CN105080581A - 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
- Publication number
- CN105080581A CN105080581A CN201510575561.9A CN201510575561A CN105080581A CN 105080581 A CN105080581 A CN 105080581A CN 201510575561 A CN201510575561 A CN 201510575561A CN 105080581 A CN105080581 A CN 105080581A
- Authority
- CN
- China
- Prior art keywords
- chloride
- mercury
- catalyst
- hydrochloric acid
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
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 the low solid mercury catalyst of a kind of compound for acetylene hydrochlorination and preparation method.
Background technology
Vinyl chloride is the monomer preparing polyvinyl chloride (PVC) and copolymer thereof, is one of most important chemical products arranged side by side with ethene and NaOH etc. in the world, is widely used in the every field of national economy.The PVC industry of China, in develop rapidly, according to the energy general layout of domestic " oil-poor, rich coal, weak breath ", adopts acetylene hydrochlorination method to produce in the highest flight.And the use amount of mercuric chleride catalyst to mercury needed for acetylene hydrochlorination method accounts for 60% of national mercury use amount.Step fastener along with the plan of domestic and international mercury pollution prevention and control forces the day by day exhausted of domestic mercury resource into a draw, and generated by polyvinyl chloride by calcium carbide enterprise is faced with baptism.
According to " generated by polyvinyl chloride by calcium carbide industry mercury pollution integrated control scheme " that China puts into effect, calcium carbide legal system PVC used catalyst will progressively to the even mercuryless transformation of low mercury.The large multiplex noble metal platinum of catalyst without mercury newly developed, palladium, gold etc. as main catalytic composition, high cost; Also the various compounds of useful base metal tin, bismuth, copper, zinc etc. are as main catalytic component, expression activitiy is high, but stability is inadequate, also there is the problem of loss, so the industrial applications of catalyst without mercury to there is cost high always, the bottleneck that stability is bad, and the research and development of low-mercury catalyst and promote extremely urgent.
For solving the problem, Some Enterprises and scientific research institutions have carried out the research about mercury catalyst improvement aspect, and this kind of catalyst has been reported in the literature.Patent CN102489306A and CN102441409A adopts step impregnation method to prepare low-mercury catalyst, with active carbon or zeolite as carrier, floods 2-4 time, first floods the auxiliary agents such as bismuth chloride, zinc chloride, titanium chloride, manganese chloride, final impregnating mercury chloride.This method reduces the consumption of mercury chloride while ensureing catalyst performance, reduces catalyst cost.Patent CN102921473A with various material with carbon element (normal activated carbon, spherical activated charcoal, CNT etc.) for raw material, with melamine or urea for modifier, obtain nitrogen modified carbonaceous components, this materials application is made catalyst carrier in acetylene hydrochlorination reaction, and catalyst performance improves.Patent CN102872887A for carrier, first floods mercury chloride with asphaltic base, coal-based or active fruit shell carbon, then with certain proportioning dipping nickel chloride, obtains a kind of Hg-Ni catalyst for acetylene hydrochlorination.Active carbon after drying, is used urea liquid reflow treatment in acid and oxidizing condition surperficial removal of impurities by patent CN102380407A; After heating eliminates urea, with the active carbon after the solution impregnation process of the mercury chloride be dissolved in hydrochloric acid and the auxiliary agent such as bismuth chloride, cerium chloride, then after salt acid elution, be drying to obtain the low-mercury catalyst for acetylene hydrochlorination.This catalyst mercury chloride load capacity is little, and cost is lower, but active and stability is not high.Patent 102500421A first soaks with chloroazotic acid and refluxes in the aqueous solution of triethylamine simultaneously and stir pretreatment ature of coal high-area carbon, then by certain mass ratio add mercury chloride, the chlorination of surfactant cetyl trimethyl by with auxiliary agent nickel chloride, flood in rotary evaporation in vacuo mode, obtained low mercury composite catalyst.Patent CN102085485A and CN102085484A adopts infusion process to prepare low-mercury catalyst, by adding different auxiliary agent, makes catalyst by higher activity or stability.Patent CN102085486A adopts the obtained solid mercury catalyst of infusion process, by adding auxiliary element A (cobalt chloride or manganese chloride) and auxiliary element B (ammonium chloride or potassium chloride), catalyst stability being improved, reducing mercury chloride and running off.Patent CN103551139A take wood activated charcoal as carrier, the adsorbing chlorinated mercury in center, and a kind of ultralow mercury catalyst made by collaborative promoter zinc chloride, barium chloride, potassium chloride and bismuth chloride.Coal mass active carbon after patent CN102151573A adopts process makes carrier, uses vacuum impregnation technology the mercury chloride of lower content and other auxiliary agents to be carried on carrier, and obtains low-mercury catalyst by dry means such as rotary evaporations.
