CN105080581B - Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof - Google Patents
Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite low solid mercury catalyst used for acetylene hydrochlorination. The preparation method comprises the steps of firstly dissolving mercury chloride and alkali chloride into a hydrochloric acid solution to prepare impregnation liquid A, dissolving a chloride assistant into the hydrochloric acid solution to prepare impregnation liquid B, sufficiently impregnating pretreated activated carbon in the impregnation liquid A, then sufficiently impregnating the impregnated activated carbon in the impregnation liquid B, and drying to prepare the composite low mercury catalyst. In the prepared composite low solid mercury catalyst, the loading amount of mercury chloride is 4-6.5wt%, the loading amount of alkali chloride is 0.5-10wt%, and the loading amount of the chloride assistant is 1-10wt%. According to the preparation method, two impregnation steps are adopted, wherein in the first impregnation step, mercury chloride is introduced to the surface of a carrier in a negative ion manner by adopting the co-impregnation method of a solid mercury agent and mercury chloride, the adsorption effect of mercury chloride of the low mercury catalyst can be effectively improved, the volatilization amount of mercury chloride can be reduced, and the stability of the catalyst can be improved; and in the second impregnation step, other active metal chloride is added, so that the composite low solid mercury catalyst with high stability and high activity can be obtained.
Description
Technical field
The present invention relates to a kind of compound low solid mercury catalyst and preparation method for acetylene hydrochlorination.
Background technology
Vinyl chloride is the monomer for preparing polrvinyl chloride (PVC) and its copolymer, is in the world and ethylene and sodium hydroxide
Etc. one of most important chemical products arranged side by side, the every field of national economy is widely used in.The PVC industries of China are rapidly being sent out
Exhibition, according to the energy general layout of domestic " oil-poor, rich coal, few gas ", is produced in the highest flight using acetylene hydrochlorination method.And acetylene hydrogen
Mercuric chleride catalyst needed for chloridising accounts for the 60% of national hydrargyrum usage amount to the usage amount of hydrargyrum.With domestic and international mercury pollution prevention and control
The step fastener of plan force the day by day exhausted of domestic hydrargyrum resource into a draw, generated by polyvinyl chloride by calcium carbide enterprise is faced with baptism.
Put into effect according to China《Generated by polyvinyl chloride by calcium carbide industry mercury pollution integrated control scheme》, used by carbide legal system PVC
Catalyst will progressively to the even mercuryless transformation of low hydrargyrum.The conducts such as catalyst without mercury newly developed big multiplex noble metal platinum, palladium, gold
Main catalytic composition, high cost；Also the various compounds of useful base metal stannum, bismuth, copper, zinc etc. are living as main catalytic component
Property it is higher, but stability is not enough, the problem of loss is there is also, so the industrial applications of catalyst without mercury have always cost
Height, the bad bottleneck of stability, and the research and development of low-mercury catalyst and popularization are extremely urgent.
