CN102380407B - Low-mercury catalyst for acetylene hydrochlorination - Google Patents
Low-mercury catalyst for acetylene hydrochlorination Download PDFInfo
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Abstract
Disclosed is a low-mercury catalyst for acetylene hydrochlorination. Mercuric chloride is carried on activated carbon. Raw materials comprise, by weight, 100 parts of activated carbon, 4-5 parts of mercuric chloride, 8-10 parts of total essential assistant, 1-5 parts of total non-essential assistant, wherein the essential assistant comprises 2-5 parts of bismuth chloride, 1-5 parts of cerium chloride, 1-5 parts of barium chloride and 2-5 parts of copper chloride; and the non-essential assistant comprises at least one of potassium chloride, phosphoric acid, zinc chloride and cuprous chloride. After being subjected to surface subtraction and drying on acid and oxidizing conditions, activated carbon is in reflux treatment with urea solution; and the catalyst can be prepared by soaking the treated activated carbon with HgC12 dissolved in hydrochloric acid and assistant solution sufficiently after urea is removed by steps of heating, washing the activated carbon with hydrochloric acid and finally drying the same. The carrying capacity of mercuric chloride in the catalyst is lower so that cost for the catalyst is reduced and consumption of mercury resources is decreased. Furthermore, activity and stability of the low-mercury catalyst are much higher than those of the existing high-mercury catalyst, and reforming rate and selectivity of reaction of vinyl chloride can be 99.7% and be higher than 99.8%. Accordingly, the low-mercury catalyst for acetylene hydrochlorination is suitable for industry production and is environment-friendly.
Description
Technical field
The present invention relates to a kind of for by the catalyst of acetylene through the low mercury content of preparing vinyl chloride by hydrochlorination, and the preparation method of this catalyst.
Background technology
By the synthetic polyvinyl chloride (PVC) of VCM, be one of thermoplastic articles raw material of output maximum in the world, be widely used in the fields such as materials for construction, packaging material, electric equipment products, medical industry, coating and adhesive.
The suitability for industrialized production of present synthesizing chloroethylene monomer in the world is take ethylene process as main.Be subjected to the larger impact of crude oil price fluctuation, by acetylene, through hydrochlorinate, produce PVC and occupy at home critical role.At present industrial acetylene hydrochlorination reaction, what mainly use is that the mercury chloride load capacity is 12% ~ 15% high mercury catalyst, its consumption to mercury accounts for 60% of domestic mercury use amount, and environment and the mankind's health is caused to serious harm.
For the acetylene hydrochlorination reaction, have been reported both at home and abroad to use and using the noble metals such as platinum, palladium, gold as the main catalytic composition, though activity is higher, stability is not as high mercury catalyst, and high cost, is difficult to realize industrial production.And while using the base metal compounds such as tin, bismuth, copper, zinc as the main catalytic composition, the loss of its active component is comparatively serious again.
For the rare of mercury resource with to the pollution of environment, and domestic and international day by day severe to mercury pollution prevention and control policy, in research in the urgent need to the improvement to the mercury chloride performance and high-performance environment protection type catalyst, have breakthrough, when meeting the industrial production needs, decrease mercury resource consumption and to pollution and the harm of environment and human health.
Summary of the invention
The present invention In view of the foregoing namely, a kind of acetylene hydrochlorination reaction and eco-friendly low-mercury catalyst of can be used for is provided, the load capacity of its mercury chloride is little, has reduced consumption and the catalyst cost of mercury resource, and activity and stability are all higher than existing high mercury catalyst.
The said low-mercury catalyst for the acetylene hydrochlorination reaction of the present invention, be that mercury chloride is carried on active carbon equally, and the part by weight of its each raw material is:
100 parts of active carbons,
4 ~ 5 parts, mercury chloride,
8 ~ 10 parts of necessary assistant total amounts,
1 ~ 5 part of inessential auxiliary agent total amount,
Wherein, the specific area of active carbon is 500 ~ 1500 m
2/ g, average pore volume is 0.25 ~ 0.9 ml/g, aperture≤50 nm; Said necessary assistant is 2 ~ 5 parts of bismuth chlorides, 1 ~ 5 part of cerium chloride, 2 ~ 5 parts of 1 ~ 5 part of barium chloride and copper chlorides; Said inessential auxiliary agent comprises at least a in potassium chloride, phosphoric acid, zinc chloride and stannous chloride.