As everyone knows, mercury chloride belongs to covalent compound, and fusing point is 276 DEG C, and boiling point is 302 DEG C, trace volatilization during normal temperature, HgCl
2start volatilization at 114 DEG C, volatilized completely to 180 DEG C.Mercury chloride water soluble, in water, most of mercury chloride is with non-dissociated HgCl
2molecular forms exists, and only has and on a small quantity dissociation occurs, if with the direct load of the mercury chloride of molecular forms on absorbent charcoal carrier, because mercury chloride and absorbent charcoal carrier do not have firmly binding site, just cannot fundamentally solve above-mentioned volatility problem.Therefore want the service life of improving mercuric chleride catalyst, Key technique problem is the volatilization solving mercury chloride, makes firmly combining with carrier of mercury chloride.In addition above patent and report in, although carried out modulation in the modification of the infusion process of low-mercury catalyst, the formula of low-mercury catalyst and carrier, but fundamentally do not solve the loading problem of covalent compound mercury chloride, therefore fundamentally can not solve the stability problem of low-mercury catalyst.
Summary of the invention
In order to overcome that the pollution existed in the preparation method of existing low-mercury catalyst is large, cost is high, catalyst stability is low and the shortcoming of poor activity etc., the invention provides a kind of preparation method of the compound low-mercury catalyst for acetylene hydrochlorination.The present invention adopts two step infusion processes, makes mercury chloride and the muriatic hydrochloric acid solution complexing of alkali metal containing, first in maceration extract, form M in first step dipping process
2hgCl
4complex, covalent compound HgCl
2become HgCl
4 2-the form of complex ion, makes mercury chloride exist with the form of ion, is more easily adsorbed onto on absorbent charcoal carrier, and then introduces other effective auxiliary agents, prepares low-mercury catalyst thus; By weight percentage, catalyst containing the mercury chloride of 4-6.5wt%, the alkali metal chloride of 0.5-10wt%, the chloride auxiliary agents such as the zinc chloride of 1-10wt%, copper chloride, barium chloride and cerium chloride.The stability that the catalyst that the present invention prepares has had in acetylene hydrochlorination reaction, effectively inhibits the volatilization of mercury chloride, thus plays the effect of solid mercury.
The technical solution used in the present invention is:
A preparation method for the low solid mercury catalyst of compound for acetylene hydrochlorination, described preparation method comprises the following steps:
(1) with Pre-Treatment of Activated charcoal for carrier, mercury chloride and alkali metal chloride being dissolved in mass fraction is in the hydrochloric acid solution A of 1 ~ 12wt% (preferably 5 ~ 12wt%), preparation obtains maceration extract A, chloride auxiliary agent being dissolved in mass fraction is in the hydrochloric acid solution B of 1 ~ 12wt% (preferably 5 ~ 12wt%), preparation obtains maceration extract B, the gross mass of mercury chloride, alkali metal chloride, Pre-Treatment of Activated charcoal and chloride auxiliary agent is raw material gross mass, and wherein the mass ratio of mercury chloride, alkali metal chloride and raw material gross mass is 4 ~ 6.5:0.5 ~ 10:100; Described chloride auxiliary agent and the mass ratio of raw material gross mass are 1 ~ 10:100; 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 maceration extract A, fully takes out after dipping, be dried to constant weight, obtain the active carbon after dipping;
(3) active carbon after dipping step (2) obtained adds in maceration extract B, fully takes out after dipping, is dried to constant weight, obtains the low solid mercury catalyst of described compound.
