CN108187721A - The preparation method and its application method of a kind of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene - Google Patents

The preparation method and its application method of a kind of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene Download PDF

Info

Publication number
CN108187721A
CN108187721A CN201810022904.2A CN201810022904A CN108187721A CN 108187721 A CN108187721 A CN 108187721A CN 201810022904 A CN201810022904 A CN 201810022904A CN 108187721 A CN108187721 A CN 108187721A
Authority
CN
China
Prior art keywords
sample
nitrogen
temperature
powder
doped carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810022904.2A
Other languages
Chinese (zh)
Other versions
CN108187721B (en
Inventor
李伟
乔贤亮
关庆鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nankai University
Original Assignee
Nankai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nankai University filed Critical Nankai University
Priority to CN201810022904.2A priority Critical patent/CN108187721B/en
Publication of CN108187721A publication Critical patent/CN108187721A/en
Application granted granted Critical
Publication of CN108187721B publication Critical patent/CN108187721B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of preparation methods and its application method of the nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, belong to field of material synthesis technology.This method uses the silkworm cocoon of natural high nitrogen content as presoma, and nitrogen-doped carbon non-metal catalyst is obtained by being carbonized and activating.The method have the characteristics that catalyst is presoma by the biomass of natural high nitrogen content, step is introduced without complicated nitrogen, it is easy to operate, it is cost-effective, and after the carbonization and activation for passing through preparation process, nitrogen can be evenly distributed in catalyst.The present invention develops a kind of Novel non-metal catalyst and proposes technology of preparing, which is applied in the reaction of fixed bed preparing chloroethylene by acetylene hydrochlorination, has certain catalytic activity and selectivity.