Active carbon in above-mentioned raw materials, preferably granularity is 20～50 orders, and is 850 ~ 1100 m through BET detection specific area
2/ g, average pore volume 0.48 ~ 0.88 ml/g and average pore size are 2 ~ 3nm, the amorphous cocoanut active charcoal of 2.2 ~ 2.3 nm more preferably.
For improving the performances such as its catalytic activity, stability and service life, in mercuric chleride catalyst, usually need add the auxiliary agent of suitable type, quantity and/or ratio.For example, in the high mercury catalyst that uses at present, usually need be added with bismuth chloride and potassium chloride as auxiliary agent.The inventor, through a large amount of experiment and screening, has determined that in above-mentioned catalyst the auxiliary agent that need be used in conjunction with comprises necessary and inessential two classes, and has determined the consumption mixing ratio of different auxiliary agents.Inessential auxiliary agent wherein can be according to the different situations choice for use.For example, the electrode potential of zinc chloride, stannous chloride and copper chloride is suitable, when the copper chloride load capacity is low, can select zinc chloride and/or stannous chloride, is conducive to improve the activity stability of catalytic reaction process.Phosphoric acid can provide proton and C
2H
2Form pi complex, form carbonium ion, in the stronger catalyst system of acidity, add, be conducive to the stability of enhanced activity.Potassium chloride, due to the ionic activity that can regulate in maceration extract, adds when therefore the ion concentration in maceration extract is excessive, can help each uniform ion to be distributed in carrier surface.
Take above-mentioned each composition as raw material, the preparation process of the said low-mercury catalyst of the present invention, unanimous on the whole with currently reported and/or the high mercury catalyst that uses.For example, a kind of typical preparation process can be carried out with mode in the steps below:
1': by active carbon after abundant surperficial removal of impurities under acid and oxidizing condition washing deacidify, ℃ heating, drying surface moisture in temperature≤60, then under≤90 ℃ of heating conditions vacuum drying to constant weight;
2': the active carbon after upper step is processed is in the urea liquid that for 3 ~ 5 times of its volumes, concentration is 1.5 ~ 5wt% fully after reflow treatment, with 1' step the same manner heating, drying and vacuum drying to constant weight, after in (such as usually can in the equipment such as Muffle furnace, carrying out) under the decomposition temperature condition of anaerobic and urea, being fired to constant weight again, standby;
3': by HgCl
2After with said auxiliary agent, with the dissolving with hydrochloric acid of concentration 1 ~ 3 mol/L, becoming the solution of chloride containing mercury 0.007 ~ 0.009 mol/L, with isopyknic this solution of active carbon, fully to flood the standby active carbon of upper step at least;
4': the active carbon after dipping, after drying under the heating condition of≤90 ℃, is the hydrochloric acid solution washing of 0.005 ~ 0.04mol/L with concentration, then under the heating condition of≤90 ℃, is dried to constant weight, obtains said low-mercury catalyst.
In above-mentioned preparation method, when the 1' step makes active carbon carry out the pretreatment of surperficial removal of impurities with acid and oxidizing condition, can wait simultaneously the difference of mode because adopting substep or a step, to said acidity is corresponding with oxidizing condition, also different selections can be arranged.For example, except adding appropriate hydrogen peroxide processes active carbon with hydrochloric acid, preferred mode is that employing concentration is the salpeter solution processing of 1 ~ 3 mol/L, utilize its acidity that has simultaneously and oxidisability characteristics, both can complete the removal of impurities pretreatment to active carbon, also effectively avoid other too much impurity of easy introducing.
Experiment shows, for more being conducive to the completeness of activated carbon surface removal of impurities, a kind of further optimal way, be that to be adopted as 3 ~ 5 times of active carbon volumes, concentration be that the nitric acid of 1.5 ~ 2.5mol/L is processed, active carbon refluxed processed in 2.5 ~ 3.5 hours more preferred in this salpeter solution.
