CN103566947A - Normal-temperature dearsenic agent as well as preparation method thereof - Google Patents
Normal-temperature dearsenic agent as well as preparation method thereof Download PDFInfo
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Abstract
The invention relates to a normal-temperature dearsenic agent as well as a preparation method thereof, belonging to the technical field of dearsenic purifying. The normal-temperature dearsenic agent consists of active ingredients and auxiliaries, wherein the auxiliaries are one or more of a binder, a pore-forming agent and an extruding aid; the active ingredients comprise the following components: 40wt%-60wt% of manganese dioxide, 5wt%-15wt% of copper oxide and 5wt%-15wt% of zinc oxide; and content of the auxiliaries is 15wt%-20wt%. In the normal-temperature dearsenic agent disclosed by the invention, the manganese dioxide, the copper oxide and the zinc oxide with proper component content are matched, so that competing reaction of H2S and the copper oxide is restrained, and therefore, a using range of copper-series dearsenic agents is broadened, the copper-series dearsenic agents are enabled to be capable of being suitable for an H2S-contaning substance with arsenic to be removed, dearsenic activity of the dearsenic agent is ensured, dearsenic efficiency is improved, and cost of the dearsenic agent is lowered.
Description
Technical field
The present invention relates to a kind of arsenic removal catalyst and preparation method thereof, belong to dearsenification purification techniques field.
Background technology
In ethylene industry, in the processes such as hydrocarbon cracking, catalytic reforming, hydrogenation technique, in feedstock oil, can contain the arsenide of minute quantity, although the content of arsenide is very low, but but can cause catalyst poisoning, thereby cause catalysqt deactivation, therefore need to as much as possible the arsenide in feedstock oil be removed.For many years, researcher is exploring various effective arsenide removal methods always, to arsenide in petroleum hydrocarbon processing is reduced to bottom line to the poisoning effect of catalyst.
Existing Hydrodearsenic Catalyst product mainly comprises nickel system, plumbous system, manganese system, copper based de-arsenic catalyst; Wherein, nickel based de-arsenic catalyst belongs to hydrogenation arsenic removal catalyst, that is to say that using nickel based de-arsenic catalyst to carry out dearsenification must carry out under the condition of hydrogenation.
Chinese patent literature CN101590409C discloses a kind of lead-based de-arsenic catalyst, and it adopts one or more transition metal oxides and PbO is active component, and this Hydrodearsenic Catalyst is applicable to the dearsenification of liquid hydrocarbon and gaseous hydrocarbon, and dearsenification effect is better.But lead belongs to heavy metal, lead-based de-arsenic catalyst serious environment pollution, therefore belongs to the Hydrodearsenic Catalyst agent kind being eliminated gradually.
The appearance of manganese based de-arsenic catalyst has solved the problem of using the heavy metal pollution that lead-based de-arsenic catalyst causes, such as Chinese patent literature CN101485971A, disclose a kind of arsenic removal catalyst, its main active component is manganese dioxide and di-iron trioxide, the proper combination of this Hydrodearsenic Catalyst by manganese dioxide and di-iron trioxide makes it have higher arsenic to hold, and one of selection manganese dioxide is active component, because manganese dioxide price is low, thereby reduced on the whole the manufacturing cost of Hydrodearsenic Catalyst, and do not there is the contaminative of heavy metal.But, use manganese dioxide dearsenification when reducing costs, also can there is corresponding reduction for the arsenic-removing rate of active component than independent use such as di-iron trioxide, cupric oxide etc.