To solve the above problems, Some Enterprises and scientific research institutions carried out about mercury catalyst improvement in terms of research, this
Class catalyst has been reported in the literature.Patent CN102489306A and CN102441409A prepare low hydrargyrum using step impregnation method
Catalyst, with activated carbon or zeolite as carrier, impregnates 2-4 time, first impregnates bismuth chloride, zinc chloride, titanium chloride, manganese chloride etc. and helps
Agent, final impregnating mercuric chloride.This method reduces the consumption of mercuric chloride while catalyst performance is ensured, reduce catalyst into
This.Patent CN102921473A with various material with carbon elements (normal activated carbon, ball shape active carbon, CNT etc.) as raw material, with three
Poly cyanamid or carbamide are modifying agent, obtain nitrogen modified carbonaceous components, the materials application is made into catalyst in acetylene hydrochlorination reaction and is carried
Body, catalyst performance is improved.Patent CN102872887A impregnates chlorination as carrier, first with asphaltic base, coal base or active fruit shell carbon
Hydrargyrum, then with certain proportioning dipping Nickel dichloride., obtain a kind of Hg-Ni catalyst for acetylene hydrochlorination.Patent
Activated carbon in acid and oxidizing condition surface remove impurity and after drying, is used urea liquid reflow treatment by CN102380407A；Heating
After eliminating carbamide, use and be dissolved in the activated carbon after the solution impregnation of the auxiliary agent such as the mercuric chloride in hydrochloric acid and bismuth chloride, cerium chloride is processed,
It is drying to obtain the low-mercury catalyst for acetylene hydrochlorination Jing after salt acid elution again.The catalyst mercuric chloride load capacity is little, cost
It is relatively low, but activity and stability is not high.Patent 102500421A is first returned simultaneously with chloroazotic acid immersion and in the aqueous solution of triethylamine
Pretreatment ature of coal high-area carbon is flowed and stirs, then by certain mass than adding mercuric chloride, surfactant cetyl trimethyl
Chlorination is pressed and auxiliary agent Nickel dichloride., is impregnated in rotary evaporation in vacuo mode, and low hydrargyrum composite catalyst is obtained.Patent
CN102085485A and CN102085484A prepare low-mercury catalyst using infusion process, by adding different auxiliary agents, make catalyst
By higher activity or stability.Patent CN102085486A is obtained solid mercury catalyst using infusion process, is aided in into by adding
Divide A (cobaltous chloride or manganese chloride) and auxiliary element B (ammonium chloride or potassium chloride), improve catalyst stability, reduce mercuric chloride
It is lost in.Patent CN103551139A with wood activated charcoal as carrier, the adsorbing chlorinated hydrargyrum in center, collaboration accelerator zinc chloride,
Barium chloride, potassium chloride and bismuth chloride make a kind of ultralow mercury catalyst.Patent CN102151573A is lived using the ature of coal after processing
Property charcoal make carrier, the mercuric chloride of lower content and other auxiliary agents are carried on carrier using vacuum impregnation technology, and by rotation
The drying means such as evaporation are obtained low-mercury catalyst.
It is well known that mercuric chloride belongs to covalent compound, fusing point is 276 DEG C, and boiling point is 302 DEG C, micro volatilization during room temperature,
HgCl2Start volatilization at 114 DEG C, volatilized completely to 180 DEG C.Mercuric chloride water soluble, in water most of mercuric chloride with
Non-dissociated HgCl2Molecular forms are present, and only dissociate on a small quantity, if being directly loaded in work with the mercuric chloride of molecular forms
On property high-area carbon, because mercuric chloride and absorbent charcoal carrier do not have firm binding site, above-mentioned waving just cannot be fundamentally solved
Send out sex chromosome mosaicism.Therefore the service life for improving mercuric chleride catalyst is wanted, Key technique problem is the volatilization for solving mercuric chloride, is made
Obtain the firm with carrier of mercuric chloride to combine.In other above patent and report, although the infusion process, low hydrargyrum to low-mercury catalyst is urged
Modulation is carried out on the formula of agent and the modified of carrier, but has not fundamentally solved the negative of covalent compound mercuric chloride
Load problem, therefore can not fundamentally solve the stability problem of low-mercury catalyst.
The content of the invention
In order to overcome big pollution present in the preparation method of existing low-mercury catalyst, high cost, catalyst stability low
With the shortcoming of poor activity etc., a kind of preparation method of the compound low-mercury catalyst for acetylene hydrochlorination of present invention offer.This
It is bright to adopt two step infusion processes, mercuric chloride and the muriatic hydrochloric acid solution complexation of alkali metal containing are made in first step dipping process, it is first
First M is formed in impregnation liquid2HgCl4Coordination compound, covalent compound HgCl2Become HgCl4 2-The form of complex ion, makes chlorination
Hydrargyrum is in the form of ion, it is easier to be adsorbed onto on absorbent charcoal carrier, is then re-introduced into other effective auxiliary agents, is thus prepared into
To low-mercury catalyst；By weight percentage, mercuric chloride of the catalyst containing 4-6.5wt%, the alkali metal chlorination of 0.5-10wt%
The chloride auxiliary agents such as thing, the zinc chloride of 1-10wt%, copper chloride, barium chloride and cerium chloride.The catalyst that the present invention is prepared
The stability having had in acetylene hydrochlorination reaction, effectively inhibits the volatilization of mercuric chloride, so as to play the effect of solid hydrargyrum.
