CN109317169A - A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof - Google Patents
A kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof Download PDFInfo
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- CN109317169A CN109317169A CN201811386897.0A CN201811386897A CN109317169A CN 109317169 A CN109317169 A CN 109317169A CN 201811386897 A CN201811386897 A CN 201811386897A CN 109317169 A CN109317169 A CN 109317169A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- C07—ORGANIC CHEMISTRY
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- 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
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Abstract
The invention discloses a kind of graphite oxide support type catalyst without mercury and preparation method for synthesis vinyl chloride thereof, graphene oxide, tri-chlorination barium, alkaline earth metal chloride and rare earth element chloride are made after the preparation of graphene oxide carrier, the preparation of maceration extract and the load of active component these steps.The present invention is using can be using the graphene oxide of large-scale industrial production as carrier, the preparation method for the multicomponent compounding that catalyst has used cost more cheap, active component uses the isometric mode of loading of vacuum, using unique preparation process, while utmostly guaranteeing catalytic performance, the cost of manufacture for reducing catalyst improves the cost performance of catalyst.
Description
Technical field
The present invention relates to the catalyst without mercury preparation technical fields more particularly to catalyst without mercury of acetylene method synthesis vinyl chloride thereof
Preparation method.
Background technique
Polyvinyl chloride (PVC) is one of maximum general-purpose plastics of yield on our times, very widely used.In Building wood
Material, industrial product, daily necessities, flooring laminate, floor tile, artificial leather, tubing, wire and cable, packaging film, bottle, foamed material, sealing
Material, fiber etc. are widely used.Shown according to national statistics office data: in May, 2017 China polyvinyl chloride yield
It is 146.2 ten thousand tons, increases by 1.5% on year-on-year basis, 1 ~ 5 month to date yield in 2017 is 768.1 ten thousand tons, increases by 6.8% on year-on-year basis.Society is to poly-
The demand of vinyl chloride is also being growing.
Since polyvinyl chloride is synthesized by vinyl chloride (VCM), select suitable VCM synthesis particularly important, currently
The VCM synthesis technique in the world is more, has acetylene method synthesis vinyl chloride thereof from using to distinguish on raw material mainly, and ethylene process synthesizes chlorine
Ethylene, it is the main technique of VC in China synthesis that domestic any particular energy source structure, which promotes acetylene method synthesis vinyl chloride thereof,.Current
The mercury catalyst toxicity that acetylene method synthesis vinyl chloride thereof uses is big, is easy to run off, and mercury chloride recycling is difficult, and consumption is big, domestic mercury money
Source is increasingly poor.14 department such as Domestic Environment protection portion indicates that " Minamata about mercury is public in No. 16 publication bulletins of in August, 2017
It is about " formally effective to China.Bulletin content includes the primary mercury ore for forbidding exploitation new from August 16th；Vinyl chloride monomer produces work
Skill uses mercury, mercury compound as catalyst or uses containing mercury catalyst etc..Environmental Protection Department vice-minister Zhao Yingmin expression, environment
Protection portion will continue to cooperate with each relevant ministries and commissions, actively promote the application and popularization of the low mercury technology of mercury-free, realize mercury pollution emission reduction and
With mercury products substitution；Chemical substance environment and health risk assessment are carried on, sternly to high risk chemicals production, using progress
Lattice limitation, and it is phased out substitution.It is imperative to explore development catalyst without mercury, develops the nothing for being suitable for domestic energy resource structure
Mercury catalyst has great importance to the production of polyvinyl chloride.
Exploration state is constantly in for the research and development of catalyst without mercury both at home and abroad, years of researches have summed up some rule
Rule: polynary to be formulated the catalyst for being obviously better than one pack system on conversion of alkyne and stability, metal chlorination in polynary formula
Object cation electron affinity, electronic standard electrode potential, metal chloride the enthalpy of formation, the valence shell electron of metal ion
Number can significantly influence the conversion ratio of acetylene, and the acid-base property of carrier can significantly influence the catalytic performance and catalyst of catalyst
Service life, the surface functional group type and content of carrier can significantly influence the catalytic performance of catalyst without mercury.It is public at present
The patent opened is high using the catalyst conversion of alkyne that the chloride of gold, silver and platinum metal is main active component but prepares
With high costs, there is very serious economy problems, the non-noble metal chloride preparation such as copper, bismuth, barium and tin in industrialized production
Catalyst all have that conversion of alkyne is low, and stability is poor to a certain extent, the service life is short, is lost the problems such as fast.
Summary of the invention
The present invention be directed to the defect of the prior art and deficiencies, provide a kind of using polynary formula, the gold of the lower enthalpy of formation
Belong to chloride, carrier has the preparation method of the compound prescription catalyst without mercury of oxygen-containing group abundant.