Chinese patent literature CN101591556A discloses a kind of copper based de-arsenic catalyst, and this Hydrodearsenic Catalyst is for the arsenide of all kinds of oil products of deep removal, and it comprises CuO, ZnO isoreactivity component.CuO is as dearsenification active component, and its dearsenification activity is high, still, and H in treating dearsenification product
2when S and arsenic coexist, H in competitive Adsorption process
2s has the stronger ability of being combined with CuO, ZnO than arsenic, makes CuO, ZnO isoreactivity component elder generation and H
2s reacts, thereby consumed a part of active component, the amount of the real active component for dearsenification is reduced, cause arsenic-removing rate to reduce, so must first will treat that the sulphur in dearsenification product removes totally while using this Hydrodearsenic Catalyst, and then carry out dearsenification, so just limited the scope of application of this Hydrodearsenic Catalyst.In view of CuO has excellent dearsenification activity, so those skilled in the art have been placed on Research Emphasis, how avoid CuO active component and treat the H in dearsenification product
2the problem that S reacts, thus dearsenification efficiency guaranteed.But up to the present, this technical problem never solves.
Summary of the invention
Technical problem to be solved by this invention is in prior art that Hydrodearsenic Catalyst exists that cost is high, heavy metal pollution, arsenic-removing rate are not high, and is applied to H
2the problems such as dearsenification Efficiency Decreasing when dearsenification thing that S and arsenic coexist, and provide that a kind of production cost is low, production technology is simple, dead catalyst is rationally recycled and has at normal temperatures higher arsenic-removing rate, and is applicable to H
2the Hydrodearsenic Catalyst for the treatment of dearsenification thing that S and arsenic coexist, and the preparation method of this Hydrodearsenic Catalyst is further provided.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
, by active component and auxiliary agent, being formed, described auxiliary agent is one or more in binding agent, pore creating material, extrusion aid;
Described active component comprises manganese dioxide, described active component also comprises cupric oxide and zinc oxide, and the content of described manganese dioxide is 40-60wt%, and the content of described cupric oxide is 5-15wt%, the content of described zinc oxide is 5-15wt%, and the content of described auxiliary agent is 15-20wt%.
Described cupric oxide and zinc oxide come from the useless agent of catalyst.
The useless agent of described catalyst is for take the useless agent of catalst for synthesis of methanol that aluminium oxide is carrier.
The particle diameter of the useless agent of described catalyst is less than or equal to 10nm.
Described binding agent is one or more in kaolin, attapulgite, sheep liver soil, alumino-silicate cement and molecular screen primary powder.
Described pore creating material is one or more in cellulose powder, sesbania powder, activated carbon powder and carbonic hydroammonium.
Described extrusion aid is one or more in cellulose powder, sesbania powder and citric acid.
The preparation method of described arsenic removal catalyst, comprises the steps:
(1) pore creating material is mixed with to slurries;
(2) manganese dioxide, cupric oxide, zinc oxide and binding agent are mixed;
(3) slurries that prepare in step (1) are added in the mixture in step (2), stir
Evenly, more wherein add the aqueous solution of extrusion aid or extrusion aid to stir;
(4) material step (3) being obtained is mediated, moulding, obtains article shaped;
(5) article shaped step (4) being obtained is dried, roasting.
The preparation method of described arsenic removal catalyst, in step (5), baking temperature is 100-120 ℃, and be 3-4 hour drying time, and sintering temperature is 350-400 ℃, and roasting time is 3-4 hour.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) arsenic removal catalyst of the present invention, its active component is manganese dioxide, cupric oxide and zinc oxide.Wherein, the crystalline structure of manganese dioxide powder is octahedral structure, is the mineral typically with pore passage structure, because it has broad pore passage structure, due to the special structure of manganese dioxide, when being applied to H
2s and arsenic coexist when dearsenification thing, the manganese dioxide of suitable constituent content coordinates with cupric oxide, zinc oxide, makes H
2the competitive reaction of S and cupric oxide has obtained inhibition, thereby has widened the scope of application of copper based de-arsenic catalyst, and copper based de-arsenic catalyst is gone for containing H
2s treats dearsenification thing, and has also guaranteed that the dearsenification of this Hydrodearsenic Catalyst is active, has improved dearsenification efficiency, reduced the cost of Hydrodearsenic Catalyst.