Description

A kind of nitrogen-doped carbon for fixed bed preparing vinyl chloride by hydrochlorination of acetylene is catalyzed The preparation method and its application method of agent
Technical field
The present invention proposes a kind of preparation of the nitrogen-doped carbon catalyst for fixed bed acetylene hydrochlorination reaction preparing chloroethylene Method and its application method, belong to field of material synthesis technology.This method uses the silk cocoon of natural high nitrogen content using this method Shell is presoma, and nitrogen-doped carbon catalyst is obtained by being carbonized and activating in inert gas.The catalyst is applied to fix In the reaction of bed preparing chloroethylene by acetylene hydrochlorination, there is certain catalytic activity and selectivity.
Background technology
Polyvinyl chloride is China first, second-biggest-in-the-world resins for universal use material, and application field is very extensive, and vinyl chloride is to close Into the principal monomer of polyvinyl chloride.In China, mainly using acetylene as raw material, reaction is mainly born with activated carbon for the production of vinyl chloride The mercury chloride of load is as catalyst.But the catalyst has the following disadvantages：During the reaction, the mercurous ingredient in catalyst Readily volatilized loss, seriously pollutes environment, threatens the health of the mankind.To realize the high-efficiency cleaning production of vinyl chloride, research and produce Novel mercury-free catalyst substitutes extremely urgent containing mercury catalyst.
At present, the research of catalyst without mercury is mainly based on noble metal.Huctings et al. has studied numerous metal chlorinations Performance of the object in acetylene hydrochlorination reaction, and speculate should there is optimal catalytic performance containing Au catalyst.Later, gold catalysis Agent, which receives, widely to be studied and obtains important breakthrough.It is contemplated that the cost problem of commercial Application, Au catalyst are high Its further genralrlization of price limit and application.Recently, non-metal catalyst especially nitrogen-doped carbon material, which is increasingly becoming, grinds The hot spot studied carefully.G-C prepared by Dai Bin professors et al. research3N4/ AC catalyst is shown good in acetylene hydrochlorination reaction Catalytic activity；SiC@C-N and h-BN catalyst prepared by the packet letter and academician of Dalian chemistry and physics Institute et al. research Excellent catalytic performance is shown in the reaction, but the preparation process of catalyst is more, condition requires more harshness, is unfavorable for Mass production.
Patent CN201310518594.0 and CN201410532264.1 disclose a kind of non-metal catalyst for solid Fixed bed acetylene hydrochlorination reacts, and the preparation of catalyst is mainly used activity component impregnation in the carriers such as activated carbon and molecular sieve On, it differs greatly in terms of catalyst formulation with preparation method with this patent.Catalyst described in this patent is by natural high nitrogen content Biomass is presoma, avoids complicated nitrogen in the synthesis process and introduces step, easy to operate, easy mass production.
Invention content
It is an object of the invention to propose a kind of nitrogen-doped carbon catalysis for fixed bed preparing chloroethylene by acetylene hydrochlorination The preparation method and its application method of agent, this method is presoma by the biomass silkworm cocoon of natural high nitrogen content, without complexity Nitrogen introduce step, it is easy to operate, it is cost-effective, and after the carbonization and activation for passing through preparation process, nitrogen can be equal It is distributed in the catalyst, which is applied in the reaction of fixed bed preparing chloroethylene by acetylene hydrochlorination evenly, have one Fixed catalytic activity and selectivity.
The specific technical solution of the present invention is as described below：
Scheme 1：A kind of preparation method of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, Characterized by the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the air atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, wherein volume of air air speed is 180 h-1, the pre- target temperature that is carbonized is 250 ~ 350 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake is dried at 100 ~ 120 DEG C, obtain nitrogen-doped carbon catalysis Agent.
Scheme 2：A kind of preparation side of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene Method, it is characterised in that include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the air atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, wherein volume of air air speed is 180 h-1, the pre- target temperature that is carbonized is 250 ~ 350 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, gained filter cake at 100 ~ 120 DEG C is dried and obtains sample C；
4) sample C with the KOH powder of certain mass is mixed, mixture is transferred in tube furnace after being fully ground, flowed Inert gas atmosphere under, 180 ~ 200 DEG C and constant temperature at least 1 h, then with 1 ~ 5 are warming up to the heating rate of 5 ~ 10 DEG C/min DEG C/heating rate of min is continuously heating to target temperature and carries out activation process, and constant temperature at least 2 h under target temperature, later The cooled to room temperature under inert atmosphere purging, the mass ratio for obtaining sample D, wherein KOH and sample C are 1 ~ 4, inert gas For N2, one kind in He or Ar, activation target temperature is 450 ~ 1200 DEG C；