In described step (1), described Pre-Treatment of Activated charcoal generally processes acquisition by the following method: by activated carbon raw material except deashing, at 80 ~ 150 DEG C, be dried to constant weight, obtains Pre-Treatment of Activated charcoal.This is conventional Activated Carbon Pretreatment mode.
Further, mechanical strength >=95% of preferred described activated carbon raw material, specific area 800 ㎡/g ~ 1500 ㎡/g.
Further, preferred described activated carbon raw material is coal-based, wood based or active fruit shell carbon.
In described step (1), described alkali metal chloride is lithium chloride, sodium chloride, potassium chloride, rubidium chloride or cesium chloride.
In described step (1), the mass ratio of preferred mercury chloride, alkali metal chloride and raw material gross mass is 4 ~ 6.5:0.8 ~ 8:100;
Preferably described chloride auxiliary agent and the mass ratio of raw material gross mass are 3 ~ 8:100.
Preferably, step (2) is with step (3), and dipping generally carries 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 be dried to constant weight be generally at 80 ~ 150 DEG C forced air drying to constant weight.
In described step (1), the volumetric usage of described hydrochloric acid solution A generally counts 1.0 ~ 10.0L/kg with the quality consumption of Pre-Treatment of Activated charcoal, preferably 1 ~ 5L/kg; The volumetric usage of described hydrochloric acid solution B generally counts 1 ~ 10L/kg with the quality consumption of Pre-Treatment of Activated charcoal, preferably 1 ~ 5L/kg.The digital code of hydrochloric acid solution A, B, for distinguishing the hydrochloric acid solution for preparing different maceration extract, only playing and referring to differentiation effect, not having chemical sense.
Preferably, in step (1), described chloride auxiliary agent is one of following: the mixing of copper chloride and cerium chloride, the mixing of copper chloride and barium chloride, zinc chloride mix with barium chloride.
Preferred, in described step (1), described chloride auxiliary agent is one of following:
A () chloride auxiliary agent is the mixing of copper chloride and cerium chloride, wherein the mass ratio 3:1:100 of copper chloride, cerium chloride and Pre-Treatment of Activated charcoal;
B () chloride auxiliary agent is copper chloride and the mixing of barium chloride, the wherein mass ratio 5:5:100 of copper chloride, barium chloride and Pre-Treatment of Activated charcoal;
C () chloride auxiliary agent is zinc chloride and the mixing of barium chloride, the wherein mass ratio 3:4:100 of zinc chloride, barium chloride and Pre-Treatment of Activated charcoal.
The present invention also provides the compound prepared by said method low solid mercury catalyst, described catalyst, the mercury chloride containing 4-6.5wt%, the alkali metal chloride of 0.5-10wt%, the chloride auxiliary agent of 1-10wt%.
The low solid mercury catalyst of compound provided by the invention can be used for catalyzing acetylene hydrochlorination.
Beneficial effect of the present invention is embodied in: the present invention adopts two step impregnation technologies, the first step adopts the method for solid mercurial (alkali metal chloride) and mercury chloride total immersion stain that mercury chloride is incorporated into carrier surface with the form of anion, effectively can improve the mercury chloride adsorption effect of low mercury catalyst, reduce the volatilization of mercury chloride, thus improve the stability of catalyst, second step adds other activated metal chloride again, thus obtains the low solid mercury catalyst of the highly active compound of high stability.
The stability of the low solid mercury catalyst of compound prepared by the present invention is better than existing high mercury catalyst, replace expensive mercury chloride with the chloride that price is lower simultaneously, obtained catalyst price is low, and environmental pollution is little, is the low solid mercury catalyst of a kind of desirable high stability compound.Two step impregnation technologies effectively can improve the mercury chloride adsorption effect of low mercury catalyst, and improve its stability in use, thus improve the Activity and stabill of low-mercury catalyst.By low mercury catalyst prepared by this technique, prepare in vinyl chloride reaction at acetylene method, effectively reduce the mercury chloride consumption of low mercury catalyst in use procedure, cost-saving, be a kind of low mercury catalyst preparation technology of environmental protection.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Embodiment 1
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 70g mercury chloride and 10g potassium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 20 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 30g copper chloride and 10g cerium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,25 DEG C flood 15 hours, then at 150 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 6.15%, dries the loss late 1.8% of burning 3 hours mercury chloride under 250 DEG C of conditions, lower than national standard requires 3%, complies with the national standard requirements.Be used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 2:
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 5wt%, volume is 2.5L, dissolves 80g mercury chloride and 100g potassium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 80 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 5wt%, volume is 2.5L, dissolves 50g copper chloride and 50g barium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,80 DEG C flood 15 hours, then at 120 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 5.65%, dries the loss late 0.8% of burning 3 hours mercury chloride under 250 DEG C of conditions, is used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 3:
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 12wt%, volume is 2.0L, dissolves 80g mercury chloride and 100g cesium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 80 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 5wt%, volume is 2.5L, dissolves 50g copper chloride and 50g barium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,80 DEG C flood 15 hours, then at 120 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 6.25%, dries the loss late 1.3% of burning 3 hours mercury chloride under 250 DEG C of conditions, is used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 4:
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 12wt%, volume is 2.0L, dissolves 80g mercury chloride and 100g rubidium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 80 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 5wt%, volume is 2.5L, dissolves 50g copper chloride and 50g barium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,80 DEG C flood 15 hours, then at 120 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 6.02%, dries the loss late 1.2% of burning 3 hours mercury chloride under 250 DEG C of conditions, is used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 5
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 70g mercury chloride and 50g sodium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 20 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 30g copper chloride and 10g cerium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,25 DEG C flood 15 hours, then at 150 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 5.85%, dries the loss late 1.5% of burning 3 hours mercury chloride under 250 DEG C of conditions, lower than national standard requires 3%, complies with the national standard requirements.Be used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 6
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 70g mercury chloride and 50g sodium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 20 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 2.5L, dissolves 30g zinc chloride and 40g barium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,25 DEG C flood 15 hours, then at 150 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 5.85%, dries the loss late 0.50% of burning 3 hours mercury chloride under 250 DEG C of conditions, lower than national standard requires 3%, complies with the national standard requirements.Be used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Embodiment 7
1. by active carbon through pretreatment, except deashing, at 120 DEG C, being dried to constant weight, obtaining pretreated active carbon;
2. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 1L, dissolves 80g mercury chloride and 100g sodium chloride, as maceration extract A in aqueous hydrochloric acid solution;
3. taking the pretreated active carbon that 1kg is dried to constant weight adds in maceration extract A, 20 DEG C of dippings 15 hours, and the absorbent charcoal carrier that will impregnated of active component takes out, at 120 DEG C, be dried to constant weight;
4. prepare the aqueous hydrochloric acid solution of 10wt%, volume is 5L, dissolves 30g zinc chloride and 40g barium chloride, as maceration extract B in aqueous hydrochloric acid solution;
5. add in maceration extract B by the active carbon after the dipping obtained in step 3,25 DEG C flood 15 hours, then at 150 DEG C, are dried to constant weight, obtain a kind of high stability compound low mercury catalyst.
Testing product meets " VCM synthesis low mercury catalyst " HG/T4192-2011 standard-required, chloride containing mercury 6.0%, dries the loss late 1.20% of burning 3 hours mercury chloride under 250 DEG C of conditions, lower than national standard requires 3%, complies with the national standard requirements.Be used in acetylene hydrochlorination reaction, conversion of alkyne is greater than 99%, and vinyl chloride is selective is greater than 99%.Loss late index is starkly lower than commodity low-mercury catalyst, has better stability and service life.
Claims (8)
1., for a preparation method for the low solid mercury catalyst of compound of acetylene hydrochlorination, it is characterized in that said method comprising the steps of:
(1) with Pre-Treatment of Activated charcoal for carrier, mercury chloride and alkali metal chloride being dissolved in mass fraction is in the hydrochloric acid solution A of 1 ~ 12wt%, preparation obtain maceration extract A; Chloride auxiliary agent being dissolved in mass fraction is in the hydrochloric acid solution B of 1 ~ 12wt%, preparation obtains maceration extract B, the gross mass of mercury chloride, alkali metal chloride, Pre-Treatment of Activated charcoal and chloride auxiliary agent is raw material gross mass, and wherein the mass ratio of mercury chloride, alkali metal chloride and raw material gross mass is 4 ~ 6.5:0.5 ~ 10:100; Described chloride auxiliary agent and the mass ratio of raw material gross mass are 1 ~ 10:100; 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 maceration extract A, fully takes out after dipping, be dried to constant weight, obtain the active carbon after dipping;
(3) active carbon after dipping step (2) obtained adds in maceration extract B, fully takes out after dipping, is dried to constant weight, obtains the low solid mercury catalyst of described compound.
2. the method for claim 1, is characterized in that, in described step (1), described alkali metal chloride is lithium chloride, sodium chloride, potassium chloride, rubidium chloride or cesium chloride.
3. the method for claim 1, is characterized in that in described step (1), and the volumetric usage of described hydrochloric acid solution A counts 1.0 ~ 10.0L/kg with the quality consumption of Pre-Treatment of Activated charcoal; The volumetric usage of described hydrochloric acid solution B counts 1 ~ 10L/kg with the quality consumption of Pre-Treatment of Activated charcoal.
4. the method for claim 1, is characterized in that in described step (1), and described chloride auxiliary agent is one of following: the mixing of copper chloride and cerium chloride, the mixing of copper chloride and barium chloride, zinc chloride mix with barium chloride.
5. the method for claim 1, is characterized in that, in described step (1), described Pre-Treatment of Activated charcoal processes acquisition by the following method: by activated carbon raw material except deashing, at 80 ~ 150 DEG C, be dried to constant weight, obtains Pre-Treatment of Activated charcoal.
6. method as claimed in claim 5, is characterized in that mechanical strength >=95% of described activated carbon raw material, specific area 800 ㎡/g ~ 1500 ㎡/g.
7. method as claimed in claim 5, is characterized in that described activated carbon raw material is coal-based, wood based or active fruit shell carbon.
8. the low solid mercury catalyst of the compound that the method as described in one of claim 1 ~ 7 prepares, the low solid catalyst of described compound by weight percentage, mercury chloride containing 4-6.5wt%, the alkali metal chloride of 0.5-10wt% and the chloride auxiliary agent of 1-10wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510575561.9A CN105080581B (en) | 2015-09-11 | 2015-09-11 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510575561.9A CN105080581B (en) | 2015-09-11 | 2015-09-11 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105080581A true CN105080581A (en) | 2015-11-25 |
| CN105080581B CN105080581B (en) | 2017-05-17 |
Family
ID=54562446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510575561.9A Active CN105080581B (en) | 2015-09-11 | 2015-09-11 | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105080581B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110227508A (en) * | 2019-06-17 | 2019-09-13 | 浙江工业大学 | A kind of monatomic mercury catalyst and its preparation method and application |
| 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 |
| 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 |
| CN111346662A (en) * | 2020-04-16 | 2020-06-30 | 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| CN102527415A (en) * | 2010-12-14 | 2012-07-04 | 新晃新中化工有限责任公司 | Low-mercury compound mercury catalyst and its preparation method |
| CN103203241A (en) * | 2013-04-25 | 2013-07-17 | 新疆天业（集团）有限公司 | Low-mercury catalyst for hydrochlorination of acetylene |
| US20140213437A1 (en) * | 2013-01-30 | 2014-07-31 | Tsinghua University | Gold-based catalysts for acetylene hydrochlorination |
-
2015
- 2015-09-11 CN CN201510575561.9A patent/CN105080581B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527415A (en) * | 2010-12-14 | 2012-07-04 | 新晃新中化工有限责任公司 | Low-mercury compound mercury catalyst and its preparation method |
| CN102380407A (en) * | 2011-08-25 | 2012-03-21 | 成都惠恩精细化工有限责任公司 | Low-mercury catalyst for acetylene hydrochlorination |
| CN102489306A (en) * | 2011-11-25 | 2012-06-13 | 贵州大学 | Low-mercury catalyst for synthesizing vinyl chloride |
| US20140213437A1 (en) * | 2013-01-30 | 2014-07-31 | Tsinghua University | Gold-based catalysts for acetylene hydrochlorination |
| CN103203241A (en) * | 2013-04-25 | 2013-07-17 | 新疆天业（集团）有限公司 | Low-mercury catalyst for hydrochlorination of acetylene |
Non-Patent Citations (5)
| Title |
|---|
| 吴晓茜: "乙炔氢氯化反应低汞催化剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 吴晓茜等: "乙炔法合成氯乙烯催化剂的研究进展", 《工业催化》 * |
| 周莹等: "乙炔氢氯化低汞催化剂的研究进展", 《聚氯乙烯》 * |
| 支林轩等: "乙炔氢氯化反应制备氯乙烯低固汞催化剂失活机理", 《化学反应工程与工艺》 * |
| 王鹏程等: "多元配方乙炔氢氯化反应催化剂研究进展", 《聚氯乙烯》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN110227508A (en) * | 2019-06-17 | 2019-09-13 | 浙江工业大学 | A kind of monatomic mercury catalyst and its preparation method and application |
| 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 |
| CN111346662A (en) * | 2020-04-16 | 2020-06-30 | 郑州大学 | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105080581B (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105080581A (en) | Composite low solid mercury catalyst used for acetylene hydrochlorination and preparation method thereof | |
| CN105126878B (en) | A kind of composition metal salt catalyst for acetylene hydrochlorination reaction | |
| CN103272619A (en) | Anion modified mercury-free catalyst for ethyne hydrochlorination reaction, and preparation method thereof | |
| CN101332992A (en) | Method for preparing tung cell-based active carbon by zinc chloride chemical activation method | |
| CN108295876A (en) | A kind of preparation method of low-mercury catalyst and application | |
| CN102151573B (en) | Preparation method of low-mercury catalyst for preparing vinyl chloride | |
| CN105060290A (en) | Preparation method of coal-based activated carbon with low ash and high specific surface area | |
| CN103203241B (en) | Low-mercury catalyst for hydrochlorination of acetylene | |
| CN108273536A (en) | A kind of preparation method of N doping three-dimensional porous nano ferrum-based catalyst | |
| CN103191764B (en) | Mercury-free catalyst for synthesizing vinyl chloride through acetylene hydrochlorination and preparation method thereof | |
| CN103586006A (en) | Method of aminopyridine modified resin for adsorbing rhodium octanoate dimer and metal ions | |
| CN104667935A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN104998631A (en) | Nitrogen-doped graphene, Pd-loaded nitrogen-doped graphene catalyst and preparation method and application thereof | |
| CN104667985A (en) | Catalytic wet oxidation catalyst and preparation method thereof | |
| CN105664850B (en) | A kind of preparation method and applications of high performance carbon base carbon dioxide sorbing material | |
| CN102085486A (en) | Solid mercury catalyst for acetylene hydrochlorination | |
| CN107434980A (en) | A kind of preparation of activated carbon and the method for the absorption desulfurization of refinery's distillate | |
| CN105080574B (en) | A kind of highly acid multiplex catalyst for acetylene hydrochlorination reaction | |
| CN113941344A (en) | Phosphorus modified activated carbon and low-mercury catalyst prepared by taking phosphorus modified activated carbon as carrier | |
| CN111346662B (en) | Preparation method, product and application of nitrogen-doped activated carbon-loaded ultralow-mercury catalyst | |
| CN105032455A (en) | Ultralow-mercury catalyst used for acetylene hydrochlorination | |
| CN108786802A (en) | A kind of room temperature purify the air of a room pollutant method for preparing catalyst and its application | |
| CN105858659A (en) | Peanut shell activated carbon capable of adsorbing formaldehyde and preparation method thereof | |
| CN104667936A (en) | Method for preparing catalytic wet oxidation catalyst | |
| CN110227507A (en) | A kind of ultralow mercury catalyst of high stability and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |