by chemical vapor deposition method in 750 DEG C, obtain NCNT as protection gas；
3）, prepare and activation C3N4：Using -3 methylimidazolium chloride of 1- octyl groups ([Bmim] Cl) as template, melamine is
Reactant, self-assembling reaction generates meso-g-C in ethanol solution under certain temperature3N4 ；
4）, by 0wt%~20wt% activation NCNT and 80wt%~100wt% activation C3N4It is dispersed in 20ml ethyl alcohol and 30ml
In the mixed solution of concentrated hydrochloric acid；In 70 DEG C of constant temperature, 4h is stirred to react to get catalyst without mercury（NCNT/C3N4）.
2. the preparation method of the catalyst without mercury of acetylene hydrochlorination reaction according to claim 1, which is characterized in that step
2）It is middle that obtained head product is dispersed in 8.0molL-112h in HCl is centrifuged, and distills water washing, obtained substance is divided again
It is scattered to 8.0molL-112h in HCl is centrifuged, and distills water washing；Then product is distributed to 6.0molL-1In HF solution, stir
1h is mixed, detaches, be filtered, washed, 70 DEG C of dry 12h.
3. the preparation method of the catalyst without mercury of acetylene hydrochlorination reaction described in claim 1, which is characterized in that step 2）In
NCNT activation methods are：A certain amount of NCNT is dispersed in 10molL-1HNO3In solution, 8h is handled in 0 DEG C of water bath with thermostatic control.
4. the preparation method of the catalyst without mercury of acetylene hydrochlorination reaction according to claim 1, which is characterized in that step
3）Middle synthesis C3N4Reaction temperature for 230 DEG C, reaction time 48h.
5. the preparation method of the catalyst without mercury of acetylene hydrochlorination reaction according to claim 1, which is characterized in that activation
NCNT and activation C3N4Dosage be respectively 15wt% and 85wt%.
6. a kind of application of the catalyst without mercury of acetylene hydrochlorination reaction, utilizes 5%NCNT/95% C3N4Catalyzing acetylene hydrogen chloride is closed
Into ethylene, by 0.3g C3N4It is put into quartz ampoule, in 180 DEG C, 12sccmHCl activates 15min, in C2H2With HCl flow-rate ratios Q
(C2H2/HCl)=1:1.3, gas hourly space velocity 180h-1, temperature 180 DEG C of hours reaction 120min, conversion of alkyne is
12%, selective acetylene 97%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647523A (en) * | 2018-12-25 | 2019-04-19 | 南开大学 | A kind of preparation method and its application method of the non-metal catalyst for fixed bed preparing chloroethylene by acetylene hydrochlorination |
| CN113649057A (en) * | 2021-09-14 | 2021-11-16 | 浙江师范大学 | Platinum catalyst for preparing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof |
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| CN102631942A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Composite metal salt catalyst for hydrochlorination reaction of acetylene |
| CN103381369A (en) * | 2013-07-10 | 2013-11-06 | 清华大学 | Nitrogen doped carbon material loaded catalyst |
| CN103894208A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof |
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2017
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Patent Citations (3)
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| CN102631942A (en) * | 2012-04-17 | 2012-08-15 | 清华大学 | Composite metal salt catalyst for hydrochlorination reaction of acetylene |
| CN103894208A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647523A (en) * | 2018-12-25 | 2019-04-19 | 南开大学 | A kind of preparation method and its application method of the non-metal catalyst for fixed bed preparing chloroethylene by acetylene hydrochlorination |
| CN109647523B (en) * | 2018-12-25 | 2021-10-29 | 南开大学 | Preparation method and use method of metal-free catalyst for preparing vinyl chloride by hydrochlorinating acetylene in fixed bed |
| CN113649057A (en) * | 2021-09-14 | 2021-11-16 | 浙江师范大学 | Platinum catalyst for preparing vinyl chloride by hydrochlorinating acetylene and preparation method and application thereof |
| CN113649057B (en) * | 2021-09-14 | 2023-10-03 | 浙江师范大学 | Platinum catalyst for preparing chloroethylene by hydrochlorination of acetylene as well as preparation method and application thereof |
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