CN107185533A - Induction period controllable VCM synthesis Au-based catalyst and preparation method thereof - Google Patents
Induction period controllable VCM synthesis Au-based catalyst and preparation method thereof Download PDFInfo
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- CN107185533A CN107185533A CN201710359077.1A CN201710359077A CN107185533A CN 107185533 A CN107185533 A CN 107185533A CN 201710359077 A CN201710359077 A CN 201710359077A CN 107185533 A CN107185533 A CN 107185533A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
Abstract
It is controllable VCM synthesis Au-based catalyst of a kind of induction period and preparation method thereof the present invention relates to VCM synthesis Au-based catalyst technical field, the induction period controllable VCM synthesis is obtained in the steps below with Au-based catalyst：The first step, pickling；Second step, is pre-processed to the absorbent charcoal carrier after pickling.Induction period of the present invention controllable VCM synthesis is active higher than the Au-based catalyst that is prepared using existing method with Au-based catalyst, the present invention passes through simple and effective oxidation or reduction treatment, induction period is controlled, the effective rate of utilization of active component chlorauride is improved by controlling induction period to reach, so as to improve the activity of induction period controllable VCM synthesis Au-based catalyst, make induction period of the invention controllable VCM synthesis Au-based catalyst and preparation method thereof that there is actual industrial application value.
Description
Technical field
It is a kind of controllable VCM synthesis of induction period the present invention relates to VCM synthesis Au-based catalyst technical field
With Au-based catalyst and preparation method thereof.
Background technology
Polyvinyl chloride is one of big thermoplastic engineering plastic in the world five, and being widely used in building, agricultural, medical treatment etc., each is led
Domain, and vinyl chloride, as the monomer of polyvinyl chloride, its demand is also continuously increased.Due to the energy resource structure of the oil-poor many coals of China,
The main technique of current China's production vinyl chloride is the hydrogen chloride of acetylene：Pass through mercurous catalyst acetylene and hcl reaction
Generate vinyl chloride.With the pressure in terms of the drastically decline, and Environmental security of mercury storage level in recent years, urged used in acetylene hydrochlorination
Agent goes the mercuration imperative.
Because mercury catalyst is preparing and used security present in process and environmentally friendly sex chromosome mosaicism long-standing, at present
In the presence of a large amount of researchs for being directed to vinyl chloride catalyst without mercury.Wherein, on support type chlorination Au catalyst research the most system,
In detail, catalysis technique associated therewith is also the mercury-free catalysis technique of the most possible industrial applications that take the lead in realizing.
The research of Cardiff University of Britain Hutchings professors et al.（Journal of catalysis,2012,297:
128-136）Show, the excessive Au of support type chlorauride catalyst surface3+And without catalytic activity, and predict Au3+With carrier
Connection collectively constituted with synergy avtive spot.Absorbent charcoal carrier surface has substantial amounts of functional group, according to load
The connected mode of body surface face carbon atom and oxygen atom, can be divided into hydroxyl（-C-OH）, ketone group（-C=O）, carboxyl（-COOH）, no
It is different to the adsorption capacity of chlorauride with functional group.According to David seminars of Cardiff University achievement in research（Journal of
catalysis,2015,323:10-18）Show, hydroxyl is to Au3+Adsorption capacity it is most strong, but easily make chlorauride in activated carbon
Surface is agglomerated into larger nano-particle, is reduced to Au0；And the ketone group of carrier surface is to Au3+Adsorption capacity, chlorination is made just
Gold is with Au3+Form is attached to carrier surface.
For absorbent charcoal carrier, its surface functional group very abundant, but various group contents are different.For many
Number activated carbon, its surface has substantial amounts of carboxylic group, and chlorauride load is somebody's turn to do in carrier surface, but major part Au3+With carboxyl phase
Even, catalytic activity will not be shown at once.And for a part of activated carbon, great amount of hydroxy group is contained on its surface, hydroxyl has reduction
Property, it is intended to make Au3+Reunite and be Au originally0, so that Au3+Catalyst surface can not be uniformly adhered to.Due on its surface
Ketone group is less, the Au effectively utilized3+Less, therefore, existing Au-based catalyst activity is relatively low.
The activity level of catalyst needs to undergo Induction Process or referred to as induction period time that one section of activity slowly rises, and urges
Activity of the agent in induction period is interval does not have the most highly active for reaching catalyst.
The Chinese patent literature of Publication No. 102416323 discloses a kind of preparation method of catalyst, and wherein carrier is pre-
Reagent treatment includes the oxidizing substances such as nitric acid, potassium permanganate and hydrogen peroxide, its object is to modified support surface functional group,
Improve the dispersiveness of the palladium metal loaded on carrier.Its oxidizing species nitric acid used and potassium permanganate due to property excessively
Acutely, catalyst pore passage structure can be destroyed, the preparation for the load type gold catalyst not being suitable for involved by this paper, and palladium catalyst
Reaction mechanism and load type gold catalyst mechanism are different, do not have document to refer to its induction period problem, its accompanying method and sheet
Text has difference fundamentally.The Chinese patent literature of Publication No. 104415793 refers to a kind of preparation method of oxygen modified support,
Purpose is the content of surface oxygen for changing the carriers such as silica, molecular sieve, activated carbon and carborundum, so as to change carrier negative
Carry catalytic activity during other metals.Its oxidant used includes nitric acid, potassium permanganate and hydrogen peroxide, but it is not directed to catalysis
The related properties of agent induction period, and wherein the oxidizing species such as nitric acid and potassium permanganate are not suitable for the support type involved by this paper
The preparation of Au catalyst.
The content of the invention
The invention provides controllable VCM synthesis Au-based catalyst of a kind of induction period and preparation method thereof, overcome
The deficiency of above-mentioned prior art, it can effectively solve existing VCM synthesis Au-based catalyst and have that catalytic activity is relatively low to ask
Topic.
One of technical scheme is realized by following measures：A kind of controllable VCM synthesis of induction period
With Au-based catalyst, obtain in the steps below：The first step, will obtain absorbent charcoal carrier after pickling after absorbent charcoal carrier pickling；The
Two steps, absorbent charcoal carrier after pickling pre-process to obtain pretreated absorbent charcoal carrier；3rd step, barium chloride is dissolved
Barium chloride solution is obtained into deionized water, then pretreated absorbent charcoal carrier is impregnated into barium chloride solution, will be soaked
Precursor is obtained after pre- absorbent charcoal carrier drying after stain；4th step, auxiliary agent and gold trichloride are dissolved into deionized water and obtained
Mixed solution, then adds dispersant into mixed solution and stirring obtains stirring liquid, then, precursor is impregnated into stirring liquid
In, induction period controllable VCM synthesis Au-based catalyst will be obtained after the precursor drying after dipping, wherein, gold trichloride is accounted for
The mol ratio of the 0.05% to 0.5% of catalyst gross mass, dispersant and gold trichloride is 30 to 50, and auxiliary agent and gold trichloride rub
You are than being 5 to 10.