(2) arsenic removal catalyst of the present invention, its active component cupric oxide and zinc oxide is from the useless agent of catalyst, both effectively utilized the catalyst agent of giving up, and greatly reduces again cost; Although obtaining the catalytic performance of the useless agent of catalyst after using has reduced a lot, but still can bring into play certain activity, meanwhile, between manganese dioxide and cupric oxide, there is certain synergy, further strengthened the effect of dearsenification, the dearsenification efficiency and the arsenic that have improved Hydrodearsenic Catalyst hold.The synthetic main copper-based catalysts that uses of current industrial methyl alcohol, copper-based catalysts is a kind of low-temp low-pressure methanol synthesis catalyst, and its key component is CuO/ZnO/Al2O3 (Cu-Zn-Al), is characterized in active good, and conversion per pass is 7%-8%; Selective high, be greater than 99%, its impurity only has micro-methane, dimethyl ether, methyl formate, and highly purified refined methanol is easy to get.The recycling of the dead catalyst after using for Cu-Zn-Al low temperature conversion catalyst, low change protective agent and low pressure methanol synthesis catalyst; generally with adopting again chloride volatility process or smelting process recovering copper or zinc after acid or the separated Al2O3 of alkali treatment; refining zinc and copper can be made the raw material that raw catelyst is produced in regeneration thus; but these complex process are with high costs.The annual dead catalyst quantity of using of China is very large, and especially methyl alcohol is short with the connection alcohol catalyst life-span, generally only uses some months just to need to change.Therefore, waste copper catalyst is recycled and had very high economic worth and social value.
(3) preparation method of arsenic removal catalyst of the present invention, first pore creating material is become to slurries with solvent, again slurries are mixed with manganese dioxide powder, cupric oxide, zinc oxide and binding agent, can guarantee that like this pore creating material penetrates in mixture with the form of slurries, mobilization by slurries mixes pore creating material equably with other raw materials, thereby make prepared Hydrodearsenic Catalyst have rational pore passage structure, the dearsenification efficiency and the arsenic that have further improved Hydrodearsenic Catalyst hold.
(4) preparation method of arsenic removal catalyst of the present invention, the aqueous solution of extrusion aid or extrusion aid is joined in mixture and stirred, extrusion aid is joined separately in mixture and can make extrusion aid mix more even with the active component in Hydrodearsenic Catalyst raw material, when extrusion aid joins in mixture with the form of the aqueous solution, mobilization by the aqueous solution can drive extrusion aid high degree of dispersion in mixture, thereby be conducive to improve equably Hydrodearsenic Catalyst compression strength everywhere, make Hydrodearsenic Catalyst be easy to extruded moulding.
(5) arsenic removal catalyst of the present invention, preparation method is simple, and raw materials for production are cheap, and saving production cost etc., aspect is suitable for large-scale industrial production.Meanwhile, the processing problem for the useless agent of catalyst has obtained good solution.
For content of the present invention is more likely to be clearly understood, below according to a particular embodiment of the invention, the present invention is further detailed explanation.
The specific embodiment
embodiment 1
Cupric oxide and zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 15 grams, sheep liver soil, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M1, and the performance data of M1 is in Table 1 after tested.
embodiment 2
Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 5 grams of cupric oxide powders, 5 grams of Zinc oxide powders, 15 grams of kaolin, 5 grams of cellulose powders, and suitable quantity of water, mixing stirs makes mixture, the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M2, and the performance data of M2 is in Table 1 after tested.
embodiment 3
Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 50 grams, manganese ore powder, 15 grams of cupric oxide powders, 15 grams of Zinc oxide powders, 15 grams of alumino-silicate cement, 5 grams of cellulose powders, and suitable quantity of water, mixing stirs makes mixture, the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M3, and the performance data of M3 is in Table 1 after tested.
embodiment 4
Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 50 grams, manganese ore powder, 15 grams of cupric oxide powders, 15 grams of Zinc oxide powders, 10 grams, sesbania powder, 5 grams of cellulose powders, 5 grams of kaolin, and suitable quantity of water, mixing stirs makes mixture, and the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M4, and the performance data of M4 is in Table 1 after tested.
embodiment 5
Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 10 grams of attapulgites, 5 grams of alumino-silicate cement, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M5, and the performance data of M5 is in Table 1 after tested.
embodiment 6
3 grams of cellulose powders are added and in 70 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 17 grams of attapulgites, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M6, and the performance data of M6 is in Table 1 after tested.
embodiment 7
3 grams of cellulose powders are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 40 grams, manganese ore powder, 15 grams of cupric oxide powders, 15 grams of Zinc oxide powders, 10 grams of molecular screen primary powders, 7 grams of kaolin, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M7, and the performance data of M7 is in Table 1 after tested.
embodiment 8
2 grams of sesbania powder are added and in 60 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 50 grams, manganese ore powder, 20 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 10 grams, sheep liver soil, 8 grams of alumino-silicate cement, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M8, and the performance data of M8 is in Table 1 after tested.
embodiment 9
3 grams of activated carbon powders are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 12 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 5 grams of attapulgites, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then in mixture, add 10 grams of sesbania powder, mix; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M9, and the performance data of M9 is in Table 1 after tested.
embodiment 10
3 grams of carbonic hydroammonium are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 50 grams, manganese ore powder, 15 grams of cupric oxide powders, 15 grams of Zinc oxide powders, 7 grams, sheep liver soil, 3 grams of kaolin, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then in mixture, add 7 grams of citric acids, mix; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M10, and the performance data of M10 is in Table 1 after tested.
embodiment 11
3 grams of sesbania powder are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 10 grams, sheep liver soil, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then to the aqueous solution that adds 5 grams of citric acids and sesbania powder in mixture, wherein the mass ratio of citric acid and sesbania powder is 1:1, and said mixture is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M11, and the performance data of M11 is in Table 12 after tested.
embodiment 12
3 grams of cellulose powders are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 50 grams, manganese ore powder, 15 grams of cupric oxide powders, 15 grams of Zinc oxide powders, 6 grams, high ridge, 5 grams of alumino-silicate cement, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then to the aqueous solution that adds 6 grams of citric acids and sesbania powder in mixture, wherein the mass ratio of citric acid and sesbania powder is 2:1, mixes; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M12, and the performance data of M12 is in Table 1 after tested.
embodiment 13
3 grams of sesbania powder are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 60 grams, manganese ore powder, 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 10 grams, sheep liver soil, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then to the aqueous solution that adds 5 grams of citric acids and sesbania powder in mixture, wherein the mass ratio of citric acid and sesbania powder is 1:1, and said mixture is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product M13, and M13 is applied to have H
2the dearsenification thing for the treatment of of S carries out dearsenification, after tested, and H
2the surplus of S is in Table 2.
comparative example 1
Take 80 grams, manganese ore powder, 50 grams of di-iron trioxides, 15 grams, sheep liver soil, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product D1, and the performance data of D1 is in Table 1 after tested.
comparative example 2
Take 60 grams, manganese ore powder, 40 grams of di-iron trioxides, 15 grams, sheep liver soil, 10 grams of kaolin, 10 grams of alumino-silicate cement, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product D2, and the performance data of D2 is in Table 1 after tested.
comparative example 3
3 grams of sesbania powder are added and in 50 grams of water, are mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to 200 microns of following powder, take 10 grams of cupric oxide powders, 10 grams of Zinc oxide powders, 10 grams, sheep liver soil, mixing stirs makes mixture, then above-mentioned pore creating material slurries is added in mixture and is stirred; Then to the aqueous solution that adds 5 grams of citric acids and sesbania powder in mixture, wherein the mass ratio of citric acid and sesbania powder is 1:1, and said mixture is stirred; The material that said process is obtained is put into after kneader is fully mediated evenly repeatedly and is inserted banded extruder, and material is extruded into φ 4 * 2-10mm strip article shaped; Article shaped is placed at 120 ℃ and is dried 3 hours, and roasting 3-4 hour at 350-400 ℃, obtains arsenic removal catalyst finished product D3, and D3 is applied to have H
2the dearsenification thing for the treatment of of S carries out dearsenification, after testing, and H
2the surplus of S is in Table 2.
