CN103566947B - A kind of arsenic removal catalyst and preparation method thereof - Google Patents
A kind of arsenic removal catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of arsenic removal catalyst and preparation method thereof, belong to dearsenification purification techniques field.Described arsenic removal catalyst is made up 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, 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%.Manganese dioxide and the cupric oxide of Suitable ingredients content in arsenic removal catalyst of the present invention, the coordinating of zinc oxide, make H
2the competitive reaction of S and cupric oxide obtains suppression, thus 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, also ensure that the cost that the dearsenification of this Hydrodearsenic Catalyst is active, improve dearsenification efficiency, reduce Hydrodearsenic Catalyst.
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, the arsenide of minute quantity can be contained in feedstock oil, although the content of arsenide is very low, but but can cause catalyst poisoning, thus cause catalysqt deactivation, therefore need as much as possible the arsenide in feedstock oil to be removed.For many years, researcher is exploring various effective arsenide removal methods always, the poisoning effect of arsenide to catalyst in petroleum hydrocarbon processing is reduced to bottom line.
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, and that is 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 to be 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 be eliminated gradually.
The appearance of manganese based de-arsenic catalyst solves the problem of the heavy metal pollution using lead-based de-arsenic catalyst to cause, such as Chinese patent literature CN101485971A discloses a kind of arsenic removal catalyst, its main active component is manganese dioxide and di-iron trioxide, this Hydrodearsenic Catalyst makes it have higher arsenic appearance by the proper combination of manganese dioxide and di-iron trioxide, and select manganese dioxide to be one of active component, because manganese dioxide price is low, thus reduce the manufacturing cost of Hydrodearsenic Catalyst on the whole, and not there is the contaminative of heavy metal.But using manganese dioxide dearsenification while reducing costs, can be also that the arsenic-removing rate of active component has corresponding reduction than being used alone 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 used for the arsenide in all kinds of oil product of deep removal, and it comprises CuO, ZnO isoreactivity component.CuO is as dearsenification active component, and its dearsenification activity is high, but, when treating H in dearsenification product
2when S and arsenic coexist, H in competitive Adsorption process
2s has the stronger ability be combined with CuO, ZnO than arsenic, makes CuO, ZnO isoreactivity component elder generation and H
2s reacts, thus consume a part of active component, make really to reduce for the amount of the active component of dearsenification, arsenic-removing rate is caused to reduce, so must first the sulphur treated in dearsenification product be removed totally when using this Hydrodearsenic Catalyst, and then carry out dearsenification, so just limit the scope of application of this Hydrodearsenic Catalyst.In view of CuO has excellent dearsenification activity, so Research Emphasis has been placed on the H how avoiding CuO active component and treat in dearsenification product by those skilled in the art
2the problem that S reacts, thus ensure dearsenification efficiency.But up to the present, this technical problem never solves.
Summary of the invention
Technical problem to be solved by this invention to be 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 the dearsenification efficiency reduction when dearsenification thing that S and arsenic coexist, and provide that a kind of production cost is low, production technology is simple, rationally recycle dead catalyst and have higher arsenic-removing rate at normal temperatures, and is applicable to H
2the Hydrodearsenic Catalyst of what S and arsenic coexisted treat dearsenification thing, and the preparation method of this Hydrodearsenic Catalyst is provided further.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of arsenic removal catalyst, is made up 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, 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 catalyst and to give up agent.
The agent of giving up of described catalyst is be that the catalst for synthesis of methanol of carrier gives up agent with aluminium oxide.
The give up particle diameter of 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 slurries;
(2) manganese dioxide, cupric oxide, zinc oxide and binding agent are mixed;
(3) slurries prepared in step (1) are added in the mixture in step (2), stir
Evenly, more wherein the aqueous solution adding extrusion aid or extrusion aid stirs;
(4) material that step (3) obtains is carried out mediate, shaping, obtain article shaped;
(5) drying, roasting are carried out to the article shaped that step (4) obtains.