5) sample D is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 100 ~ 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst by water washing.
Scheme 3：A kind of preparation side of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene Method, it is characterised in that include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the inert atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, and wherein inert gas is N2, He Or one kind in Ar, volume space velocity are 180 h-1, the pre- target temperature that is carbonized is 250 ~ 450 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake is dried at 100 ~ 120 DEG C, obtain nitrogen-doped carbon catalysis Agent.
Scheme 4：A kind of preparation side of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene Method, it is characterised in that include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the inert atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, and wherein inert gas is N2, He Or one kind in Ar, volume space velocity 180h-1, the pre- target temperature that is carbonized is 250 ~ 450 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake at 100 ~ 120 DEG C is dried and obtains sample C；
4) sample C with the KOH powder of certain mass is mixed, mixture is transferred in tube furnace after being fully ground, flowed Inert gas atmosphere under, 180 ~ 200 DEG C and constant temperature at least 1 h, then with 1 ~ 5 are warming up to the heating rate of 5 ~ 10 DEG C/min DEG C/heating rate of min is continuously heating to target temperature and carries out activation process, and constant temperature at least 2 h under target temperature, later The cooled to room temperature under inert atmosphere purging, the mass ratio for obtaining sample D, wherein KOH and sample C are 1 ~ 4, inert gas For N2, one kind in He or Ar, activation target temperature is 450 ~ 1200 DEG C；
5) sample D is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 100 ~ 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst by water washing.
Scheme 5：A kind of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, feature exist In 1 ~ 4 any one of them preparation method of operational version is made.
Scheme 6：A kind of application method of nitrogen-doped carbon catalyst described in scheme 5, feature specifically include following steps：
1) 1mL catalyst is taken to be placed in fixed bed reactors, 160 ~ 260 DEG C and constant temperature are warming up under the inert gas of flowing extremely Few 1 h, the wherein volume space velocity of inert gas are 15 ~ 45 h-1；
2) inert gas is closed, is switched to the hydrogen chloride gas of flowing, and constant temperature at least 1h, the volume space velocity of wherein hydrogen chloride are 15~45 h-1；
3) acetylene gas is passed through, acetylene volume space velocity is 15 ~ 45h-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 catalyst of existing preparing vinyl chloride by hydrochlorination of acetylene it is main based on metallic catalyst, no metal is urged Active specy is mostly impregnated on the carriers such as activated carbon, the molecular sieve of Large ratio surface or on in-situ deposition to SiC carriers by agent, Complex steps, experimental condition requirement are harsh.The present invention has following significantly innovation compared with the prior art：
(1) present invention has synthesized a kind of novel nitrogen-doped carbon for fixed bed preparing vinyl chloride by hydrochlorination of acetylene and has been catalyzed Agent has certain catalytic activity and stability, part is expected to instead of traditional metallic catalyst, especially containing mercury catalyst It uses, reduces the pollution to environment；
(2) catalyst is presoma by the biomass silkworm cocoon of natural high nitrogen content, effectively prevents complicated external nitrogen member Element doping step, enormously simplifies the preparation flow of catalyst, and can prepare in batches；
(3) the catalyst precursor silkworm cocoon is made of the silk fiber albumen of a large amount of micron-scales, itself is had certain Space structure, by subsequent carbonization and activation process, can realize nitrogen being uniformly distributed, and be conducive in the catalyst The mass transfer of catalytic process and heat transfer improve catalytic efficiency；
(4) in view of China is there are excessive biological material, the design and preparation of the catalyst can be efficiently use it is discarded Biological material provides thinking and reference, this also complies with the demand for development of green chemistry chemical technology.
Description of the drawings
Fig. 1：The SEM figures of nitrogen-doped carbon catalyst prepared by embodiment 4.
Fig. 2：The SEM figures of nitrogen-doped carbon catalyst prepared by embodiment 5.
Specific embodiment