test case
In order to be illustrated more clearly in the dearsenification efficiency of the arsenic removal catalyst that the present invention prepares, carried out following test, test condition is: in unstripped gas containing arsenic hydride 20～30ppm, containing H
2s(5～10) ppm, the carrier gas in unstripped gas is nitrogen, and in dearsenification device, the loadings of arsenic removal catalyst is 2ml, and granularity is 0.45～0.9mm, and air speed is 1000～2000h
-1, the data that obtain arsenic removal catalyst dearsenification efficiency after running in 240 hours are in Table 1.Wherein: total arsenic content * 100% in arsenic-removing rate=(in unstripped gas after total arsenic content-dearsenification in gas arsenic content)/unstripped gas.
Table 1
Table 2
By the data in table 1, can find out, the Hydrodearsenic Catalyst that the present invention prepares, when reducing production costs, still has very high dearsenification efficiency.By comparative example data, can be found out, take merely the Hydrodearsenic Catalyst dearsenification poor effect that manganese ore powder and di-iron trioxide prepared as raw material, within equal service cycle, conversion ratio obviously declines, the Hydrodearsenic Catalyst that dearsenification effect is prepared not as good as the present invention.
By the data in table 2, can find out, the Hydrodearsenic Catalyst that the present invention prepares is being applied to containing H
2s when dearsenification thing, still there is very high dearsenification efficiency.By comparative example data, can be found out, take merely the Hydrodearsenic Catalyst that cupric oxide and zinc oxide prepared as raw material, cupric oxide and zinc oxide are easily and H
2s reacts, H
2s content declines, and causes reducing for the raw material of dearsenification, and arsenic-removing rate reduces, the Hydrodearsenic Catalyst that dearsenification effect is prepared not as good as the present invention.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the claims in the present invention.
Claims (9)
1. an arsenic removal catalyst, is comprised of active component and auxiliary agent, and described auxiliary agent is one or more in binding agent, pore creating material, extrusion aid;
Described active component comprises manganese dioxide, it is characterized in that, described active component also comprises cupric oxide and zinc oxide, the content of described manganese dioxide is 40-60wt%, the content of described cupric oxide is 5-15wt%, and the content of described zinc oxide is 5-15wt%, and the content of described auxiliary agent is 15-20wt%.
2. arsenic removal catalyst according to claim 1, is characterized in that, described cupric oxide and zinc oxide come from the useless agent of catalyst.
3. arsenic removal catalyst according to claim 2, is characterized in that, the useless agent of described catalyst is for take the useless agent of catalst for synthesis of methanol that aluminium oxide is carrier.
4. according to the arsenic removal catalyst described in claim 2 or 3, it is characterized in that, the particle diameter of the useless agent of described catalyst is less than or equal to 10nm.
5. according to the arbitrary described arsenic removal catalyst of claim 1-4, it is characterized in that, described binding agent is one or more in kaolin, attapulgite, sheep liver soil, alumino-silicate cement and molecular screen primary powder.
6. arsenic removal catalyst according to claim 5, is characterized in that, described pore creating material is one or more in cellulose powder, sesbania powder, activated carbon powder and carbonic hydroammonium.
7. arsenic removal catalyst according to claim 6, is characterized in that, described extrusion aid is one or more in cellulose powder, sesbania powder and citric acid.
8. the preparation method of arsenic removal catalyst claimed in claim 7, comprises the steps:
(1) pore creating material is mixed with to slurries;
(2) manganese dioxide, cupric oxide, zinc oxide and binding agent are mixed;
(3) slurries that prepare in step (1) are added in the mixture in step (2), stir
Evenly, more wherein add the aqueous solution of extrusion aid or extrusion aid to stir;
(4) material step (3) being obtained is mediated, moulding, obtains article shaped;
(5) article shaped step (4) being obtained is dried, roasting.