The technical solution used in the present invention is：
A kind of preparation method of the compound low solid mercury catalyst for acetylene hydrochlorination, described preparation method includes following
Step：
(1) with Pre-Treatment of Activated charcoal as carrier, by mercuric chloride and alkali metal chloride be dissolved in mass fraction for 1~
In the hydrochloric acid solution A of 12wt% (preferably 5~12wt%), preparation obtains impregnation liquid A, and chloride auxiliary agent is dissolved in into mass fraction
In hydrochloric acid solution B for 1~12wt% (preferably 5~12wt%), preparation obtains impregnation liquid B, mercuric chloride, alkali metal chloride,
The gross mass of Pre-Treatment of Activated charcoal and chloride auxiliary agent is raw material gross mass, and wherein mercuric chloride, alkali metal chloride and raw material is total
The mass ratio of quality is 4~6.5:0.5~10：100；Described chloride auxiliary agent is 1~10 with the mass ratio of raw material gross mass：
100；Described chloride auxiliary agent is one or more the mixing in zinc chloride, copper chloride, cerium chloride and barium chloride；
(2) Pre-Treatment of Activated charcoal is dipped in impregnation liquid A, takes out after being sufficiently impregnated with, is dried to constant weight, after being impregnated
Activated carbon；
(3) activated carbon after the dipping for obtaining step (2) is added in impregnation liquid B, is taken out after being sufficiently impregnated with, and is dried to perseverance
Weight, obtains described compound low solid mercury catalyst.
In the step (1), the Pre-Treatment of Activated charcoal is typically processed by the following method and obtained：Activated carbon raw material is removed
Ash, is dried to constant weight at 80~150 DEG C, obtains Pre-Treatment of Activated charcoal.This is conventional Activated Carbon Pretreatment mode.
Further, mechanical strength >=95% of the preferred activated carbon raw material, 800 ㎡ of specific surface area/g~1500 ㎡/g.
Further, preferably the activated carbon raw material is coal base, wooden base or active fruit shell carbon.
In the step (1), the alkali metal chloride is lithium chloride, Sodium Chloride, potassium chloride, Rubinorm (Ifi). or cesium chloride.
In the step (1), the mass ratio of preferred mercuric chloride, alkali metal chloride and raw material gross mass is 4~6.5:0.8
~8：100；
It is preferred that described chloride auxiliary agent is 3~8 with the mass ratio of raw material gross mass：100.
Preferably, in step (2) and step (3), dipping is typically carried out at 20~80 DEG C, and dip time is preferably 2~
24 hours, more preferably 15~24 hours.
Preferably, in step (2) and step (3), described drying to constant weight is usually the forced air drying at 80~150 DEG C
To constant weight.
In the step (1), the volumetric usage of the hydrochloric acid solution A is typically calculated as with the quality consumption of Pre-Treatment of Activated charcoal
1.0~10.0L/kg, preferably 1~5L/kg；The volumetric usage of described hydrochloric acid solution B is with the quality consumption of Pre-Treatment of Activated charcoal
Typically it is calculated as 1~10L/kg, preferably 1~5L/kg.The digital code of hydrochloric acid solution A, B is used to distinguish for preparing different dippings
The hydrochloric acid solution of liquid, only plays and refers to differentiation effect, not with chemical sense.
Preferably, in step (1), the chloride auxiliary agent is one of following：The mixing of copper chloride and cerium chloride, copper chloride
The mixing of mixing, zinc chloride and barium chloride with barium chloride.
It is furthermore preferred that in the step (1), the chloride auxiliary agent is one of following：
A () chloride auxiliary agent is the mixing of copper chloride and cerium chloride, wherein copper chloride, cerium chloride and Pre-Treatment of Activated charcoal
Mass ratio 3：1：100；
B () chloride auxiliary agent is the mixing of copper chloride and barium chloride, wherein copper chloride, barium chloride and Pre-Treatment of Activated charcoal
Mass ratio 5：5：100；
C () chloride auxiliary agent is the mixing of zinc chloride and barium chloride, wherein zinc chloride, barium chloride and Pre-Treatment of Activated charcoal
Mass ratio 3：4：100.
The present invention also provides the compound low solid mercury catalyst prepared by said method, and the catalyst is with weight percent
Than meter, the mercuric chloride containing 4-6.5wt%, the alkali metal chloride of 0.5-10wt%, the chloride auxiliary agent of 1-10wt%.
The compound low solid mercury catalyst that the present invention is provided can be used for catalyzing acetylene hydrochlorination.
Beneficial effects of the present invention are embodied in：The present invention adopts two step impregnation technologies, and the first step is using solid mercurial (alkali metal
Chloride) and the method for mercuric chloride co-impregnation mercuric chloride is incorporated into into carrier surface in the form of anion, can effectively improve
The mercuric chloride adsorption effect of low mercury catalyst, reduces the volatilization of mercuric chloride, and so as to improve the stability of catalyst, second step is added
Other activated metal chlorides, so as to obtain the low solid mercury catalyst of the highly active compound recipe of high stability.
The stability of compound low solid mercury catalyst prepared by the present invention is better than existing high mercury catalyst, while relatively low with price
Chloride replace expensive mercuric chloride, obtained catalyst price is low, and environmental pollution is little, is a kind of preferable high stability
Compound low solid mercury catalyst.Two step impregnation technologies can effectively improve the mercuric chloride adsorption effect of low mercury catalyst, and improve it and make
Stability with during, so as to improve the Activity and stabill of low-mercury catalyst.The low mercury catalyst prepared by the technique,
Prepare in chloroethene alkene reaction in acetylene method, effectively reduce low mercury catalyst in the mercuric chloride consumption using process, it is cost-effective, it is one
The low mercury catalyst preparation technology for planting environmental protection.
Specific embodiment
Illustrate technical scheme, but protection scope of the present invention not limited to this with specific embodiment below.
Embodiment 1
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 70g mercuric chloride and 10g are dissolved in aqueous hydrochloric acid solution
Potassium chloride, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 20 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 30g copper chlorides and 10g are dissolved in aqueous hydrochloric acid solution
Cerium chloride, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 25 DEG C impregnate 15 hours, then 150
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
6.15%, the loss rate 1.8% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, 3% required less than national standard meets state
Family's standard is required.In acetylene hydrochlorination reaction, conversion of alkyne is more than 99%, and vinyl chloride selectivity is more than 99%.Loss
Rate index is significantly lower than commodity low-mercury catalyst, with more preferable stability and service life.
Embodiment 2：
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 5wt% is prepared, volume is 2.5L, 80g mercuric chloride and 100g are dissolved in aqueous hydrochloric acid solution
Potassium chloride, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 80 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 5wt% is prepared, volume is 2.5L, 50g copper chlorides and 50g chlorine are dissolved in aqueous hydrochloric acid solution
Change barium, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 80 DEG C impregnate 15 hours, then 120
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
5.65%, the loss rate 0.8% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, in acetylene hydrochlorination reaction, acetylene turns
Rate is more than 99%, and vinyl chloride selectivity is more than 99%.Loss rate index is significantly lower than commodity low-mercury catalyst, with more preferably steady
Qualitative and service life.
Embodiment 3：
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 12wt% is prepared, volume is 2.0L, 80g mercuric chloride and 100g are dissolved in aqueous hydrochloric acid solution
Cesium chloride, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 80 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 5wt% is prepared, volume is 2.5L, 50g copper chlorides and 50g chlorine are dissolved in aqueous hydrochloric acid solution
Change barium, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 80 DEG C impregnate 15 hours, then 120
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
6.25%, the loss rate 1.3% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, in acetylene hydrochlorination reaction, acetylene turns
Rate is more than 99%, and vinyl chloride selectivity is more than 99%.Loss rate index is significantly lower than commodity low-mercury catalyst, with more preferably steady
Qualitative and service life.