With inorganic ammonia (or ammonium) salt, or the active carbon after the organic amine treatment surface removal of impurities of fat/aromatics processing, to remove the acid site of carrier inner surface, add the highly basic center, be also the mode that usually adopts in present mercuric chleride catalyst preparation, can strengthen the binding ability of mercury chloride and activated carbon surface.2' step in the above-mentioned preparation of the present invention, active carbon employing after surperficial removal of impurities is processed is refluxed in urea liquid, both be conducive to reduce and avoided introducing too much impurity component postorder is processed to bring unfavorable, make urea can be released and remove by being decomposed into ammonia and carbon dioxide in subsequent processes, it also is conducive to expand aperture and the specific area of active carbon in the process that release is removed, and simple to operation, cost is lower.Experiment shows, a kind of optimal way that in above-mentioned preparation, the 2' step is processed is that employing is that the mode that refluxes in the urea liquid of 2 ~ 4wt% is processed in 3.5 ~ 4.5 times of active carbon volumes, concentration, and reflow treatment got final product in 2.5 ~ 3.5 hours usually.
3' step in above-mentioned preparation process, be used to dissolving HgCl
2With the preferred concentration of the hydrochloric acid solution of auxiliary agent, can be 1.5 ~ 2.5mol/L.
Experiment shows, when use contains the hydrochloric acid solution Immesion active carbon of mercury chloride and auxiliary agent, make the consumption volume of hydrochloric acid solution of mercury chloride greater than impregnated active carbon, can be conducive to improve the dispersing uniformity of active component, but the while also can bring greatly because of the amount of dipping solution the follow-up workloads such as its recovery.And the incipient impregnation rule is the mode that the most extensively adopts industrial because being conducive to fine adjustment adsorbance and the advantage such as easy to operate.for this reason, the present invention shows through experiment, when the mercury chloride hydrochloric acid solution that adopts equal volume amounts floods, except can by the modes such as proper extension dip time (such as flooding 8 ~ 12 hours or longer) be conducive to improve its dispersed, at initial 10 ~ 45 minutes of dipping process if adopt take frequency as 40KHz and power is the ultrasonic wave assistant load of 100W, to help to make active component form uniform load with monolayer in active carbon, strengthened the binding ability of active component and carrier, reduce the distillation inactivation, uniform load to active component can produce significant effect, life-span that can also extending catalyst.
Experiment shows, in above-mentioned preparation 4' step, the concentration of hydrochloric acid solution of the active carbon of active component arranged be used to washing the dipping back loading, and preferably 0.01 ~ 0.03mol/L, can be conducive to keep stability and the catalytic activity of active component load more.
To the dipping back loading drying of active carbon of active component, and the active carbon after the hydrochloric acid solution washing carries out drying, preferred heating-up temperature all can be 75 ℃～85 ℃.
Experimental result shows, the preparation of the above-mentioned low-mercury catalyst of the present invention is simple, and the load capacity of mercury chloride is little, but its activity and stability etc. all can be higher than existing high mercury catalysts, conversion ratio for acetylene hydrochlorination when reaction can reach 99.7%, vinyl chloride selectively greater than 99.8%.Simultaneously, because mercury content significantly reduces, reduce the consumption to the mercury resource, not only reduced the catalyst cost, also greatly reduced the harm to environment and person health, also extended the service life of catalyst.Therefore, the present invention is to provide a kind of PVC industry production and environmentally friendly catalyst of being applicable to, have great economic benefit and environmental benefit.
The specific embodiment by the following examples is described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Without departing from the idea case in the present invention described above, various replacements or change according to ordinary skill knowledge and customary means are made, all should comprise within the scope of the invention.
The specific embodiment
Embodiment 1
Activated Carbon Pretreatment (following each example all herewith): (specific area is 500 ~ 1500 m by commercially available active carbon
2/ g, average pore volume is 0.25 ~ 0.9 ml/g, aperture≤50 nm), preferred size is 20～50 orders, specific area is 850 ~ 1100 m
2/ g, average pore volume 0.48 ~ 0.88 ml/g and average pore size are the amorphous cocoanut active charcoal of 2 ~ 3nm, particularly 2.2 ~ 2.3 nm, the concentration that is placed in 3 ~ 5 times of volumes (being preferably 4 times) is that 1.5mol/L ~ 2.5mol/L(is preferably 2mol/L) nitric acid, after heating is stirred to and refluxed 2.5 ~ 3.5 hours, active carbon is washed to pH=6 ~ 7 with distilled water, under 45 ℃ ~ 55 ℃, dry surface moisture, then in 75 ~ 85 ℃ of vacuum drying to constant weight.The concentration that this active carbon is placed in to 3.5 ~ 4.5 times of its volumes is the urea liquid of 2% ~ 4wt%, after heating is stirred to and refluxed 2.5 ~ 3.5 hours, suction filtration is also dried surface moistures in 45 ℃ ~ 55 ℃, again in 75 ~ 85 ℃ of vacuum drying to constant weight, then be placed in Muffle furnace and be fired to constant weight in 160 ℃ (decomposition temperatures of urea), obtain the active carbon that pretreatment completes, standby.