In order to achieve the above object, the technical solution of the invention is as follows:
A kind of graphite oxide support type catalyst without mercury for synthesis vinyl chloride thereof, it is characterised in that it is matched by following weight
Raw material be made: 27.3~98.45 parts of graphene oxide, 1~50 part of auxiliary active constituent, helps 0.49~2.7 part of main active constituent
0.05~20 part of agent；
Wherein, main active constituent is titanium trichloride, and auxiliary active constituent is alkaline earth metal chloride, and auxiliary agent is rare earth element chlorination
Object.
The alkaline earth metal chloride is barium chloride, magnesium chloride or calcium chloride.
The rare earth element chloride is cerium chloride or lanthanum chloride.
A kind of preparation method of the graphite oxide support type catalyst without mercury for synthesis vinyl chloride thereof, comprising the following steps:
(1) preparation of graphene oxide carrier: first graphite powder and anhydrous nitric acid sodium, which are added to, is placed in 0~5 DEG C in ice bath 98% dense
In sulfuric acid, using potassium permanganate is added under magnetic stirrer, reaction temperature is 0~25 DEG C, reacts warm 0.5~10h of the time,
It is warming up to 25~50 DEG C to continue to be stirred to react 10~60min, having reacted subsequent temperature of continuing rising is 80~100 DEG C, and distilled water is added to dilute
To 500~1000ml, remaining potassium permanganate and manganese dioxide are restored with the hydrogen peroxide of volume fraction 3%, so that it becomes it is colourless,
It filters, washs 2~5 times, until filtrate added drop-wise hydrogen peroxide does not become glassy yellow, sulfate radical washes clean while hot.Then in vacuum
Dry 5~48h obtains graphene oxide to get pretreated graphene oxide carrier is arrived in 40~80 DEG C of drying box；
(2) preparation of maceration extract: main active component, auxiliary active component and auxiliary agent are being dissolved under 25~60 DEG C of stirrings
In certain density hydrochloric acid solution, when dissolution, adds plastic foil to completely cut off air；
(3) load of active component: being put into round-bottomed flask for a certain amount of graphene oxide carrier, using vacuum pump filter 5~
60min, then the maceration extract vacuum prepared is loaded in equal volume in pretreated graphene oxide carrier, and in 25~80 DEG C
Lower revolving stirs 3~12h, and drying obtains required catalyst at 101~125 DEG C, and drying time is 12~48h.
It is 0.5~10% that main active component in the step 3), which accounts for carrier quality percentage composition, the auxiliary active component
Mass percentage be 1~50%, the mass percentage of the auxiliary agent is 0.05~20%, the concentration of hydrochloric acid 0.1
~5mol/L.
Compared with prior art, the invention has the benefit that
1, for the present invention using can be using the graphene oxide of large-scale industrial production as carrier, catalyst have used cost more cheap
Multicomponent compounding preparation method, active component uses the isometric mode of loading of vacuum, using unique preparation process,
While utmostly guaranteeing catalytic performance, the cost of manufacture of catalyst is reduced, the cost performance of catalyst is improved.
2, the present invention used in graphene oxide the preparation reaction time it is short, reaction process asepsis environment-protecting, safety compared with
The graphene oxide specific surface area of height, preparation is higher than general carrier active carbon, is suitble to the recipe ingredient of load high-content；Oxygen
Graphite alkene surface has richer functional group more modified than normal activated carbon that can effectively tie such as carboxyl, hydroxyl, epoxy group
It closes acetylene and participates in catalysis reaction, reduce reaction activity, while itself having certain catalytic capability；Due to carbon nano tube surface
With certain alkalinity, repulsion of the carrier to active component can be reduced by acidification, increase binding force, carrier introduces phosphate
Group can increase catalyst activity.
3, the present invention is compounded using base metal chloride titanium trichloride, alkaline earth metal chloride, rare earth element, multicomponent
Compounding has collaboration and facilitation between each other, not only ensure that cost is less expensive but also obtains higher catalytic performance, simultaneously
Improve the stability of catalyst.
4, the present invention can be to avoid the generation of tail washings using incipient impregnation, and resource utilization is high, and easy to operate, vacuum
Can by carrier it is mesoporous in evacuating air, preferably provide maceration extract load space.