Here is the further optimization and/or improvements to one of foregoing invention technical scheme：
It is above-mentioned when the carboxyl-content on absorbent charcoal carrier surface is more than hydroxy radical content, pretreatment in second step is at reproducibility
Reason, reproducibility pretreatment is carried out using any of hydrogen, carbon monoxide, hydrogen sulfide, hydrazine hydrate, acetylene reducing substances.
In above-mentioned second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：By activated carbon after pickling
Carrier is encased in fixed bed reactors, using air speed as 80h-1To 200h-1Flow velocity, be passed through into fixed bed reactors hydrogen,
Any of carbon monoxide, hydrogen sulfide, acetylene reducibility gas, is kept for 1 hour to 1.5 at a temperature of 150 DEG C to 200 DEG C
Hour, after then heating to 500 DEG C to 700 DEG C and being kept for 3 hours, stopping is passed through reducibility gas, and stopping is passed through reproducibility gas
Nitrogen is passed through while body into fixed bed reactors, is passed through after nitrogen and the temperature of fixed bed reactors is continued to lift up 20 DEG C extremely
30 DEG C and keep 2 hours after, stop heating, be down at a temperature of fixed bed reactors after room temperature and obtain pretreated activity
High-area carbon；Or, in second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：Hydrazine hydrate is dissolved in
The hydrazine hydrate solution that mass concentration is 1% to 20% is obtained in deionized water, to mass concentration in 1% to 20% hydrazine hydrate solution
Add pickling after absorbent charcoal carrier and stood at 50 DEG C to 70 DEG C it is closed preserve 24 hours to 26 hours after obtain mixture, will
By washing, suction filtration separation, pretreated activated carbon sequentially is obtained after the filter cake drying obtained after suction filtration is separated for mixture
Carrier, the use quality for the hydrazine hydrate solution that mass concentration is 1% to 20% is 2.5 times of absorbent charcoal carrier total suction after pickling
To 5 times.
It is above-mentioned when the hydroxy radical content on absorbent charcoal carrier surface is more than carboxyl-content, pretreatment in second step is oxidisability
Processing, oxidisability pretreatment is carried out using any of oxygen, ozone and hydrogen peroxide oxidizing substance.
In above-mentioned second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：By activated carbon after pickling
Carrier is encased in fixed bed reactors, and any of oxygen or ozone oxidizing gas are passed through into fixed bed reactors simultaneously
Kept for 1 hour to 1.5 hours, after being then warming up to 350 DEG C to 400 DEG C and being kept for 10 hours to 12 hours, stopped at room temperature
Oxidizing gas is passed through, stopping is passed through nitrogen while being passed through oxidizing gas, is passed through after nitrogen, by the temperature of fixed bed reactors
After degree lifts 20 DEG C to 30 DEG C and kept for 2 hours, stop heating, be down to when the temperature of fixed bed reactors after room temperature and obtain pre- place
Absorbent charcoal carrier after reason；Or, in second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：Will be double
Oxygen water is dissolved in the hydrogen peroxide solution for obtaining that mass concentration is 1% to 20% in deionized water；Pair for being 1% to 20% to mass concentration
Add under absorbent charcoal carrier after pickling, room temperature condition, mixed after standing closed preserve 24 hours to 25 hours in the oxygen aqueous solution
Compound, mixture is sequentially separated by washing, suction filtration, obtains pretreated after the filter cake drying obtained after suction filtration is separated
Absorbent charcoal carrier, the quality for the hydrogen peroxide solution that mass concentration is 1% to 20% is 2.5 times to 5 times of absorbent charcoal carrier after pickling.
In the above-mentioned first step, absorbent charcoal carrier carries out pickling as follows：Absorbent charcoal carrier is added to mass concentration
For in 1% to 10% hydrochloric acid solution, the quality of hydrochloric acid solution is 2.5 times to 5 times of absorbent charcoal carrier total suction, room temperature condition
Under, closed preservation 24 hours to 25 hours are stood, are then filtered obtained mixture one after washing, suction filtration and separation
Cake, obtains absorbent charcoal carrier after pickling after filter cake is dried；Or/and, dispersant is one in isopropanol, isobutanol and n-butanol
More than kind；Or/and, auxiliary agent is one or more of sodium thiosulfate and ATS (Ammonium thiosulphate)；Or/and, the 3rd step is molten by barium chloride
Solution obtains barium chloride solution into deionized water, and pretreated absorbent charcoal carrier then is impregnated into chlorine using incipient wetness impregnation method
Change in barium solution, the pre- absorbent charcoal carrier after dipping is stood into closed storage 3 hours to 4 hours, then at 120 DEG C to 130 DEG C
At a temperature of dry after obtain precursor, wherein, barium chloride accounts for induction period controllable VCM synthesis Au-based catalyst gross mass
1% to 5%；Or/and, in the 4th step, mixing time is 3 hours to 6 hours, and dipping is impregnated using incipient wetness impregnation method；Or/
With, in the 4th step, the precursor after dipping first stand it is closed storage 24 hours to 25 hours, then temperature be 130 DEG C to 150 DEG C
Under conditions of dry after obtain induction period controllable VCM synthesis Au-based catalyst.
The two of technical scheme are realized by following measures：A kind of controllable VCM synthesis of induction period
With the preparation method of Au-based catalyst, carry out in the steps below：The first step, will obtain active after pickling after absorbent charcoal carrier pickling
High-area carbon；Second step, absorbent charcoal carrier after pickling pre-process to obtain pretreated absorbent charcoal carrier；3rd step, will
Barium chloride, which is dissolved into deionized water, obtains barium chloride solution, and it is molten that pretreated absorbent charcoal carrier then is impregnated into barium chloride
In liquid, precursor will be obtained after the pre- absorbent charcoal carrier drying after dipping；4th step, deionization is dissolved into by auxiliary agent and gold trichloride
Mixed solution is obtained in water, dispersant is then added into mixed solution and stirring obtains stirring liquid, then, precursor is impregnated into
Stir in liquid, induction period controllable VCM synthesis Au-based catalyst will be obtained after the precursor drying after dipping, wherein, trichlorine
Change gold and account for the 0.05% to 0.5% of catalyst gross mass, the mol ratio of dispersant and gold trichloride is 30 to 50, auxiliary agent and tri-chlorination
The mol ratio of gold is 5 to 10.
Here is two further optimization and/or improvements to foregoing invention technical scheme：
It is above-mentioned when the carboxyl-content on absorbent charcoal carrier surface is more than hydroxy radical content, pretreatment in second step is at reproducibility
Reason, reproducibility pretreatment is carried out using any of hydrogen, carbon monoxide, hydrogen sulfide, hydrazine hydrate, acetylene reducing substances.