Embodiment 4：
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 12wt% is prepared, volume is 2.0L, 80g mercuric chloride and 100g are dissolved in aqueous hydrochloric acid solution
Rubinorm (Ifi)., as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 80 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 5wt% is prepared, volume is 2.5L, 50g copper chlorides and 50g chlorine are dissolved in aqueous hydrochloric acid solution
Change barium, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 80 DEG C impregnate 15 hours, then 120
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
6.02%, the loss rate 1.2% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, in acetylene hydrochlorination reaction, acetylene turns
Rate is more than 99%, and vinyl chloride selectivity is more than 99%.Loss rate index is significantly lower than commodity low-mercury catalyst, with more preferably steady
Qualitative and service life.
Embodiment 5
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 70g mercuric chloride and 50g are dissolved in aqueous hydrochloric acid solution
Sodium Chloride, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 20 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 30g copper chlorides and 10g are dissolved in aqueous hydrochloric acid solution
Cerium chloride, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 25 DEG C impregnate 15 hours, then 150
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
5.85%, the loss rate 1.5% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, 3% required less than national standard meets state
Family's standard is required.In acetylene hydrochlorination reaction, conversion of alkyne is more than 99%, and vinyl chloride selectivity is more than 99%.Loss
Rate index is significantly lower than commodity low-mercury catalyst, with more preferable stability and service life.
Embodiment 6
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 70g mercuric chloride and 50g are dissolved in aqueous hydrochloric acid solution
Sodium Chloride, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 20 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 2.5L, 30g zinc chloride and 40g are dissolved in aqueous hydrochloric acid solution
Barium chloride, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 25 DEG C impregnate 15 hours, then 150
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
5.85%, the loss rate 0.50% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, 3% required less than national standard meets
National standard is required.In acetylene hydrochlorination reaction, conversion of alkyne is more than 99%, and vinyl chloride selectivity is more than 99%.Damage
Mistake rate index is significantly lower than commodity low-mercury catalyst, with more preferable stability and service life.
Embodiment 7
Activated carbon is preprocessed 1., except deashing, it is dried at 120 DEG C to constant weight, obtain pretreated activated carbon；
2. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 1L, 80g mercuric chloride and 100g chlorine are dissolved in aqueous hydrochloric acid solution
Change sodium, as impregnation liquid A；
3. weigh 1kg to be dried into the pretreated activated carbon addition impregnation liquid A of constant weight, 20 DEG C impregnate 15 hours, will
Take out impregnated of the absorbent charcoal carrier of active component, be dried to constant weight at 120 DEG C；
4. the aqueous hydrochloric acid solution of 10wt% is prepared, volume is 5L, 30g zinc chloride and 40g chlorine are dissolved in aqueous hydrochloric acid solution
Change barium, as impregnation liquid B；
5. the activated carbon after the dipping obtained in step 3 is added in impregnation liquid B, 25 DEG C impregnate 15 hours, then 150
It is dried to constant weight at DEG C, obtains a kind of compound low mercury catalyst of high stability.
Detection product meets《VCM synthesis low mercury catalyst》The requirement of HG/T4192-2011 standards, chloride containing hydrargyrum
6.0%, the loss rate 1.20% of 3 hours mercuric chloride of fire under the conditions of 250 DEG C, 3% required less than national standard meets state
Family's standard is required.In acetylene hydrochlorination reaction, conversion of alkyne is more than 99%, and vinyl chloride selectivity is more than 99%.Loss
Rate index is significantly lower than commodity low-mercury catalyst, with more preferable stability and service life.
Claims (8)
1. a kind of preparation method of the compound low solid mercury catalyst for acetylene hydrochlorination, it is characterised in that methods described include with
Lower step：
(1) with Pre-Treatment of Activated charcoal as carrier, it is 1~12wt%'s that mercuric chloride and alkali metal chloride are dissolved in into mass fraction
In hydrochloric acid solution A, preparation obtains impregnation liquid A；Chloride auxiliary agent is dissolved in into the hydrochloric acid solution B that mass fraction is 1~12wt%
In, preparation obtains impregnation liquid B, and the gross mass of mercuric chloride, alkali metal chloride, Pre-Treatment of Activated charcoal and chloride auxiliary agent is raw material
The mass ratio of gross mass, wherein mercuric chloride, alkali metal chloride and raw material gross mass is 4~6.5:0.5~10：100；Described
Chloride auxiliary agent is 1~10 with the mass ratio of raw material gross mass：100；Described chloride auxiliary agent is zinc chloride, copper chloride, chlorine
Change cerium and one or more the mixing in barium chloride；
(2) Pre-Treatment of Activated charcoal is dipped in impregnation liquid A, takes out after being sufficiently impregnated with, is dried to constant weight, the activity after being impregnated
Charcoal；
(3) activated carbon after the dipping for obtaining step (2) is added in impregnation liquid B, is taken out after being sufficiently impregnated with, and is dried to constant weight,
Obtain described compound low solid mercury catalyst.
2. the method for claim 1, it is characterised in that in the step (1), the alkali metal chloride be lithium chloride,
Sodium Chloride, potassium chloride, Rubinorm (Ifi). or cesium chloride.
3. the method for claim 1, it is characterised in that in the step (1), the volumetric usage of the hydrochloric acid solution A with
The quality consumption of Pre-Treatment of Activated charcoal is calculated as 1.0~10.0L/kg；The volumetric usage of described hydrochloric acid solution B is with Pre-Treatment of Activated
The quality consumption of charcoal is calculated as 1~10L/kg.
4. the method for claim 1, it is characterised in that in the step (1), the chloride auxiliary agent is one of following：
The mixing of the mixing of copper chloride and cerium chloride, the mixing of copper chloride and barium chloride, zinc chloride and barium chloride.
5. the method for claim 1, it is characterised in that in the step (1), the Pre-Treatment of Activated charcoal is pressed with lower section
Method process is obtained：By activated carbon raw material except deashing, it is dried at 80~150 DEG C to constant weight, obtains Pre-Treatment of Activated charcoal.
6. method as claimed in claim 5, it is characterised in that mechanical strength >=95% of the activated carbon raw material, specific surface area
800 ㎡/g~1500 ㎡/g.
7. method as claimed in claim 5, it is characterised in that the activated carbon raw material is coal base, wooden base or shell activity
Charcoal.
8. the compound low solid mercury catalyst that the method as described in one of claim 1~7 is prepared, it is described to be combined low solid catalysis
Agent by weight percentage, the mercuric chloride containing 4-6.5wt%, the alkali metal chloride of 0.5-10wt% and the chlorine of 1-10wt%
Compound auxiliary agent.
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| CN107456989A (en) * | 2017-08-29 | 2017-12-12 | 贵州重力科技环保有限公司 | A kind of high degree of dispersion nanometer catalyst without mercury of acetylene hydrochlorination and preparation method thereof |
| CN107486224A (en) * | 2017-08-29 | 2017-12-19 | 贵州重力科技环保有限公司 | A kind of ultralow solid mercury catalyst of high catalytic conversion and preparation method thereof |
| CN110756192A (en) * | 2018-07-27 | 2020-02-07 | 安徽华塑股份有限公司 | High-activity composite environment-friendly low-mercury catalyst and production process thereof |
| CN110227508B (en) * | 2019-06-17 | 2021-12-07 | 浙江工业大学 | Monoatomic mercury catalyst and preparation method and application thereof |
| CN110833838A (en) * | 2019-11-18 | 2020-02-25 | 铜仁市万山区昊海化工有限公司 | Ultra-low mercury catalyst and preparation method thereof |
| CN111346662B (en) * | 2020-04-16 | 2023-03-31 | 郑州大学 | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst |
| CN113941344A (en) * | 2021-09-30 | 2022-01-18 | 浙江工业大学 | Phosphorus modified activated carbon and low-mercury catalyst prepared by taking phosphorus modified activated carbon as carrier |
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