Specific embodiment
Embodiment one:
First 30g graphite powder and 5g anhydrous nitric acid sodium (NaNO3) are added in the 200ml98% concentrated sulfuric acid for being placed in 0 DEG C in ice bath,
Using 30g potassium permanganate is added under magnetic stirrer, reaction temperature is 10 DEG C, reacts warm time 2h, be warming up to 40 DEG C after
Continuous to be stirred to react 30min, having reacted subsequent temperature of continuing rising is 80 DEG C, adds distilled water to be diluted to 500ml, with the dioxygen of volume fraction 3%
Water restores remaining potassium permanganate and manganese dioxide, so that it becomes colourless.Filter while hot, washing until filtrate added drop-wise hydrogen peroxide not
Become glassy yellow, then dry 12h obtains graphene oxide in 50 DEG C of vacuum oven, i.e., pretreated graphene oxide
Carrier.2g titanium trichloride, 1g barium chloride and 0.5g lanthanum chloride are dissolved into 2mol/L hydrochloric acid under stirring at normal temperature state, add modeling
Expect that film completely cuts off air；Liquid vacuum incipient impregnation will be loaded into the pretreated graphene oxide carrier of 30g, and at 80 DEG C
Revolving stirring 5h, drying obtains required catalyst, drying time 15h at 110 DEG C.Utilize the catalyst acetylene hydrogen
Chlorination synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed 15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1, and conversion of alkyne is
96.1 %, ethylene selectivity 99.7%.
Embodiment two:
First 60g graphite powder and 5g anhydrous nitric acid sodium are added in the 200ml98% concentrated sulfuric acid for being placed in 0 DEG C in ice bath, use magnetic force
Blender is added with stirring 50g potassium permanganate, and reaction temperature is 15 DEG C, reacts warm time 1h, is warming up to 40 DEG C and continues stirring instead
20min is answered, having reacted subsequent temperature of continuing rising is 70 DEG C, and distilled water is added to be diluted to 800ml, is restored with the hydrogen peroxide of volume fraction 3% surplus
Remaining potassium permanganate and manganese dioxide, so that it becomes colourless.It filters while hot, washing does not become bright orange until filtrate added drop-wise hydrogen peroxide
Color, then dry 10h obtains graphene oxide in 60 DEG C of vacuum oven, i.e., pretreated graphene oxide carrier.?
4g titanium trichloride, 2g barium chloride and 1g lanthanum chloride are dissolved into 2mol/L hydrochloric acid under stirring at normal temperature state, plastic foil is added to completely cut off
Air；Liquid vacuum incipient impregnation will be loaded into the pretreated graphene oxide carrier of 60g, and rotate stirring at 70 DEG C
5h, drying obtains required catalyst, drying time 8h at 125 DEG C.It is synthesized using the catalyst acetylene hydrochlorination
Vinyl chloride, 140 DEG C of reaction temperature, air speed 15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1, and conversion of alkyne is 95.1 %, second
Alkene is selectively 99.5%.
Embodiment three:
Preparation process is identical as example one, only change potassium permanganate additional amount be 40g be added after the reaction time be 3h, other
Part is constant, gained catalyst be used for catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed 15h-1, acetylene conversion
Rate is 96.5%, and hydrogen chloride and acetylene volume ratio are 1.2:1, and ethylene selectivity is 99.7 %.
Example IV:
Preparation process is identical as example one, and only changing main active component titanium trichloride additional amount is that 5g hydrochloric acid molar concentration is
3mol/L, other conditions are constant, gained catalyst be used for catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed
15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1, conversion of alkyne 96.3%, ethylene selectivity 99.8%.
Embodiment five:
Preparation process is identical as example one, and only changing main active component titanium trichloride additional amount is that 2g hydrochloric acid molar concentration is
1mol/L, other conditions are constant, gained catalyst be used for catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed
15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1, conversion of alkyne 94.3%, ethylene selectivity 99.7%.
Embodiment six:
Preparation process is identical as example two, and only heating up 40 DEG C after change addition potassium permanganate first set reaction is 60 DEG C, continues to stir
60min is reacted, having reacted subsequent temperature of continuing rising is 80 DEG C, adds distilled water to be diluted to 1000ml, other conditions are constant, gained catalyst
For catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed 15h-1, hydrogen chloride and acetylene volume ratio are 1.2:
1, conversion of alkyne 94.7%, ethylene selectivity 99.7%.
Embodiment seven:
Preparation process is identical as example two, and whipping temp is changed to be 50 DEG C when configuring maceration extract, by 5g titanium trichloride, 2.5g chlorination
Barium and 0.7g lanthanum chloride are dissolved into 2.5mol/L hydrochloric acid, and plastic foil is added to completely cut off air, and load liquid vacuum incipient impregnation is arrived
In the pretreated graphene oxide carrier of 60g, and the revolving stirring 5h at 50 DEG C, other conditions are constant, and gained catalyst is used
In catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, air speed 15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1,
Conversion of alkyne is 95.6%, ethylene selectivity 99.7%.
Embodiment eight:
Preparation process is identical as example two, and alkaline earth metal chloride is changed to magnesium chloride in multicomponent compound prescription, and rare earth element changes
For cerium chloride, other conditions are constant, and gained catalyst is used for catalyzing acetylene hydrogen chloride synthesis vinyl chloride thereof, 140 DEG C of reaction temperature, empty
Fast 15h-1, hydrogen chloride and acetylene volume ratio are 1.2:1, conversion of alkyne 95.3%, ethylene selectivity 99.8%.
Claims (5)
1. a kind of graphite oxide support type catalyst without mercury for synthesis vinyl chloride thereof, it is characterised in that it is matched by following weight
The raw material of ratio is made: 27.3~98.45 parts of graphene oxide, 0.49~2.7 part of main active constituent, 1~50 part of auxiliary active constituent,
0.05~20 part of auxiliary agent；
Wherein, main active constituent is titanium trichloride, and auxiliary active constituent is alkaline earth metal chloride, and auxiliary agent is rare earth element chlorination
Object.
2. a kind of graphite oxide support type catalyst without mercury for synthesis vinyl chloride thereof according to claim 1, feature
Be: the alkaline earth metal chloride is barium chloride, magnesium chloride or calcium chloride.
3. a kind of graphite oxide support type catalyst without mercury for synthesis vinyl chloride thereof according to claim 1, feature
Be: the rare earth element chloride is cerium chloride or lanthanum chloride.
4. the graphite oxide support type catalyst without mercury described in any one of claim 1 to 3 for synthesis vinyl chloride thereof
Preparation method, comprising the following steps:
(1) preparation of graphene oxide carrier: first graphite powder and anhydrous nitric acid sodium, which are added to, is placed in 0~5 DEG C in ice bath 98% dense
In sulfuric acid, using potassium permanganate is added under magnetic stirrer, reaction temperature is 0~25 DEG C, reacts warm 0.5~10h of the time,
It is warming up to 25~50 DEG C to continue to be stirred to react 10~60min, having reacted subsequent temperature of continuing rising is 80~100 DEG C, and distilled water is added to dilute
To 500~1000ml, remaining potassium permanganate and manganese dioxide are restored with the hydrogen peroxide of volume fraction 3%, so that it becomes it is colourless,
It filters, washs 2~5 times, until filtrate added drop-wise hydrogen peroxide does not become glassy yellow, sulfate radical washes clean, then in vacuum while hot
Dry 5~48h obtains graphene oxide to get pretreated graphene oxide carrier is arrived in 40~80 DEG C of drying box；
(2) preparation of maceration extract: main active component, auxiliary active component and auxiliary agent are being dissolved under 25~60 DEG C of stirrings
In certain density hydrochloric acid solution, when dissolution, adds plastic foil to completely cut off air；
(3) load of active component: being put into round-bottomed flask for a certain amount of graphene oxide carrier, using vacuum pump filter 5~
60min, then the maceration extract vacuum prepared is loaded in equal volume in pretreated graphene oxide carrier, and in 25~80 DEG C
Lower revolving stirs 3~12h, and drying obtains required catalyst at 101~125 DEG C, and drying time is 12~48h.
5. for the graphite oxide support type catalyst without mercury of synthesis vinyl chloride thereof described in wanting 4 according to claim according to right
Preparation method, it is characterised in that: it is 0.5~10% that the main active component in the step 3), which accounts for carrier quality percentage composition, described
The mass percentage of auxiliary active component be 1~50%, the mass percentage of the auxiliary agent is 0.05~20%, described
0.1~5mol/L of concentration of hydrochloric acid.
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| US4792643A (en) * | 1987-06-16 | 1988-12-20 | Kaiser Aluminum & Chemical Corporation | Catalyst and process for 1,1,1,2-tetrafluoroethane by vapor phase reaction |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| CN103495416A (en) * | 2013-10-24 | 2014-01-08 | 新疆大学 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
| CN104437565A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
| CN108043467A (en) * | 2017-11-27 | 2018-05-18 | 宁夏新龙蓝天科技股份有限公司 | Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof |
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2018
- 2018-11-20 CN CN201811386897.0A patent/CN109317169A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4792643A (en) * | 1987-06-16 | 1988-12-20 | Kaiser Aluminum & Chemical Corporation | Catalyst and process for 1,1,1,2-tetrafluoroethane by vapor phase reaction |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| CN103495416A (en) * | 2013-10-24 | 2014-01-08 | 新疆大学 | Carbon-material supported catalyst for acetylene hydrochlorinate reaction |
| CN104437565A (en) * | 2014-11-03 | 2015-03-25 | 扬州大学 | Method for preparing chloroethylene by reaction of chloroform and acetylene, and catalyst used in method |
| CN108043467A (en) * | 2017-11-27 | 2018-05-18 | 宁夏新龙蓝天科技股份有限公司 | Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof |
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Application publication date: 20190212 |