0.575g mercury chloride, 0.65g bismuth chloride, 0.39g potassium chloride, 0.13g cerium chloride, 0.26g barium chloride and 0.13g copper chloride are dissolved in the hydrochloric acid solution that concentration is 3mol/L simultaneously, and wherein the concentration of mercury chloride is 0.008mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, normal temperature incipient impregnation 8 hours, wherein initial 15min adds the ultrasonic wave assistant load; In temperature, be evaporate to dryness 2 hours in the water-bath of 90 ℃, then be the normal temperature drying in oven surface moisture 3 hours of 70 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.03mol/L, remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 80 ~ 90 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction for preparing chloroethylene by acetylene hydrochlorination, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.08, the acetylene air speed is 65h
-1, 120 ℃ of reaction temperatures, catalyst amount 10.8g, hydrogen chloride soak time 0.5 hour, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 94 ~ 95%, vinyl chloride selective>=99.8%.
Embodiment 2
0.65g mercury chloride, 0.52g bismuth chloride, 0.13g cerium chloride, 0.26g barium chloride and 0.45g copper chloride are dissolved in the hydrochloric acid solution that concentration is 2mol/L simultaneously, and wherein the concentration of mercury chloride is 0.009mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, and normal temperature incipient impregnation 12 hours, wherein added the ultrasonic wave assistant load in initial 0.5 hour; In temperature, be evaporate to dryness 2 hours in the water-bath of 80 ℃, then be the normal temperature drying in oven surface moisture 2 hours of 80 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.02mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 80 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction for the acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.25, the acetylene air speed is 65h
-1, 140 ℃ of reaction temperatures, catalyst amount 11g, hydrogen chloride soak time 1 hour, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 99 ~ 99.7%, vinyl chloride selective>=99.8%.
Embodiment 3
0.52g mercury chloride, 0.65g bismuth chloride, 0.39g cerium chloride, 0.26g barium chloride and 0.26g copper chloride are dissolved in the hydrochloric acid solution that concentration is 2.5mol/L simultaneously, and wherein the concentration of mercury chloride is 0.007mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, and normal temperature dipping 10 hours, wherein added the ultrasonic wave assistant load in initial 0.5 hour; In temperature, be evaporate to dryness 2 hours in the water-bath of 80 ℃, then be the normal temperature drying in oven surface moisture 2 hours of 70 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.02mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 80 ~ 85 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction of acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.25, the acetylene air speed is 33h
-1, 150 ℃ of reaction temperatures, catalyst amount 10g, hydrogen chloride soak time 2 hours, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 93 ~ 94%, vinyl chloride selective>=99.8%.
Embodiment 4
0.65g mercury chloride, 0.65g bismuth chloride, 0.13g cerium chloride, 0.13g barium chloride, 0.13g copper chloride and 0.63g phosphoric acid are dissolved in the hydrochloric acid solution that concentration is 1mol/L simultaneously, and wherein the concentration of mercury chloride is 0.009mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, normal temperature incipient impregnation 8 hours, wherein initial 45min adds the ultrasonic wave assistant load; In temperature, be evaporate to dryness 1 hour in the water-bath of 75 ~ 80 ℃, then be the normal temperature drying in oven surface moisture 2 hours of 85 ~ 90 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.03mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 70 ~ 75 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction for the acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.15, the acetylene air speed is 33h
-1, 120 ℃ of reaction temperatures, catalyst amount 10.9g, hydrogen chloride soak time 0.5 hour, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 95 ~ 96%, vinyl chloride selective>=99.8%.
Embodiment 5
0.52g mercury chloride, 0.65g bismuth chloride, 0.26g cerium chloride, 0.26g barium chloride, 0.13g copper chloride and 0.13g zinc chloride are dissolved in the hydrochloric acid solution that concentration is 1.5mol/L simultaneously, and wherein the concentration of mercury chloride is 0.007mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, normal temperature incipient impregnation 10 hours, wherein initial 10min adds the ultrasonic wave assistant load; In temperature, be evaporate to dryness 2 hours in the water-bath of 75 ~ 80 ℃, then be the normal temperature drying in oven surface moisture 2 hours of 80 ~ 85 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.01mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 80 ~ 85 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction of acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.2, the acetylene air speed is 65h
-1, 140 ℃ of reaction temperatures, catalyst amount 11.2g, hydrogen chloride soak time 1 hour, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 94 ~ 95%, vinyl chloride selective>=99.8%.