In above-mentioned second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：By activated carbon after pickling
Carrier is encased in fixed bed reactors, using air speed as 80h-1To 200h-1Flow velocity, be passed through into fixed bed reactors hydrogen,
Any of carbon monoxide, hydrogen sulfide, acetylene reducibility gas, is kept for 1 hour to 1.5 at a temperature of 150 DEG C to 200 DEG C
Hour, after then heating to 500 DEG C to 700 DEG C and being kept for 3 hours, stopping is passed through reducibility gas, and stopping is passed through reproducibility gas
Nitrogen is passed through while body into fixed bed reactors, is passed through after nitrogen and the temperature of fixed bed reactors is continued to lift up 20 DEG C extremely
30 DEG C and keep 2 hours after, stop heating, be down at a temperature of fixed bed reactors after room temperature and obtain pretreated activity
High-area carbon；Or, in second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：Hydrazine hydrate is dissolved in
The hydrazine hydrate solution that mass concentration is 1% to 20% is obtained in deionized water, to mass concentration in 1% to 20% hydrazine hydrate solution
Add pickling after absorbent charcoal carrier and stood at 50 DEG C to 70 DEG C it is closed preserve 24 hours to 26 hours after obtain mixture, will
By washing, suction filtration separation, pretreated activated carbon sequentially is obtained after the filter cake drying obtained after suction filtration is separated for mixture
Carrier, the use quality for the hydrazine hydrate solution that mass concentration is 1% to 20% is 2.5 times of absorbent charcoal carrier total suction after pickling
To 5 times.
It is above-mentioned when the hydroxy radical content on absorbent charcoal carrier surface is more than carboxyl-content, pretreatment in second step is oxidisability
Processing, oxidisability pretreatment is carried out using any of oxygen, ozone and hydrogen peroxide oxidizing substance.
In above-mentioned second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：By activated carbon after pickling
Carrier is encased in fixed bed reactors, and any of oxygen or ozone oxidizing gas are passed through into fixed bed reactors simultaneously
Kept for 1 hour to 1.5 hours, after being then warming up to 350 DEG C to 400 DEG C and being kept for 10 hours to 12 hours, stopped at room temperature
Oxidizing gas is passed through, stopping is passed through nitrogen while being passed through oxidizing gas, is passed through after nitrogen, by the temperature of fixed bed reactors
After degree lifts 20 DEG C to 30 DEG C and kept for 2 hours, stop heating, be down to when the temperature of fixed bed reactors after room temperature and obtain pre- place
Absorbent charcoal carrier after reason；Or, in second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：Will be double
Oxygen water is dissolved in the hydrogen peroxide solution for obtaining that mass concentration is 1% to 20% in deionized water；Pair for being 1% to 20% to mass concentration
Add under absorbent charcoal carrier after pickling, room temperature condition, mixed after standing closed preserve 24 hours to 25 hours in the oxygen aqueous solution
Compound, mixture is sequentially separated by washing, suction filtration, obtains pretreated after the filter cake drying obtained after suction filtration is separated
Absorbent charcoal carrier, the quality for the hydrogen peroxide solution that mass concentration is 1% to 20% is 2.5 times to 5 times of absorbent charcoal carrier after pickling.
In the above-mentioned first step, absorbent charcoal carrier carries out pickling as follows：Absorbent charcoal carrier is added to mass concentration
For in 1% to 10% hydrochloric acid solution, the quality of hydrochloric acid solution is 2.5 times to 5 times of absorbent charcoal carrier total suction, room temperature condition
Under, closed preservation 24 hours to 25 hours are stood, are then filtered obtained mixture one after washing, suction filtration and separation
Cake, obtains absorbent charcoal carrier after pickling after filter cake is dried；Or/and, dispersant is one in isopropanol, isobutanol and n-butanol
More than kind；Or/and, auxiliary agent is one or more of sodium thiosulfate and ATS (Ammonium thiosulphate)；Or/and, the 3rd step is molten by barium chloride
Solution obtains barium chloride solution into deionized water, and pretreated absorbent charcoal carrier then is impregnated into chlorine using incipient wetness impregnation method
Change in barium solution, the pre- absorbent charcoal carrier after dipping is stood into closed storage 3 hours to 4 hours, then at 120 DEG C to 130 DEG C
At a temperature of dry after obtain precursor, wherein, barium chloride accounts for induction period controllable VCM synthesis Au-based catalyst gross mass
1% to 5%；Or/and, in the 4th step, mixing time is 3 hours to 6 hours, and dipping is impregnated using incipient wetness impregnation method；Or/
With, in the 4th step, the precursor after dipping first stand it is closed storage 24 hours to 25 hours, then temperature be 130 DEG C to 150 DEG C
Under conditions of dry after obtain induction period controllable VCM synthesis Au-based catalyst.
Induction period of the present invention controllable VCM synthesis is prepared with Au-based catalyst ratio using existing method
Au-based catalyst activity will height, the present invention by simple and effective oxidation or reduction treatment, induction period is controlled, lead to
Spending control induction period reaches the effective rate of utilization for improving active component chlorauride, so as to improve induction period controllable VCM synthesis
With the activity of Au-based catalyst, there is induction period of the invention controllable VCM synthesis Au-based catalyst and preparation method thereof
Actual industrial application value.
Brief description of the drawings
Accompanying drawing 1 is conversion of alkyne and the graph of a relation in reaction time.
Embodiment
The present invention is not limited by following embodiments, can technique according to the invention scheme and actual conditions it is specific to determine
Embodiment.Various chemical reagent and chemical article are previously mentioned in the present invention unless otherwise specified, is public in the prior art
Know public chemical reagent and chemical article；Percentage in the present invention is as being mass percent without specified otherwise；This hair
It is the aqueous solution that solvent is water, for example, hydrochloric acid solution is aqueous hydrochloric acid solution if the solution in bright is without specified otherwise；This
Normal temperature, room temperature in invention refer generally to 15 DEG C to 25 DEG C of temperature, are commonly defined as 25 DEG C.
With reference to embodiment, the invention will be further described：
Embodiment 1：The induction period controllable VCM synthesis Au-based catalyst, is obtained by following preparation methods：The first step, will
Absorbent charcoal carrier after pickling is obtained after absorbent charcoal carrier pickling；Second step, absorbent charcoal carrier after pickling is pre-processed
Pretreated absorbent charcoal carrier；3rd step, barium chloride is dissolved into deionized water and obtains barium chloride solution, then will be located in advance
Absorbent charcoal carrier after reason is impregnated into barium chloride solution, will obtain precursor after the pre- absorbent charcoal carrier drying after dipping；4th
Step, auxiliary agent and gold trichloride are dissolved into deionized water and obtain mixed solution, then add dispersant simultaneously into mixed solution
Stirring is obtained stirring liquid, then, and precursor is impregnated into stirring liquid, controllable by induction period is obtained after the precursor drying after dipping
VCM synthesis Au-based catalyst, wherein, gold trichloride accounts for the 0.05% to 0.5% of catalyst gross mass, dispersant and trichlorine
The mol ratio for changing gold is 30 to 50, and the mol ratio of auxiliary agent and gold trichloride is 5 to 10.
Method according to the present embodiment can be by controlling induction period to reach the controllable vinyl chloride conjunction of raising induction period
Into the effective rate of utilization with the active component chlorauride in Au-based catalyst, so that the induction period improved described in the present embodiment is controllable
VCM synthesis Au-based catalyst activity.
Before the pretreatment of second step is carried out, pickling operation is carried out to absorbent charcoal carrier, the gold such as Fe, K, Ca can be removed
Belong to ion, it is to avoid
When carrying out the pretreatment of second step, pretreatment is that agent is reacted with metal ion, thus reduces pretreating effect.And soak
Before the mixed solution of stain chlorauride, by the way of barium chloride pre-preg, thus, it is possible to improve Au on absorbent charcoal carrier surface
Immobilized ability.
Barium chloride solution can be the barium chloride solution of any concentration.
Embodiment 2：The induction period controllable VCM synthesis Au-based catalyst, is obtained by following preparation methods：First
Step, will obtain absorbent charcoal carrier after pickling after absorbent charcoal carrier pickling；Second step, absorbent charcoal carrier after pickling is pre-processed
Obtain pretreated absorbent charcoal carrier；3rd step, barium chloride is dissolved into deionized water and obtains barium chloride solution, then will
Pretreated absorbent charcoal carrier is impregnated into barium chloride solution, will obtain precursor after the pre- absorbent charcoal carrier drying after dipping；
4th step, auxiliary agent and gold trichloride are dissolved into deionized water and obtain mixed solution, are then added into mixed solution scattered
Agent and stir obtain stir liquid, then, by precursor be impregnated into stirring liquid in, by after dipping precursor drying after obtain induction period can
The VCM synthesis Au-based catalyst of control, wherein, gold trichloride accounts for the 0.05% or 0.5% of catalyst gross mass, dispersant and
The mol ratio of gold trichloride is 30 or 50, and the mol ratio of auxiliary agent and gold trichloride is 5 or 10.
Embodiment 3：As the optimization of above-described embodiment, when the carboxyl-content on absorbent charcoal carrier surface is more than hydroxy radical content
When, the pretreatment in second step is reproducibility processing, is reduced using any of hydrogen, carbon monoxide, hydrogen sulfide, hydrazine hydrate
Property material carry out reproducibility pretreatment.
Reproducibility pretreatment is carried out using any of hydrogen, carbon monoxide, hydrogen sulfide, hydrazine hydrate reducing substances
When, the reducing substances can by with Au3+Connected carboxyl reduction into ketone group so that obtain ketone group with catalytic activity with
Au3+Mutually the activated centre of complexing, by the effect of reducing substances, can shorten the induction period of catalyst, improve Au3+Have
Utilization rate is imitated, the activity of induction period controllable VCM synthesis Au-based catalyst is improved.
The reproducibility for the reducing substances that the present embodiment is used is gentleer, therefore the reproducibility thing described in the present embodiment
Matter will not be damaged to the pore passage structure of active carrier.
The content of the group such as carboxyl, hydroxyl in activated carbon（Quantity etc.）XPS in the prior art can be passed through（Chemical analysis electricity
Sub- power spectrum）Determined Deng characterizing, by measurement result, the phase of absorbent charcoal carrier surface-bound carboxylic content and hydroxy radical content can be known
To amount, so as to take different pretreatment modes.
Embodiment 4：As the optimization of above-described embodiment 3, in second step, absorbent charcoal carrier is carried out as follows after pickling
Reproducibility processing：Absorbent charcoal carrier after pickling is encased in fixed bed reactors, using air speed as 80h-1To 200h-1Flow velocity,
Any of hydrogen, carbon monoxide, hydrogen sulfide reducibility gas is passed through into fixed bed reactors, at 150 DEG C to 200 DEG C
At a temperature of keep 1 hour to 1.5 hours, then heat to 500 DEG C to 700 DEG C and keep 3 hours after, stopping be passed through reproducibility gas
Body, stopping is passed through nitrogen into fixed bed reactors while being passed through reducibility gas, is passed through fixed bed reactors after nitrogen
Temperature continue to lift up 20 DEG C to 30 DEG C and keep 2 hours after, stop heating, room temperature is down at a temperature of fixed bed reactors
After obtain pretreated absorbent charcoal carrier；Or, in second step, absorbent charcoal carrier carries out reproducibility as follows after pickling
Processing：Hydrazine hydrate is dissolved in the hydrazine hydrate solution for obtaining that mass concentration is 1% to 20% in deionized water, is 1% to mass concentration
Into 20% hydrazine hydrate solution add pickling after absorbent charcoal carrier and stood at 50 DEG C to 70 DEG C it is closed preserve 24 hours to 26
Mixture is obtained after hour, mixture is sequentially separated by washing, suction filtration, after the filter cake drying obtained after suction filtration is separated
To pretreated absorbent charcoal carrier, the use quality for the hydrazine hydrate solution that mass concentration is 1% to 20% is activated carbon after pickling
2.5 times to 5 times of carrier total suction.
Reducing substances and Au can be avoided by being passed through nitrogen or deionization washing3+Reaction, so as to ensure according to the present embodiment
The activity of obtained induction period controllable VCM synthesis Au-based catalyst.
Embodiment 5：As the optimization of above-described embodiment 1 to embodiment 2, exist with the difference of embodiment 3 and embodiment 4
In when the hydroxy radical content on absorbent charcoal carrier surface is more than carboxyl-content, the pretreatment in second step is oxidizing treatment, is used
Any of oxygen, ozone and hydrogen peroxide oxidizing substance carries out oxidisability pretreatment.
For the more absorbent charcoal carrier of surface hydroxyl, handled using oxidizing substance pre-oxidation, because hydroxyl is easier to
Carboxyl is oxidized to, its induction period in initial reaction stage can be increased, but can guarantee that Au3+It is uniformly distributed on absorbent charcoal carrier surface, from
And improve Au3+Utilization rate, improve catalytic activity.
The oxidisability for the oxidizing substance that the present embodiment is used is gentleer, therefore the oxidisability thing described in the present embodiment
Matter will not be damaged to the pore passage structure of active carrier.
Embodiment 6：As the optimization of above-described embodiment 5, in second step, absorbent charcoal carrier is carried out as follows after pickling
Oxidizing treatment：Absorbent charcoal carrier after pickling is encased in fixed bed reactors, be passed through into fixed bed reactors oxygen or
Any of ozone oxidizing gas is simultaneously kept for 1 hour to 1.5 hours at room temperature, is then warming up to 350 DEG C to 400 DEG C simultaneously
After being kept for 10 hours to 12 hours, stopping is passed through oxidizing gas, and stopping is passed through nitrogen while being passed through oxidizing gas, is passed through
After nitrogen, after 20 DEG C to 30 DEG C of the temperature lifting of fixed bed reactors and being kept for 2 hours, stop heating, work as fixed bed reaction
The temperature of device, which is down to after room temperature, obtains pretreated absorbent charcoal carrier；Or, in second step, absorbent charcoal carrier is pressed after pickling
State method and carry out oxidizing treatment：Hydrogen peroxide is dissolved in obtained in deionized water mass concentration be 1% to 20% dioxygen it is water-soluble
Liquid；To mass concentration to be added in 1% to 20% hydrogen peroxide solution under absorbent charcoal carrier after pickling, room temperature condition, stand closed
Mixture is obtained after preserving 24 hours to 25 hours, mixture is sequentially separated by washing, suction filtration, obtained after suction filtration is separated
Filter cake drying after obtain pretreated absorbent charcoal carrier, the quality for the hydrogen peroxide solution that mass concentration is 1% to 20% is acid
Wash rear absorbent charcoal carrier 2.5 times to 5 times.
Embodiment 7：As the optimization of above-described embodiment, in the first step, absorbent charcoal carrier carries out pickling as follows：Will
Absorbent charcoal carrier is added in the hydrochloric acid solution that mass concentration is 1% to 10%, and the quality of hydrochloric acid solution is always inhaled for absorbent charcoal carrier
2.5 times to 5 times of water, under room temperature condition, stand it is closed preserve 24 hours to 25 hours, then by obtained mixture once
Filter cake is obtained after crossing washing, suction filtration and separation, absorbent charcoal carrier after pickling is obtained after filter cake is dried；Or/and, dispersant is different
One or more of propyl alcohol, isobutanol and n-butanol；Or/and, auxiliary agent be in sodium thiosulfate and ATS (Ammonium thiosulphate) it is a kind of with
On；Or/and, barium chloride is dissolved into deionized water and obtains barium chloride solution by the 3rd step, then will be pre- using incipient wetness impregnation method
Absorbent charcoal carrier after processing is impregnated into barium chloride solution, and the pre- absorbent charcoal carrier after dipping is stood into closed storage 3 hours
To 4 hours, precursor then is obtained after drying at a temperature of 120 DEG C to 130 DEG C, wherein, barium chloride accounts for induction period controllable chlorine
Ethylene synthase is with the 1% to 5% of Au-based catalyst gross mass；Or/and, in the 4th step, mixing time is 3 hours to 6 hours, dipping
Impregnated using incipient wetness impregnation method；Or/and, in the 4th step, it is 24 hours to 25 small that the precursor after dipping first stands closed storage
When, obtain induction period controllable VCM synthesis after being then to dry under conditions of 130 DEG C to 150 DEG C in temperature and be catalyzed with auri
Agent.
Embodiment 8：Oxidisability pretreatment is carried out to carrier using hydrogen peroxide solution.The induction period controllable VCM synthesis
With Au-based catalyst, obtained by following preparation methods：By 8.4g activated carbons（Absorbent charcoal carrier）Being added to 40mL mass concentrations is
In 4% hydrochloric acid solution, under room temperature condition, closed preservation 24 hours are stood, then by obtained mixture suction filtration, separation, afterwards
Gained filter cake is dried, absorbent charcoal carrier after pickling is obtained；Pickling is added in 40mL mass concentrations is 5% hydrogen peroxide solutions
Under absorbent charcoal carrier afterwards, room temperature condition, stand it is closed preserve 24 hours, then by the washing of gained mixture, suction filtration, separation, it
Gained filter cake is dried afterwards, pretreated absorbent charcoal carrier is obtained；0.17g barium chlorides are dissolved into deionized water and obtain chlorine
Change barium solution, pretreated absorbent charcoal carrier is impregnated into barium chloride solution using incipient wetness impregnation method, stand closed storage 3
In 130 DEG C of drying after hour, precursor is obtained；0.02g gold trichlorides, 0.12g sodium thiosulfate are dissolved into deionized water and obtained
To mixed solution, backward gold trichloride and sodium thiosulfate mixed solution in add 0.16g isopropanols and stir 3 hours
To stirring liquid, precursor is impregnated into stirring liquid using incipient wetness impregnation method, closed storage 24 hours are stood, afterwards in 130 DEG C of bakings
It is dry, induction period controllable VCM synthesis Au-based catalyst is produced, numbering is CatH2O2。
Embodiment 9：Reproducibility pretreatment is carried out to carrier using hydrogen.The induction period controllable VCM synthesis auri
Catalyst, is obtained by following preparation methods：8.4g activated carbons are added in the hydrochloric acid solution that 40mL mass concentrations are 4%, room temperature
Under the conditions of, closed preservation 24 hours are stood, then by obtained mixture suction filtration, separation, gained filter cake is dried afterwards, obtained
Absorbent charcoal carrier after pickling；Absorbent charcoal carrier after pickling is encased in fixed bed reactors, hydrogen is passed through, gas space velocity is
80h-1, kept for 1 hour at room temperature；Afterwards, reactor is heated to 200 DEG C, kept for 10 hours；Then, by temperature of reactor
Room temperature is down to, nitrogen purging is passed through, nitrogen air speed is 80h-1, kept for 1 hour；Afterwards, the activated carbon in reactor is taken out, is obtained
Pretreated absorbent charcoal carrier；0.17g barium chlorides are dissolved into deionized water and obtain barium chloride solution, using incipient wetness impregnation
Pretreated absorbent charcoal carrier is impregnated into barium chloride solution by method, is dried, is obtained at 130 DEG C after standing closed storage 3 hours
To precursor；0.02g gold trichlorides, 0.12g sodium thiosulfate are dissolved into deionized water and obtain mixed solution, backward three
0.16g isopropanols are added in the mixed solution of chlorauride and sodium thiosulfate and are stirred and obtain within 3 hours stirring liquid, using first immersion
Precursor is impregnated into stirring liquid by stain method, stands closed storage 24 hours, afterwards in 130 DEG C of drying, produces induction period controllable
VCM synthesis Au-based catalyst, numbering is CatH2。
Embodiment 10：Reproducibility pretreatment is carried out to carrier using acetylene.The induction period it is controllable VCM synthesis gold
Base catalyst, is obtained by following preparation methods：8.4g activated carbons are added in the hydrochloric acid solution that 40mL mass concentrations are 4%, room
Under the conditions of temperature, closed preservation 24 hours are stood, then by obtained mixture suction filtration, separation, gained filter cake is dried afterwards, obtained
Absorbent charcoal carrier after to pickling；Absorbent charcoal carrier after pickling is encased in fixed bed reactors, acetylene is passed through, gas space velocity is
80h-1, kept for 1 hour at room temperature；Afterwards, reactor is heated to 200 DEG C, kept for 10 hours；Then, by temperature of reactor
Room temperature is down to, nitrogen purging is passed through, nitrogen air speed is 80h-1, kept for 1 hour；Afterwards, the activated carbon in reactor is taken out, is obtained
Pretreated absorbent charcoal carrier；0.17g barium chlorides are dissolved into deionized water and obtain barium chloride solution, using incipient wetness impregnation
Pretreated absorbent charcoal carrier is impregnated into barium chloride solution by method, is dried, is obtained at 130 DEG C after standing closed storage 3 hours
To precursor；0.02g gold trichlorides, 0.12g sodium thiosulfate are dissolved into deionized water and obtain mixed solution, backward three
0.16g isopropanols are added in the mixed solution of chlorauride and sodium thiosulfate and are stirred and obtain within 3 hours stirring liquid, using first immersion
Precursor is impregnated into stirring liquid by stain method, stands closed storage 24 hours, afterwards in 130 DEG C of drying, produces induction period controllable
VCM synthesis Au-based catalyst, numbering is CatC2H2。
Embodiment 11：Reproducibility pretreatment is carried out to carrier using hydrogen sulfide.The induction period controllable VCM synthesis is used
Au-based catalyst, is obtained by following preparation methods：8.4g activated carbons are added in the hydrochloric acid solution that 40mL mass concentrations are 4%,
Under room temperature condition, closed preservation 24 hours are stood, then by obtained mixture suction filtration, separation, are afterwards dried gained filter cake,
Obtain absorbent charcoal carrier after pickling；The absorbent charcoal carrier of pickling is encased in fixed bed reactors, hydrogen sulfide, gas space is passed through
Speed is 200h-1, kept for 1 hour at room temperature；Afterwards, reactor is heated to 200 DEG C, kept for 8 hours；Then, by reactor
Temperature is down to room temperature, is passed through nitrogen purging, and nitrogen air speed is 200h-1, kept for 1 hour；Afterwards, the activity in reactor is taken out
Charcoal, obtains pretreated absorbent charcoal carrier；0.17g barium chlorides are dissolved into deionized water and obtain barium chloride solution, are used
Pretreated absorbent charcoal carrier is impregnated into barium chloride solution by incipient wetness impregnation method, is stood after closed deposit 3 hours at 130 DEG C
Drying, obtains precursor；0.02g gold trichlorides, 0.12g sodium thiosulfate are dissolved into deionized water and obtain mixed solution, it
0.16g isopropanols are added in the mixed solution of backward gold trichloride and sodium thiosulfate and are stirred and obtain within 3 hours stirring liquid, are used
Precursor is impregnated into stirring liquid by incipient wetness impregnation method, stands closed storage 24 hours, afterwards in 130 DEG C of drying, produces induction period
Controllable VCM synthesis Au-based catalyst, numbering is CatH2S。
Embodiment 12：Oxidisability pretreatment is carried out to carrier using oxygen.The induction period it is controllable VCM synthesis gold
Base catalyst, is obtained by following preparation methods：8.4g activated carbons are added in the hydrochloric acid solution that 40mL mass concentrations are 4%, room
Under the conditions of temperature, closed preservation 24 hours are stood, then by obtained mixture suction filtration, separation, gained filter cake is dried afterwards, obtained
Absorbent charcoal carrier after to pickling；Absorbent charcoal carrier after pickling is encased in fixed bed reactors, oxygen is passed through, gas space velocity is
200h-1, kept for 1 hour at room temperature；Afterwards, reactor is heated to 220 DEG C, kept for 10 hours；Then, by temperature of reactor
Room temperature is down to, nitrogen purging is passed through, nitrogen air speed is 200h-1, kept for 1 hour；Afterwards, the activated carbon in reactor is taken out, is obtained
To pretreated absorbent charcoal carrier；0.17g barium chlorides are dissolved into deionized water and obtain barium chloride solution, using first immersion
Pretreated absorbent charcoal carrier is impregnated into barium chloride solution by stain method, is dried after standing closed storage 3 hours at 130 DEG C,
Obtain precursor；0.02g gold trichlorides, 0.12g sodium thiosulfate are dissolved into deionized water and obtain mixed solution, it is backward
0.16g isopropanols are added in the mixed solution of gold trichloride and sodium thiosulfate and are stirred and obtain within 3 hours stirring liquid, using just wet
Infusion process is impregnated into liquid liquid is stirred in precursor, and stands closed storage 24 hours, afterwards in 130 DEG C of drying, produces required induction
Phase controllable VCM synthesis Au-based catalyst, numbering is CatO2。
The Au-based catalyst prepared using the conventional Au-based catalyst preparation method known to the row industry personnel of this area is made
For comparative example.Reference examples：Carrier does not carry out oxidation-reduction quality pretreatment, uses deionized water washing process, is used as check experiment.
8.4g activated carbons are added in the hydrochloric acid solution that 40mL mass concentrations are 4%, under room temperature condition, stand closed protect
Deposit 24 hours, then by obtained mixture suction filtration, separation, gained filter cake is dried afterwards, absorbent charcoal carrier after pickling is obtained；
Under the absorbent charcoal carrier added in 40mL deionized waters after pickling, room temperature condition, closed preservation 24 hours are stood, then by institute
Mixture suction filtration, separation are obtained, gained filter cake is dried afterwards, pretreated absorbent charcoal carrier is obtained, 0.17g barium chlorides is molten
Solution obtains barium chloride solution into deionized water, and pretreated absorbent charcoal carrier is impregnated into barium chloride using incipient wetness impregnation method
In solution, dried after standing closed storage 3 hours at 130 DEG C, obtain precursor；By 0.02g gold trichlorides, 0.12g thiosulfuric acids
Sodium, which is dissolved into deionized water, obtains mixed solution, backward gold trichloride and sodium thiosulfate mixed solution in add
0.16g isopropanols and stir obtain within 3 hours stir liquid, using incipient wetness impregnation method by precursor be impregnated into stirring liquid in, stand it is closed
Storage 24 hours, afterwards in 130 DEG C of drying, produces Au-based catalyst, numbering is Cat0。
Induction period for being obtained to above-described embodiment 8 to embodiment 12 controllable VCM synthesis Au-based catalyst and right
The catalytic performance of the Au-based catalyst obtained as usual is evaluated, and evaluates catalyst activity by the conversion ratio of acetylene here
It is good and bad.
Absorbent charcoal carrier compares hydroxyl using absorbent charcoal carrier or carboxyl-content of the hydroxy radical content more than carboxyl-content in reference examples
Au-based catalyst made from absorbent charcoal carrier more than base content and the method according to reference examples in catalyst performance evaluation,
Conversion of alkyne and the relation curve in reaction time are same curve in Fig. 1.
As seen in Figure 1, the Au-based catalyst obtained relative to reference examples, is obtained using embodiment 9 to embodiment 11
To the conversion of alkyne of induction period controllable VCM synthesis Au-based catalyst can just reach and turn within the shorter time
The work of induction period that the maximum of rate, i.e. embodiment 9 are obtained to embodiment 11 controllable VCM synthesis Au-based catalyst
Property reach maximum in shorter time, and the induction period that is obtained to embodiment 11 of embodiment 9 controllable VCM synthesis is used
The conversion of alkyne of Au-based catalyst is higher than the conversion of alkyne of the Au-based catalyst obtained using reference examples, i.e., by carboxyl
Absorbent charcoal carrier of the content more than hydroxy radical content is carried out after reproducibility pretreatment, can shorten induction period, makes the catalysis of the present invention
Agent can reach maximum activity center within the shorter time, so as to make conversion of alkyne reach maximum within the shorter time
Value；
The Au-based catalyst obtained relative to reference examples, induction period for being obtained using embodiment 8, embodiment 12 controllable vinyl chloride
The conversion of alkyne of synthesis Au-based catalyst can reach the maximum of conversion ratio in longer time, and in reaction
Between be more than 3 hours after, the acetylene of induction period that embodiment 8, embodiment 12 are obtained controllable VCM synthesis Au-based catalyst
High conversion rate is in the conversion of alkyne of the Au-based catalyst obtained using reference examples, i.e., by more than carboxyl-content to hydroxy radical content
Absorbent charcoal carrier carry out after oxidisability pretreatment, although extend induction period, but final enable the catalyst of the present invention
Maximum activity center is reached, the catalytic activity of the present invention is finally improved, so as to improve conversion of alkyne.
In summary, induction period of the present invention controllable VCM synthesis uses existing method with Au-based catalyst ratio
The activity of the Au-based catalyst prepared is high, and the present invention is entered by simple and effective oxidation or reduction treatment to induction period
Row control, the effective rate of utilization of active component chlorauride is improved by controlling induction period to reach, so that it is controllable to improve induction period
The activity of VCM synthesis Au-based catalyst, makes VCM synthesis Au-based catalyst and its system that induction period of the invention is controllable
Preparation Method has actual industrial application value.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can basis
The non-essential technical characteristic of increase and decrease is actually needed, to meet the demand of different situations.
Claims (12)
1. the VCM synthesis Au-based catalyst that a kind of induction period is controllable, it is characterised in that obtain in the steps below：The first step,
Absorbent charcoal carrier after pickling will be obtained after absorbent charcoal carrier pickling；Second step, absorbent charcoal carrier after pickling is carried out to pre-process
To pretreated absorbent charcoal carrier；3rd step, barium chloride is dissolved into deionized water and obtains barium chloride solution, then will be pre-
Absorbent charcoal carrier after processing is impregnated into barium chloride solution, will obtain precursor after the pre- absorbent charcoal carrier drying after dipping；The
Four steps, auxiliary agent and gold trichloride are dissolved into deionized water and obtain mixed solution, dispersant is then added into mixed solution
And stirring obtains stirring liquid, then, precursor is impregnated into stirring liquid, it is controllable by induction period is obtained after the precursor drying after dipping
VCM synthesis Au-based catalyst, wherein, gold trichloride accounts for the 0.05% to 0.5% of catalyst gross mass, dispersant and three
The mol ratio of chlorauride is 30 to 50, and the mol ratio of auxiliary agent and gold trichloride is 5 to 10.
2. the VCM synthesis Au-based catalyst that induction period according to claim 1 is controllable, it is characterised in that work as activity
When the carboxyl-content on high-area carbon surface is more than hydroxy radical content, the pretreatment in second step is reproducibility processing, using hydrogen, an oxygen
Change any of carbon, hydrogen sulfide, acetylene, hydrazine hydrate reducing substances and carry out reproducibility pretreatment.
3. the VCM synthesis Au-based catalyst that induction period according to claim 2 is controllable, it is characterised in that second step
In, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：Absorbent charcoal carrier after pickling is encased in fixed bed anti-
Answer in device, using air speed as 80h-1To 200h-1Flow velocity, hydrogen, carbon monoxide, hydrogen sulfide, second are passed through into fixed bed reactors
Any of alkynes reducibility gas, is kept for 1 hour to 1.5 hours at a temperature of 150 DEG C to 200 DEG C, then heats to 500
DEG C to 700 DEG C and after being kept for 3 hours, stopping is passed through reducibility gas, and stopping is passed through anti-to fixed bed while reducibility gas
Answer and nitrogen be passed through in device, be passed through after nitrogen by the temperature of fixed bed reactors continue to lift up 20 DEG C to 30 DEG C and keep 2 hours after,
Stop heating, be down at a temperature of fixed bed reactors after room temperature and obtain pretreated absorbent charcoal carrier；Or, second step
In, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：Hydrazine hydrate is dissolved in deionized water and obtains quality
Concentration is 1% to 20% hydrazine hydrate solution, is carried by active carbon after addition pickling in 1% to 20% hydrazine hydrate solution to mass concentration
Body and stood at 50 DEG C to 70 DEG C it is closed preserve 24 hours to 26 hours after obtain mixture, by mixture sequentially pass through water
Wash, suction filtration is separated, obtain pretreated absorbent charcoal carrier after the filter cake drying obtained after suction filtration is separated, mass concentration is 1%
Use quality to 20% hydrazine hydrate solution is 2.5 times to 5 times of absorbent charcoal carrier total suction after pickling.
4. the VCM synthesis Au-based catalyst that induction period according to claim 1 is controllable, it is characterised in that work as activity
When the hydroxy radical content on high-area carbon surface is more than carboxyl-content, the pretreatment in second step is oxidizing treatment, using oxygen, ozone
Oxidisability pretreatment is carried out with any of hydrogen peroxide oxidizing substance.
5. the VCM synthesis Au-based catalyst that induction period according to claim 4 is controllable, it is characterised in that second step
In, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：Absorbent charcoal carrier after pickling is encased in fixed bed anti-
Answer in device, any of oxygen or ozone oxidizing gas are passed through into fixed bed reactors and is kept for 1 hour at room temperature
To 1.5 hours, after being then warming up to 350 DEG C to 400 DEG C and being kept for 10 hours to 12 hours, stopping was passed through oxidizing gas, stops
Nitrogen is passed through while being only passed through oxidizing gas, is passed through after nitrogen, the temperature of fixed bed reactors is lifted 20 DEG C to 30 DEG C
And after being kept for 2 hours, stop heating, be down to when the temperature of fixed bed reactors after room temperature and obtain pretreated carried by active carbon
Body；Or, in second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：By hydrogen peroxide be dissolved in from
The hydrogen peroxide solution that mass concentration is 1% to 20% is obtained in sub- water；It is addition in 1% to 20% hydrogen peroxide solution to mass concentration
Under absorbent charcoal carrier after pickling, room temperature condition, stand it is closed preserve 24 hours to 25 hours after obtain mixture, by mixture according to
Sequence obtains pretreated absorbent charcoal carrier, quality by washing, suction filtration separation after the filter cake drying obtained after suction filtration is separated
The quality for the hydrogen peroxide solution that concentration is 1% to 20% is 2.5 times to 5 times of absorbent charcoal carrier after pickling.
6. the VCM synthesis Au-based catalyst that induction period according to claim 1 or 2 or 3 or 4 or 5 is controllable, it is special
Levy and be in the first step, absorbent charcoal carrier carries out pickling as follows：By absorbent charcoal carrier be added to mass concentration for 1% to
In 10% hydrochloric acid solution, the quality of hydrochloric acid solution is 2.5 times to 5 times of absorbent charcoal carrier total suction, quiet under room temperature condition
Closed preservation 24 hours to 25 hours is put, obtained mixture one is then obtained into filter cake after washing, suction filtration and separation, will
Absorbent charcoal carrier after pickling is obtained after filter cake drying；Or/and, dispersant be in isopropanol, isobutanol and n-butanol it is a kind of with
On；Or/and, auxiliary agent is one or more of sodium thiosulfate and ATS (Ammonium thiosulphate)；Or/and, barium chloride is dissolved into by the 3rd step
Barium chloride solution is obtained in deionized water, pretreated absorbent charcoal carrier is then impregnated into by barium chloride using incipient wetness impregnation method
In solution, the pre- absorbent charcoal carrier after dipping is stood into closed storage 3 hours to 4 hours, then in 120 DEG C to 130 DEG C of temperature
Degree is lower dry after obtain precursor, wherein, barium chloride accounts for induction period controllable VCM synthesis with the 1% of Au-based catalyst gross mass
To 5%；Or/and, in the 4th step, mixing time is 3 hours to 6 hours, and dipping is impregnated using incipient wetness impregnation method；Or/and,
In 4th step, the precursor after dipping first stands closed storage 24 hours to 25 hours, is then 130 DEG C to 150 DEG C in temperature
Under the conditions of dry after obtain induction period controllable VCM synthesis Au-based catalyst.
7. a kind of controllable VCM synthesis of induction period according to claim 1 or 2 or 3 or 4 or 5 or 6 is catalyzed with auri
The preparation method of agent, it is characterised in that carry out in the steps below：The first step, will obtain active after pickling after absorbent charcoal carrier pickling
High-area carbon；Second step, absorbent charcoal carrier after pickling pre-process to obtain pretreated absorbent charcoal carrier；3rd step, will
Barium chloride, which is dissolved into deionized water, obtains barium chloride solution, and it is molten that pretreated absorbent charcoal carrier then is impregnated into barium chloride
In liquid, precursor will be obtained after the pre- absorbent charcoal carrier drying after dipping；4th step, deionization is dissolved into by auxiliary agent and gold trichloride
Mixed solution is obtained in water, dispersant is then added into mixed solution and stirring obtains stirring liquid, then, precursor is impregnated into
Stir in liquid, induction period controllable VCM synthesis Au-based catalyst will be obtained after the precursor drying after dipping, wherein, trichlorine
Change gold and account for the 0.05% to 0.5% of catalyst gross mass, the mol ratio of dispersant and gold trichloride is 30 to 50, auxiliary agent and tri-chlorination
The mol ratio of gold is 5 to 10.
8. the preparation method of induction period according to claim 7 controllable VCM synthesis Au-based catalyst, its feature
It is when the carboxyl-content on absorbent charcoal carrier surface is more than hydroxy radical content, the pretreatment in second step is reproducibility processing, is adopted
Reproducibility pretreatment is carried out with any of hydrogen, carbon monoxide, hydrogen sulfide, acetylene, hydrazine hydrate reducing substances.
9. the preparation method of induction period according to claim 8 controllable VCM synthesis Au-based catalyst, its feature
It is in second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：Absorbent charcoal carrier after pickling is loaded
Into fixed bed reactors, using air speed as 80h-1To 200h-1Flow velocity, hydrogen, an oxidation are passed through into fixed bed reactors
Any of carbon, hydrogen sulfide, acetylene reducibility gas, is kept for 1 hour to 1.5 hours at a temperature of 150 DEG C to 200 DEG C,
After then heating to 500 DEG C to 700 DEG C and being kept for 3 hours, stopping is passed through reducibility gas, and stopping is passed through the same of reducibility gas
When nitrogen is passed through into fixed bed reactors, be passed through after nitrogen and the temperature of fixed bed reactors continued to lift up 20 DEG C to 30 DEG C simultaneously
After being kept for 2 hours, stop heating, be down at a temperature of fixed bed reactors after room temperature and obtain pretreated carried by active carbon
Body；Or, in second step, absorbent charcoal carrier carries out reproducibility processing as follows after pickling：It will be dissolved in deionized water
The hydrazine hydrate solution that mass concentration is 1% to 20% is obtained, is added into the hydrazine hydrate solution that mass concentration is 1% to 20% after pickling
Absorbent charcoal carrier and stood at 50 DEG C to 70 DEG C it is closed preserve 24 hours to 26 hours after obtain mixture, by mixture sequentially
By washing, suction filtration separation, pretreated absorbent charcoal carrier is obtained after the filter cake drying obtained after suction filtration is separated, quality is dense
The use quality for the hydrazine hydrate solution that degree is 1% to 20% is 2.5 times to 5 times of absorbent charcoal carrier total suction after pickling.
10. the preparation method of induction period according to claim 7 controllable VCM synthesis Au-based catalyst, its feature
It is when the hydroxy radical content on absorbent charcoal carrier surface is more than carboxyl-content, the pretreatment in second step is oxidizing treatment, is adopted
Oxidisability pretreatment is carried out with any of oxygen, ozone and hydrogen peroxide oxidizing substance.
11. the preparation method of induction period according to claim 10 controllable VCM synthesis Au-based catalyst, it is special
Levy and be in second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：Absorbent charcoal carrier after pickling is filled
Enter into fixed bed reactors, any of oxygen or ozone oxidizing gas are passed through into fixed bed reactors and in room temperature
Lower to be kept for 1 hour to 1.5 hours, after being then warming up to 350 DEG C to 400 DEG C and being kept for 10 hours to 12 hours, stopping is passed through oxygen
The property changed gas, stopping is passed through nitrogen while being passed through oxidizing gas, is passed through after nitrogen, and the temperature of fixed bed reactors is lifted
20 DEG C to 30 DEG C and keep 2 hours after, stop heating, be down to when the temperature of fixed bed reactors after room temperature and obtain pretreated
Absorbent charcoal carrier；Or, in second step, absorbent charcoal carrier carries out oxidizing treatment as follows after pickling：Dioxygen is water-soluble
Solution obtains the hydrogen peroxide solution that mass concentration is 1% to 20% in deionized water；It is water-soluble for 1% to 20% dioxygen to mass concentration
Added in liquid under absorbent charcoal carrier after pickling, room temperature condition, mixture is obtained after standing closed preserve 24 hours to 25 hours, will
By washing, suction filtration separation, pretreated activated carbon sequentially is obtained after the filter cake drying obtained after suction filtration is separated for mixture
Carrier, the quality for the hydrogen peroxide solution that mass concentration is 1% to 20% is 2.5 times to 5 times of absorbent charcoal carrier after pickling.
12. induction period according to claim 7 or 8 or 9 or 10 or 11 controllable VCM synthesis Au-based catalyst
Preparation method, it is characterised in that in the first step, absorbent charcoal carrier carries out pickling as follows：Absorbent charcoal carrier is added to matter
Concentration is measured in 1% to 10% hydrochloric acid solution, the quality of hydrochloric acid solution is 2.5 times to 5 times of absorbent charcoal carrier total suction, room
Under the conditions of temperature, closed preservation 24 hours to 25 hours are stood, then by obtained mixture one after washing, suction filtration and separation
Filter cake is obtained, absorbent charcoal carrier after pickling is obtained after filter cake is dried；Or/and, dispersant is isopropanol, isobutanol and n-butanol
One or more of；Or/and, auxiliary agent is one or more of sodium thiosulfate and ATS (Ammonium thiosulphate)；Or/and, the 3rd step, by chlorine
Change barium, which is dissolved into deionized water, obtains barium chloride solution, is then soaked pretreated absorbent charcoal carrier using incipient wetness impregnation method
Pre- absorbent charcoal carrier after dipping is stood closed storage 3 hours to 4 hours, then at 120 DEG C extremely by stain into barium chloride solution
At a temperature of 130 DEG C dry after obtain precursor, wherein, barium chloride account for induction period it is controllable VCM synthesis it is total with Au-based catalyst
The 1% to 5% of quality；Or/and, in the 4th step, mixing time is 3 hours to 6 hours, and dipping is soaked using incipient wetness impregnation method
Stain；Or/and, in the 4th step, the precursor after dipping first stands closed storage 24 hours to 25 hours, is then 130 DEG C in temperature
Induction period controllable VCM synthesis Au-based catalyst is obtained after being dried under conditions of to 150 DEG C.
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