9. the preparation method of arsenic removal catalyst according to claim 8, is characterized in that, in step (5), baking temperature is 100-120 ℃, and be 3-4 hour drying time, and sintering temperature is 350-400 ℃, and roasting time is 3-4 hour.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6068034A (en) * | 1983-09-14 | 1985-04-18 | Nippon Paionikusu Kk | Process for removing poisonous component |
| EP0259883A1 (en) * | 1986-09-12 | 1988-03-16 | Sakai Chemical Industry Co., Ltd., | A method of immobilizing arsenic or arsenic compounds contained in boiler slags or high temperature gases |
| CN1047219A (en) * | 1990-02-27 | 1990-11-28 | 黄家鹄 | Remove the low-temp desulfurization agent of organosulfur in the gas |
| CN1493661A (en) * | 2002-10-28 | 2004-05-05 | 上海化工研究院 | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent |
| CN100998944A (en) * | 2006-12-30 | 2007-07-18 | 沈阳润达化工有限公司 | Production method of dearsenic agent |
| CN101485971A (en) * | 2008-05-29 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Normal temperature de-arsenic agent |
-
2012
- 2012-08-07 CN CN201210278241.3A patent/CN103566947B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6068034A (en) * | 1983-09-14 | 1985-04-18 | Nippon Paionikusu Kk | Process for removing poisonous component |
| EP0259883A1 (en) * | 1986-09-12 | 1988-03-16 | Sakai Chemical Industry Co., Ltd., | A method of immobilizing arsenic or arsenic compounds contained in boiler slags or high temperature gases |
| CN1047219A (en) * | 1990-02-27 | 1990-11-28 | 黄家鹄 | Remove the low-temp desulfurization agent of organosulfur in the gas |
| CN1493661A (en) * | 2002-10-28 | 2004-05-05 | 上海化工研究院 | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent |
| CN100998944A (en) * | 2006-12-30 | 2007-07-18 | 沈阳润达化工有限公司 | Production method of dearsenic agent |
| CN101485971A (en) * | 2008-05-29 | 2009-07-22 | 北京三聚环保新材料股份有限公司 | Normal temperature de-arsenic agent |
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|---|---|---|---|---|
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| WO2015189634A1 (en) | 2014-06-13 | 2015-12-17 | Imperial Innovations Limited | Method for reducing arsenic concentration in aqueous solutions |
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| CN105562008A (en) * | 2015-12-16 | 2016-05-11 | 沈阳三聚凯特催化剂有限公司 | Normal-temperature arsenic removal agent and preparation method and application thereof |
| CN105562008B (en) * | 2015-12-16 | 2018-11-02 | 沈阳三聚凯特催化剂有限公司 | A kind of arsenic removal catalyst and the preparation method and application thereof |
| CN107199016A (en) * | 2017-07-12 | 2017-09-26 | 江西安发环保新材料有限公司 | A kind of oil product special efficient Hydrodearsenic Catalyst |
| CN109529871A (en) * | 2018-12-13 | 2019-03-29 | 重庆工商大学 | A kind of sea urchin shape copper-based catalysts and its preparation method and application |
| CN110639466A (en) * | 2019-09-30 | 2020-01-03 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN110639466B (en) * | 2019-09-30 | 2020-12-01 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| WO2021063345A1 (en) | 2019-09-30 | 2021-04-08 | 四川润和催化新材料股份有限公司 | Dearsenification adsorbent and preparation method therefor |
| CN110813292A (en) * | 2019-10-24 | 2020-02-21 | 湖北浚然新材料有限公司 | Dearsenic agent and preparation method thereof |
| CN111849581A (en) * | 2020-08-07 | 2020-10-30 | 辽宁石油化工大学 | Preparation method of low-temperature FCC gasoline dearsenicating agent |
| CN111849581B (en) * | 2020-08-07 | 2022-04-22 | 辽宁石油化工大学 | Preparation method of low-temperature FCC gasoline dearsenicating agent |
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