Embodiment 6
By 0.65g mercury chloride, 0.65g bismuth chloride, 0.13g cerium chloride, 0.26g barium chloride, 0.13g copper chloride and 0.39g stannous chloride, be dissolved in simultaneously in the hydrochloric acid solution that concentration is 2.5mol/L, wherein the concentration of mercury chloride is 0.009mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, normal temperature incipient impregnation 12 hours, wherein initial 40min adds the ultrasonic wave assistant load; In temperature, be evaporate to dryness 2 hours in the water-bath of 75 ~ 80 ℃, then be the normal temperature drying in oven surface moisture 3 hours of 55 ~ 60 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.02mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 75 ~ 80 ℃ and dry to constant weight, cooling standby.
This catalyst is in the reaction for the acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.05, the acetylene air speed is 65h
-1, 130 ℃ of reaction temperatures, catalyst amount 11.3g, hydrogen chloride soak time 1.5 hours, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 97 ~ 98%, vinyl chloride selective>=99.8%.
Comparative Examples
1.95g mercury chloride, 0.26g bismuth chloride, 0.13g potassium chloride are dissolved in the hydrochloric acid solution that concentration is 2mol/L, and wherein the concentration of mercury chloride is 0.027mol/L; The maceration extract for preparing is joined in the active carbon that the 13g pretreatment is good, and normal temperature incipient impregnation 12 hours, wherein added the ultrasonic wave assistant load in initial 0.5 hour; In temperature, be evaporate to dryness 2 hours in the water-bath of 80 ℃, then be the normal temperature drying in oven surface moisture 2 hours of 80 ℃ in temperature; With concentration, be the hydrochloric acid solution washing active carbon of 0.02mol/L, to remove the salinity that is deposited on the active carbon outer surface, after filtration, be placed on again temperature and be in the baking oven of 80 ℃ and dry to constant weight, cooling standby.This catalyst is in the reaction of acetylene hydrochlorination preparing chloroethylene, and mole proportioning of reactor feed gas is C
2H
2/ HCl=1/1.25, the acetylene air speed is 65h
-1, 140 ℃ of reaction temperatures, catalyst amount 10.8g, hydrogen chloride soak time 1 hour, reaction end gas are through chromatography, the conversion ratio that obtains acetylene is 98.7 ~ 99.4%, vinyl chloride selective>=98%.
Claims (10)
1. for the low-mercury catalyst of acetylene hydrochlorination reaction, mercury chloride is carried on active carbon, it is characterized in that preparing with the raw material of following part by weight:
100 parts of active carbons,
4 ~ 5 parts, mercury chloride,
8 ~ 10 parts of necessary assistant total amounts,
1 ~ 5 part of inessential auxiliary agent total amount,
Wherein, the specific area of active carbon is 500 ~ 1500m
2/ g, average pore volume is 0.25 ~ 0.9mL/g, aperture≤50nm; Necessary assistant is 2 ~ 5 parts of bismuth chlorides, 1 ~ 5 part of cerium chloride, 2 ~ 5 parts of 1 ~ 5 part of barium chloride and copper chlorides; Inessential auxiliary agent comprises at least a in potassium chloride, phosphoric acid, zinc chloride and stannous chloride; Preparation process is:
1': by active carbon after abundant surperficial removal of impurities under acid and oxidizing condition washing deacidify, ℃ heating, drying surface moisture in temperature≤60, then under≤90 ℃ of heating conditions vacuum drying to constant weight;
2': the active carbon after upper step is processed is in the urea liquid that for 3 ~ 5 times of its volumes, concentration is 1.5 ~ 5wt% fully after reflow treatment, with 1' step the same manner heating, drying and vacuum drying to constant weight, after under the decomposition temperature condition of anaerobic and urea, being fired to constant weight, standby again;
3': by HgCl
2After with said auxiliary agent, with the dissolving with hydrochloric acid of concentration 1 ~ 3 mol/L, becoming the solution of chloride containing mercury 0.007 ~ 0.009 mol/L, with isopyknic this solution of active carbon, fully to flood the standby active carbon of upper step at least;
4': the active carbon after dipping, after drying under the heating condition of≤90 ℃, is the hydrochloric acid solution washing of 0.005 ~ 0.04mol/L with concentration, then under the heating condition of≤90 ℃, is dried to constant weight, obtains said low-mercury catalyst.
2. low-mercury catalyst as claimed in claim 1, is characterized in that said active carbon is that granularity is that 20～50 orders, specific area are 850 ~ 1100 m
2/ g, average pore volume 0.48 ~ 0.88 mL/g and average pore size are the amorphous cocoanut active charcoal of 2 ~ 3nm.
3. low-mercury catalyst as claimed in claim 1 or 2, is characterized in that the removal of impurities of said 1' step activated carbon surface is for concentration being the salpeter solution processing of 1 ~ 3 mol/L.
4. low-mercury catalyst as claimed in claim 3, the concentration that it is characterized in that nitric acid used is 1.5 ~ 2.5mol/L, consumption is 3 ~ 5 times of active carbon volume.
5. low-mercury catalyst as claimed in claim 4, is characterized in that the said activated carbon surface removal of impurities of 1' step is for refluxing active carbon 2.5 ~ 3.5 hours in salpeter solution.
6. low-mercury catalyst as claimed in claim 1 or 2, is characterized in that the concentration of the urea liquid in said 2' step is 2 ~ 4wt%, and consumption is 3.5 ~ 4.5 times of active carbon volume, reflow treatment 2.5 ~ 3.5 hours.
7. low-mercury catalyst as claimed in claim 1 or 2, is characterized in that in said 3' step be used to dissolving HgCl
2With the concentration of hydrochloric acid solution of auxiliary agent be 1.5 ~ 2.5mol/L.
8. low-mercury catalyst as claimed in claim 1 or 2, it is characterized in that standby active carbon in said 3' step is used with the mercury chloride hydrochloric acid solution of its equal volume amounts floods, and initial 10 ~ 45 minutes of dipping process take frequency as 40KHz, power is the ultrasonic wave assistant load of 100W.
9. low-mercury catalyst as claimed in claim 1 or 2, is characterized in that active carbon in said 4' step respectively walks drying and all under 75 ℃～85 ℃ conditions, carries out.
10. low-mercury catalyst as claimed in claim 1 or 2, is characterized in that in said 4' step, the concentration of hydrochloric acid solution for the detergent active charcoal is 0.01 ~ 0.03mol/L.
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| CN108043467B (en) * | 2017-11-27 | 2020-10-02 | 宁夏新龙蓝天科技股份有限公司 | Mercury-free catalyst for improving yield of chloroethylene and preparation method thereof |
| CN108295876A (en) * | 2018-01-30 | 2018-07-20 | 浙江工业大学 | A kind of preparation method of low-mercury catalyst 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 |
| CN111013652B (en) * | 2019-11-14 | 2023-01-24 | 贵州省万山银河化工有限责任公司 | Recycling method of carbon molecular sieve low-solid-mercury catalyst for vinyl chloride synthesis |
| CN113813998A (en) * | 2021-08-11 | 2021-12-21 | 贵州重力科技环保有限公司 | Acetylene hydrochlorination ultralow-mercury catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063827A (en) * | 1991-01-30 | 1992-08-26 | 吉林省纺织工业设计研究院 | The preparation method of catalyst for vinyl chloride synthesis |
| CN101596459A (en) * | 2009-02-11 | 2009-12-09 | 贵阳白云银星化工有限公司 | Mercuric chloride low-mercury catalyst and preparation method thereof |
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2910350B1 (en) * | 2006-12-22 | 2009-01-30 | Solvay | CATALYTIC HYDROCHLORIZATION SYSTEM AND PROCESS FOR PRODUCING VINYL CHLORIDE FROM ACETYLENE AND HYDROGEN CHLORIDE IN THE PRESENCE OF THIS CATALYTIC SYSTEM |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063827A (en) * | 1991-01-30 | 1992-08-26 | 吉林省纺织工业设计研究院 | The preparation method of catalyst for vinyl chloride synthesis |
| CN101596459A (en) * | 2009-02-11 | 2009-12-09 | 贵阳白云银星化工有限公司 | Mercuric chloride low-mercury catalyst and preparation method thereof |
| CN101890360A (en) * | 2010-08-05 | 2010-11-24 | 李伟 | Method for preparing novel catalyst used for hydrochlorination of acetylene |
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