The preparation method of described arsenic removal catalyst, in step (5), baking temperature is 100-120 DEG C, and drying time is 3-4 hour, and sintering temperature is 350-400 DEG C, 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 structure that manganese dioxide is special, when being applied to H
2s and arsenic coexist when dearsenification thing, the manganese dioxide of Suitable ingredients content and cupric oxide, the coordinating of zinc oxide, make H
2the competitive reaction of S and cupric oxide obtains suppression, thus 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 also ensure that the cost that the dearsenification of this Hydrodearsenic Catalyst is active, improve dearsenification efficiency, reduce Hydrodearsenic Catalyst.
(2) arsenic removal catalyst of the present invention, its active component cupric oxide and zinc oxide to give up agent from catalyst, both effectively make use of catalyst and to have given up agent, and greatly reduced cost again; Although obtaining the give up catalytic performance of agent of catalyst after using has reduced a lot, but still certain activity can be played, meanwhile, there is between manganese dioxide and cupric oxide certain synergy, further enhancing the effect of dearsenification, the dearsenification efficiency and the arsenic that improve Hydrodearsenic Catalyst hold.The synthesis of current industrial methyl alcohol mainly uses copper-based catalysts, and 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), and be characterized in active good, conversion per pass is 7%-8%; Selective height, is greater than 99%, and its impurity only has methane, dimethyl ether, the methyl formate of trace, and be easy to get highly purified refined methanol.The recycling of the dead catalyst after Cu-Zn-Al low temperature conversion catalyst, low change protective agent and low pressure methanol synthesis catalyst are used; general acid or alkali treatment are separated and adopt chloride volatility process or smelting process recovering copper or zinc after Al2O3 again; zinc refining thus and copper can make the raw material of regenerative ratio raw catelyst; but these complex process, with high costs.The dead catalyst quantity that China uses every year is very large, and especially methyl alcohol is short with the connection alcohol catalyst life-span, and the general some months that only uses just needs replacing.Therefore, waste copper catalyst recycling had very high economic worth and social value.
(3) preparation method of arsenic removal catalyst of the present invention, first pore creating material and solvent are mixed into slurries, again slurries are mixed with manganese dioxide powder, cupric oxide, zinc oxide and binding agent, can ensure that pore creating material penetrates in mixture in form of slurry like this, by the mobilization of slurries, pore creating material is mixed equably with other raw materials, thus making prepared Hydrodearsenic Catalyst have rational pore passage structure, the dearsenification efficiency and the arsenic that further increase 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 stirs, extrusion aid is joined separately in mixture extrusion aid can be made to mix with the active component in Hydrodearsenic Catalyst raw material evenly, when extrusion aid joins in mixture in form of an aqueous solutions, extrusion aid high degree of dispersion in the mixture can be driven by the mobilization of the aqueous solution, thus be conducive to improving Hydrodearsenic Catalyst compression strength everywhere equably, 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, in saving production cost etc., be suitable for large-scale industrial production.Meanwhile, good solution is obtained for the give up process problem of agent of catalyst.
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention, the present invention is further detailed explanation.
Detailed description of the invention
embodiment 1
Cupric oxide and zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 10 grams, Zinc oxide powder 10 grams, 15 grams, sheep liver soil, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, the material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M1, the performance data of M1 is in table 1 after tested.
embodiment 2
Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 5 grams, Zinc oxide powder 5 grams, kaolin 15 grams, cellulose powder 5 grams, and suitable quantity of water, mixing stirs makes mixture, the material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M2, the performance data of M2 is in table 1 after tested.
embodiment 3
Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 50 grams, cupric oxide powder 15 grams, Zinc oxide powder 15 grams, alumino-silicate cement 15 grams, cellulose powder 5 grams, and suitable quantity of water, mixing stirs makes mixture, the material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M3, the performance data of M3 is in table 1 after tested.
embodiment 4
Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 50 grams, cupric oxide powder 15 grams, Zinc oxide powder 15 grams, 10 grams, sesbania powder, cellulose powder 5 grams, kaolin 5 grams, and suitable quantity of water, mixing stirs makes mixture, and the material obtained by said process is put into kneader and repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M4, the performance data of M4 is in table 1 after tested.
embodiment 5
Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 10 grams, Zinc oxide powder 10 grams, attapulgite 10 grams, alumino-silicate cement 5 grams, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material obtained by said process is put into kneader and repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M5, the performance data of M5 is in table 1 after tested.
embodiment 6
3 grams of cellulose powders are added in 70 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 10 grams, Zinc oxide powder 10 grams, attapulgite 17 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M6, the performance data of M6 is in table 1 after tested.
embodiment 7
3 grams of cellulose powders are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 40 grams, cupric oxide powder 15 grams, Zinc oxide powder 15 grams, molecular screen primary powder 10 grams, kaolin 7 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M7, the performance data of M7 is in table 1 after tested.
embodiment 8
2 grams of sesbania powder are added in 60 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 50 grams, cupric oxide powder 20 grams, Zinc oxide powder 10 grams, 10 grams, sheep liver soil, alumino-silicate cement 8 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M8, the performance data of M8 is in table 1 after tested.
embodiment 9
3 grams of activated carbon powders are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 12 grams, Zinc oxide powder 10 grams, attapulgite 5 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add 10 grams of sesbania powder, mix; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M9, the performance data of M9 is in table 1 after tested.
embodiment 10
3 grams of carbonic hydroammonium are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 50 grams, cupric oxide powder 15 grams, Zinc oxide powder 15 grams, 7 grams, sheep liver soil, kaolin 3 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add 7 grams of citric acids, mix; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M10, the performance data of M10 is in table 1 after tested.
embodiment 11
3 grams of sesbania powder are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 10 grams, Zinc oxide powder 10 grams, 10 grams, sheep liver soil, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add the aqueous solution of 5 grams of citric acids and sesbania powder, wherein the mass ratio of citric acid and sesbania powder is 1:1, is stirred by said mixture; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M11, the performance data of M11 is in table 12 after tested.
embodiment 12
3 grams of cellulose powders are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 50 grams, cupric oxide powder 15 grams, Zinc oxide powder 15 grams, 6 grams, high ridge, alumino-silicate cement 5 grams, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add the aqueous solution of 6 grams of citric acids and sesbania powder, wherein the mass ratio of citric acid and sesbania powder is 2:1, mixes; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product M12, the performance data of M12 is in table 1 after tested.
embodiment 13
3 grams of sesbania powder are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take manganese mineral powder 60 grams, cupric oxide powder 10 grams, Zinc oxide powder 10 grams, 10 grams, sheep liver soil, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add the aqueous solution of 5 grams of citric acids and sesbania powder, wherein the mass ratio of citric acid and sesbania powder is 1:1, is stirred by said mixture; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtains arsenic removal catalyst finished product M13, is applied to by M13 and has H
2s treats that dearsenification thing carries out dearsenification, after tested, and H
2the surplus of S is in table 2.
comparative example 1
Take manganese mineral powder 80 grams, di-iron trioxide 50 grams, 15 grams, sheep liver soil, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material obtained by said process is put into kneader and repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product D1, the performance data of D1 is in table 1 after tested.
comparative example 2
Take manganese mineral powder 60 grams, di-iron trioxide 40 grams, 15 grams, sheep liver soil, kaolin 10 grams, alumino-silicate cement 10 grams, 5 grams, sesbania powder, and suitable quantity of water, mixing stirs makes mixture, and the material obtained by said process is put into kneader and repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtain arsenic removal catalyst finished product D2, the performance data of D2 is in table 1 after tested.
comparative example 3
3 grams of sesbania powder are added in 50 grams of water and is mixed with translucent pore creating material slurries; Cupric oxide, zinc oxide are ground to the powder of less than 200 microns, take cupric oxide powder 10 grams, Zinc oxide powder 10 grams, 10 grams, sheep liver soil, mixing stirs makes mixture, is then added in mixture by above-mentioned pore creating material slurries and stirs; Then in mixture, add the aqueous solution of 5 grams of citric acids and sesbania powder, wherein the mass ratio of citric acid and sesbania powder is 1:1, is stirred by said mixture; The material obtained by said process is put into kneader and is repeatedly fully mediated evenly and insert banded extruder, material is extruded into φ 4 × 2-10mm strip article shaped; Drying 3 hours at article shaped being placed in 120 DEG C, roasting 3-4 hour at 350-400 DEG C, obtains arsenic removal catalyst finished product D3, is applied to by D3 and has H
2s treats that dearsenification thing 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: containing arsenic hydride 20 ~ 30ppm in unstripped gas, 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, after running in 240 hours, obtain the data of arsenic removal catalyst dearsenification efficiency in table 1.Wherein: arsenic content × 100% total in arsenic-removing rate=(after arsenic content-dearsenification total in unstripped gas in gas arsenic content)/unstripped gas.
Table 1
Table 2
Can be found out by the data in table 1, the Hydrodearsenic Catalyst that the present invention prepares, while reduction production cost, still has very high dearsenification efficiency.As can be seen from comparative example data, merely with the Hydrodearsenic Catalyst dearsenification poor effect that manganese mineral powder and di-iron trioxide are prepared for raw material, within equal service cycle, conversion ratio obviously declines, and dearsenification effect is not as good as the Hydrodearsenic Catalyst prepared by the present invention.
Can be found out by the data in table 2, 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.As can be seen from comparative example data, merely with the Hydrodearsenic Catalyst that cupric oxide and zinc oxide are prepared for raw material, cupric oxide and zinc oxide are easily and H
2s reacts, H
2s content declines, and causes the raw material for dearsenification to reduce, and arsenic-removing rate reduces, and dearsenification effect is not as good as the Hydrodearsenic Catalyst prepared by the present invention.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not 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 the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the claims in the present invention.
Claims (9)
1. an arsenic removal catalyst, is made up 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%, 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 catalyst and to give up agent.
3. arsenic removal catalyst according to claim 2, is characterized in that, the agent of giving up of described catalyst is be that the catalst for synthesis of methanol of carrier gives up agent with aluminium oxide.
4. arsenic removal catalyst according to claim 2, is characterized in that, the give up particle diameter of agent of described catalyst is less than or equal to 10nm.
5. the arsenic removal catalyst according to any one of claim 1-4, 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 according to claim 7, comprises the steps:
(1) pore creating material is mixed with slurries;
(2) manganese dioxide, cupric oxide, zinc oxide and binding agent are mixed;
(3) slurries prepared in step (1) are added in the mixture in step (2), stir, then the aqueous solution adding extrusion aid or extrusion aid wherein stirs;
(4) material that step (3) obtains is carried out mediate, shaping, obtain article shaped;
(5) drying, roasting are carried out to the article shaped that step (4) obtains.
9. the preparation method of arsenic removal catalyst according to claim 8, is characterized in that, in step (5), baking temperature is 100-120 DEG C, and drying time is 3-4 hour, and sintering temperature is 350-400 DEG C, and roasting time is 3-4 hour.
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| 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 |
| CN109529871B (en) * | 2018-12-13 | 2021-10-22 | 重庆工商大学 | Sea urchin-shaped copper-based catalyst and preparation method and application 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 |
| 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 |
| 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 |
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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Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Patentee after: SHENYANG SANJU KAITE CATALYST Co.,Ltd. Address before: 17th Floor, Dahang Jiye Building, No. 33, Renda North Road, Haidian District, Beijing, 100080 Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Patentee before: SHENYANG SANJU KAITE CATALYST Co.,Ltd. |