To better illustrate this patent, following embodiment is now listed.Following embodiment is to make industry personnel 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) silkworm cocoon of 10g or so is shredded, immersion more than 6h in 50 DEG C of deionized water is placed in, to remove the impurity in silk cocoon And soluble inorganic salt, sample is filtered later, is detached, and is washed with deionized 5 times or more, is then dried at 100 DEG C Obtain sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 250 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 250 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1, 250 DEG C Constant temperature is in order to avoid the excessive oxidation of material surface group under lower temperature；
3) sample B grind into powder is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, And be washed with deionized to neutrality, and gained filter cake is dried at 120 DEG C, obtain nitrogen-doped carbon catalyst CAT-1.
Embodiment 2
1) silkworm cocoon of 10g or so is shredded, immersion more than 6h in 50 DEG C of deionized water is placed in, to remove the impurity in silk cocoon And soluble inorganic salt, sample is filtered later, is detached, and is washed with deionized 5 times or more, is then dried at 100 DEG C Obtain sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 350 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 350 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1, 350 DEG C Constant temperature is in order to avoid the excessive oxidation of material surface group under lower temperature；
3) sample B grind into powder is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake is dried at 120 DEG C, obtain nitrogen-doped carbon catalyst CAT- 2。
Embodiment 3
1) silkworm cocoon of 10g or so is shredded, is placed in 50 DEG C of deionized water and impregnates 6h, to remove the impurity in silk cocoon and can Sample is filtered, detached by soluble inorganic salt later, and is washed with deionized 5 times or more, is then dried and is obtained at 100 DEG C Sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 350 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 350 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and It is washed with deionized to neutrality, gained filter cake at 120 DEG C is dried and obtains sample C；
4) 3g samples C with 3gKOH powder is mixed, mixture is transferred in tube furnace after being fully ground, in the N of flowing2Gas Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to, then continue to heat up with the heating rate of 5 DEG C/min with the heating rate of 5 DEG C/min Activation process, and 2 h of constant temperature at 450 DEG C are carried out to 450 DEG C, later in N2The lower cooled to room temperature of atmosphere purging, obtains To sample D, wherein N2Volume space velocity is 180 h-1；
5) sample D is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst CAT-3 by water washing.
Embodiment 4
1) silkworm cocoon of 10g or so is shredded, is placed in 50 DEG C of deionized water and impregnates 6h, to remove the impurity in silk cocoon and can Sample is filtered, detached by soluble inorganic salt later, and is washed with deionized 5 times or more, is then dried and is obtained at 100 DEG C Sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 350 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 350 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and It is washed with deionized to neutrality, gained filter cake at 120 DEG C is dried and obtains sample C；
4) 3g samples C with 3gKOH powder is mixed, mixture is transferred in tube furnace after being fully ground, in the N of flowing2Gas Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to, then continue to heat up with the heating rate of 5 DEG C/min with the heating rate of 5 DEG C/min Activation process, and 2 h of constant temperature at 500 DEG C are carried out to 500 DEG C, later in N2The lower cooled to room temperature of atmosphere purging, obtains To sample D, wherein N2Volume space velocity is 180 h-1；
5) sample D is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst CAT-4 by water washing.
Embodiment 5
1) silkworm cocoon of 10g or so is shredded, is placed in 50 DEG C of deionized water and impregnates 6h, to remove the impurity in silk cocoon and can Sample is filtered, detached by soluble inorganic salt later, and is washed with deionized 5 times or more, is then dried and is obtained at 100 DEG C Sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 350 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 350 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and It is washed with deionized to neutrality, gained filter cake at 120 DEG C is dried and obtains sample C；
4) 3g samples C with 3gKOH powder is mixed, mixture is transferred in tube furnace after being fully ground, in the N of flowing2Gas Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to, then continue to heat up with the heating rate of 5 DEG C/min with the heating rate of 5 DEG C/min Activation process, and 2 h of constant temperature at 800 DEG C are carried out to 800 DEG C, later in N2The lower cooled to room temperature of atmosphere purging, obtains To sample D, wherein N2Volume space velocity is 180 h-1；
5) sample D is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst CAT-5 by water washing.
Embodiment 6
1) silkworm cocoon of 10g or so is shredded, is placed in 50 DEG C of deionized water and impregnates 6h, to remove the impurity in silk cocoon and can Sample is filtered, detached by soluble inorganic salt later, and is washed with deionized 5 times or more, is then dried and is obtained at 100 DEG C Sample A；
2) sample A is placed in tube furnace, in the air atmosphere of flowing with the heating rate of 5 DEG C/min be warming up to 350 DEG C into The pre- carbonization treatment of row, and 40 min of constant temperature at 350 DEG C obtain sample B, and wherein volume of air air speed is 180 h-1；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and It is washed with deionized to neutrality, gained filter cake at 120 DEG C is dried and obtains sample C；
4) 3g samples C with 3gKOH powder is mixed, mixture is transferred in tube furnace after being fully ground, in the N of flowing2Gas Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to, then continue to heat up with the heating rate of 5 DEG C/min with the heating rate of 5 DEG C/min Activation process, and 2 h of constant temperature at 1200 DEG C are carried out to 1200 DEG C, later in N2The lower cooled to room temperature of atmosphere purging, Obtain sample D, wherein N2Volume space velocity is 180 h-1；
5) sample D is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst CAT-6 by water washing.
Embodiment 7
1) silkworm cocoon of 10g or so is shredded, immersion more than 6h in 50 DEG C of deionized water is placed in, to remove the impurity in silk cocoon And soluble inorganic salt, sample is filtered later, is detached, and is washed with deionized 5 times or more, is then dried at 100 DEG C Obtain sample A；
2) sample A is placed in tube furnace, 400 DEG C of progress is warming up to the heating rate of 5 DEG C/min in the Ar atmosphere of flowing Pre- carbonization treatment, and 40 min of constant temperature at 400 DEG C obtain sample B, and wherein Ar air speeds are 180 h-1；
3) sample B grind into powder is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, And be washed with deionized to neutrality, and gained filter cake is dried at 120 DEG C, obtain nitrogen-doped carbon catalyst CAT-7.
Embodiment 8
1) silkworm cocoon of 10g or so is shredded, immersion more than 6h in 50 DEG C of deionized water is placed in, to remove the impurity in silk cocoon And soluble inorganic salt, sample is filtered later, is detached, and is washed with deionized 5 times or more, is then dried at 100 DEG C Obtain sample A；
2) sample A is placed in tube furnace, 400 DEG C of progress is warming up to the heating rate of 5 DEG C/min in the Ar atmosphere of flowing Pre- carbonization treatment, and 40 min of constant temperature at 400 DEG C obtain sample B, and wherein Ar air speeds are 180 h-1；
3) sample B grind into powder is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, And it is washed with deionized to neutrality, and gained filter cake at 120 DEG C is dried and obtains sample C；
4) 3g samples C with 3gKOH powder is mixed, mixture is transferred in tube furnace after being fully ground, in the Ar gas of flowing Under atmosphere, 200 DEG C and 1 h of constant temperature are warming up to, then continue to heat up with the heating rate of 5 DEG C/min with the heating rate of 5 DEG C/min Activation process, and 2 h of constant temperature at 500 DEG C are carried out to 500 DEG C, the cooled to room temperature under Ar atmosphere purging, obtains later To sample D, wherein Ar volume space velocities are 180 h-1；
5) sample D is placed in 5% dilute hydrochloric acid solution, 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst CAT-8 by water washing.
Comparative example 1
Prepare NH3The sample activated in atmosphere, it is therefore intended that make comparisons with embodiment 3, understand NH3Processing is to catalyst activity It influences.
Preparation process is same as Example 3, only by step 4 " in the N of flowing2Under atmosphere, with the heating speed of 5 DEG C/min Rate is warming up to 200 DEG C and 1 h of constant temperature, then is continuously heating to 500 DEG C of progress activation process with the heating rate of 5 DEG C/min, and 2 h of constant temperature at 500 DEG C, later in N2The lower cooled to room temperature of atmosphere purging, obtains sample D, wherein N2Volume space velocity is 180 h-1" be changed to " in 10% NH of flowing3/N2Under atmosphere, 200 DEG C and constant temperature 1 are warming up to the heating rate of 5 DEG C/min H, then 500 DEG C of progress activation process, and 2 h of constant temperature at 500 DEG C are continuously heating to the heating rate of 5 DEG C/min, later In 10% NH3/N2The lower cooled to room temperature of atmosphere purging, finally by 10% NH3/N2It is changed to the N of flowing2Atmosphere continues to purge 2 h obtain sample D, wherein 10% NH3/N2And N2Volume space velocity is 180 h-1", gained catalyst number is CAT-9.
The evaluation procedure of catalyst and condition are：
1) 1mL catalyst is taken to be placed in fixed bed reactors, 200 DEG C are warming up under the inert gas of flowing and maintains 1 h, The volume space velocity of middle inert gas is 45 h-1；
2) inert gas is closed after, is switched to the hydrogen chloride gas of flowing, and maintain 1h, the volume space velocity of wherein hydrogen chloride is 45 h-1；
3) acetylene gas is passed through, acetylene volume space velocity is 40h-1, the molar ratio of hydrogen chloride and acetylene is 1.3:1.
Qualitative and quantitative analysis is carried out to the gas after reaction using gas-chromatography.It is primary every 1 h samplings, and use gas phase Chromatography product forms, and sampling analysis, the conversion of alkyne and chlorine of different nitrogen-doped carbon catalyst are carried out to react the point of 2 h It is as shown in the table for ethylene selectivity correction data：

Claims (6)

1. a kind of preparation method of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, feature It is to include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the air atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, wherein volume of air air speed is 180 h-1, the pre- target temperature that is carbonized is 250 ~ 350 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake is dried at 100 ~ 120 DEG C, obtain nitrogen-doped carbon catalysis Agent.
2. a kind of preparation method of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, feature It is to include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the air atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, wherein volume of air air speed is 180 h-1, the pre- target temperature that is carbonized is 250 ~ 350 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, gained filter cake at 100 ~ 120 DEG C is dried and obtains sample C；
4) sample C with the KOH powder of certain mass is mixed, mixture is transferred in tube furnace after being fully ground, flowed Inert gas atmosphere under, 180 ~ 200 DEG C and constant temperature at least 1 h, then with 1 ~ 5 are warming up to the heating rate of 5 ~ 10 DEG C/min DEG C/heating rate of min is continuously heating to target temperature and carries out activation process, and constant temperature at least 2 h under target temperature, later The cooled to room temperature under inert atmosphere purging, the mass ratio for obtaining sample D, wherein KOH and sample C are 1 ~ 4, inert gas For N2, one kind in He or Ar, activation target temperature is 450 ~ 1200 DEG C；
5) sample D is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 100 ~ 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst by water washing.
3. a kind of preparation method of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, feature It is to include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the inert atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, and wherein inert gas is N2, He Or one kind in Ar, volume space velocity are 180 h-1, the pre- target temperature that is carbonized is 250 ~ 450 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake is dried at 100 ~ 120 DEG C, obtain nitrogen-doped carbon catalysis Agent.
4. a kind of preparation method of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, feature It is to include the following steps：
1) silkworm cocoon of certain mass is shredded, is placed in 30 ~ 50 DEG C of deionized water and impregnates at least 6h, later take out sample Filter, separation, and be washed with deionized for several times, then drying obtains sample A at 80 ~ 100 DEG C；
2) sample A is placed in tube furnace, target is warming up to the heating rate of 5 ~ 10 DEG C/min in the inert atmosphere of flowing Temperature carries out pre- carbonization treatment, and constant temperature at least 30 min under target temperature, obtains sample B, and wherein inert gas is N2, He Or one kind in Ar, volume space velocity are 180 h-1, the pre- target temperature that is carbonized is 250 ~ 450 DEG C；
3) sample B grind into powder is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is divided From, and be washed with deionized to neutrality, and gained filter cake at 100 ~ 120 DEG C is dried and obtains sample C；
4) sample C with the KOH powder of certain mass is mixed, mixture is transferred in tube furnace after being fully ground, flowed Inert gas atmosphere under, 180 ~ 200 DEG C and constant temperature at least 1 h, then with 1 ~ 5 are warming up to the heating rate of 5 ~ 10 DEG C/min DEG C/heating rate of min is continuously heating to target temperature and carries out activation process, and constant temperature at least 2 h under target temperature, later The cooled to room temperature under inert atmosphere purging, the mass ratio for obtaining sample D, wherein KOH and sample C are 1 ~ 4, inert gas For N2, one kind in He or Ar, activation target temperature is 450 ~ 1200 DEG C；
5) sample D is placed in dilute hydrochloric acid solution, at least 12h is stirred at room temperature, powder is filtered later, is detached, and uses deionization Gained filter cake finally at 100 ~ 120 DEG C is dried to neutrality, obtains nitrogen-doped carbon material catalyst by water washing.
5. a kind of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene, which is characterized in that use Claim 1 ~ 4 any one of them preparation method is made.
6. a kind of application method of the nitrogen-doped carbon catalyst described in claim 5, feature specifically include following steps：
1) 1mL catalyst is taken to be placed in fixed bed reactors, 160 ~ 260 DEG C and constant temperature are warming up under the inert gas of flowing extremely Few 1 h, the wherein volume space velocity of inert gas are 15 ~ 45 h-1；
2) inert gas is closed, is switched to the hydrogen chloride gas of flowing, and constant temperature at least 1h, the volume space velocity of wherein hydrogen chloride are 15~45 h-1；
3) acetylene gas is passed through, acetylene volume space velocity is 15 ~ 45h-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.
CN201810022904.2A 2018-01-10 2018-01-10 Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination Active CN108187721B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810022904.2A CN108187721B (en) 2018-01-10 2018-01-10 Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810022904.2A CN108187721B (en) 2018-01-10 2018-01-10 Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination

Publications (2)

Publication Number Publication Date
CN108187721A true CN108187721A (en) 2018-06-22
CN108187721B CN108187721B (en) 2020-11-24

Family

ID=62588590

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810022904.2A Active CN108187721B (en) 2018-01-10 2018-01-10 Preparation method and use method of nitrogen-doped carbon catalyst for preparing vinyl chloride through fixed bed acetylene hydrochlorination

Country Status (1)

Country Link
CN (1) CN108187721B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109876840A (en) * 2018-12-25 2019-06-14 南开大学 A kind of preparation method and its application method of the non-metal catalyst for preparing vinyl chloride by hydrochlorination of acetylene
CN111454118A (en) * 2019-01-22 2020-07-28 中国科学院上海有机化学研究所 Method for preparing chloroethylene by reacting acetylene with dichloroethane
CN111454119A (en) * 2019-01-22 2020-07-28 中国科学院上海有机化学研究所 Method for preparing chloroethylene by reaction of acetylene and hydrogen chloride

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104525237A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis
CN104549401A (en) * 2013-10-28 2015-04-29 天津大学 Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application
CN105502383A (en) * 2015-11-30 2016-04-20 北京化工大学 Silkworm cocoon-based hierarchical porous carbon and preparation method thereof
CN106881135A (en) * 2015-12-16 2017-06-23 中国科学院大连化学物理研究所 A kind of carbon-based non-metal catalyst for acetylene method preparing chloroethylene, preparation method and renovation process
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104549401A (en) * 2013-10-28 2015-04-29 天津大学 Nonmetallic catalyst for acetylene hydrochlorination, as well as preparation method and application
CN104525237A (en) * 2015-01-07 2015-04-22 中国科学院上海高等研究院 Nitrogen-doped active carbon catalyzer and application thereof in chloroethylene synthesis
CN105502383A (en) * 2015-11-30 2016-04-20 北京化工大学 Silkworm cocoon-based hierarchical porous carbon and preparation method thereof
CN106881135A (en) * 2015-12-16 2017-06-23 中国科学院大连化学物理研究所 A kind of carbon-based non-metal catalyst for acetylene method preparing chloroethylene, preparation method and renovation process
CN107115883A (en) * 2017-05-16 2017-09-01 浙江工业大学 A kind of starch base N doping mesopore forming charcoal and preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LU ZHANG ET AL.: "Cocoon derived nitrogen enriched activated carbon fiber networks for capacitive deionization", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 *
王永刚等: "《煤化工工艺学》", 30 September 2014, 中国矿业大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109876840A (en) * 2018-12-25 2019-06-14 南开大学 A kind of preparation method and its application method of the non-metal catalyst for preparing vinyl chloride by hydrochlorination of acetylene
CN111454118A (en) * 2019-01-22 2020-07-28 中国科学院上海有机化学研究所 Method for preparing chloroethylene by reacting acetylene with dichloroethane
CN111454119A (en) * 2019-01-22 2020-07-28 中国科学院上海有机化学研究所 Method for preparing chloroethylene by reaction of acetylene and hydrogen chloride

Also Published As

Publication number Publication date
CN108187721B (en) 2020-11-24

Similar Documents

Publication Publication Date Title
CN110813359B (en) Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof
CN101502802B (en) Preparation method of catalyst for continuous production of succinic anhydride from hydrogenation of maleic anhydride
CN108187721A (en) The preparation method and its application method of a kind of nitrogen-doped carbon catalyst for fixed bed preparing vinyl chloride by hydrochlorination of acetylene
CN108097251B (en) Catalyst for fixed bed acetylene hydrochlorination and use method thereof
CN106622218A (en) Preparation method of carbon-loaded Ru base catalyst by carbon thermal reduction
CN109529840A (en) A kind of CO2Catalyst for Low-Temperature Methanation, preparation and application
CN102069000A (en) Non-mercury catalyst for production of vinyl chloride and preparation method thereof
CN114289048A (en) Preparation method of polyvinyl chloride mercury-free catalyst
CN110465279B (en) Mercury-free catalyst carrier activated carbon for PVC production and preparation method thereof
CN104971740B (en) The continuous catalyst and preparation method and application for preparing the fluoroaniline of N isopropyls 4
CN109499592A (en) Nanometer rods molybdenum carbide/molybdenum dioxide composite material preparation method
CN110787800B (en) Method for preparing superfine ternary copper catalyst at low cost
CN113926458B (en) Preparation method of copper hydrogenation catalyst, catalyst prepared by preparation method and application of catalyst
CN111135848A (en) Wood-based carbon catalyst, preparation method thereof and method for preparing cyclohexanone by phenol hydrogenation
CN106964390A (en) Benzene catalyst processed and its production and use
CN110560135A (en) Method for catalyzing selective hydrogenation of 1, 3-butadiene by NiPdPt catalyst
CN109261145B (en) Preparation method and application of sulfur-modified activated carbon-supported noble metal catalyst
CN1061269C (en) Ni-B amorphous alloy catalyst, its preparing process and application
CN108246340B (en) Preparation and use method of metal-free catalyst for preparing vinyl chloride by fixed bed acetylene hydrochlorination
CN115212882A (en) Porous copper silicide intermetallic compound material and preparation and application thereof
CN109894131B (en) Dimethyl terephthalate (DMT) hydrogenation catalyst and preparation method thereof
CN109876840A (en) A kind of preparation method and its application method of the non-metal catalyst for preparing vinyl chloride by hydrochlorination of acetylene
CN109647523A (en) A kind of preparation method and its application method of the non-metal catalyst for fixed bed preparing chloroethylene by acetylene hydrochlorination
CN108067282B (en) Catalyst for hydrochlorination of acetylene and using method
CN106853369A (en) Catalyst and preparation method and application for acetic acid Hydrogenation acetic acid ethyl reaction

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant