CN103521046A - Method for preparing normal-temperature desulfurizing agent by use of copper-zinc waste catalyst - Google Patents
Method for preparing normal-temperature desulfurizing agent by use of copper-zinc waste catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing a normal-temperature desulfurizing agent by use of a copper-zinc waste catalyst, relating to a method for preparing a normal-temperature fine copper-zinc desulfurizing agent by taking a recovered copper-zinc waste catalyst as a raw material. The method comprises the following steps of (1) dissolving the copper-zinc waste catalyst in an acid solution to obtain a dissolved solution; (2) adding a flocculating agent into the dissolved solution obtained by the step (1), flocculating and filtering to obtain a solution containing copper and zinc ions; (3) adding a precipitating agent capable of generating carbonate radical or bicarbonate radical ions into the solution containing copper and zinc ions to obtain a copper-zinc co-precipitate; (4) mixing the co-precipitate obtained by the step (3) with an adhesive acceptable in catalyst preparation, and performing conventional after-treatment to obtain the normal-temperature desulfurizing agent. The method solves the problems of small sulfur capacity and low desulfurizing precision of the desulfurizing agent prepared by use of the existing copper-zinc waste catalyst; a desulfurizing agent preparation method of acid dissolution before flocculating filtration and precipitation is provided; the obtained desulfurizing agent has high desulfurizing precision and large sulfur capacity.
Description
Technical field
The present invention relates to a kind of preparation method of normal temperature fine desulfurizing agent, be specifically related to take dead catalyst and prepare the method for normal temperature fine desulfurizing agent as raw material, belong to desulfur technology field.
Background technology
The catalyst of cupric zinc, as Cu-Zn-Al catalyst, is mainly used in synthesizing methanol, the transformationreation of hydrogen manufacturing industrial low-temperature and catalytic hydrogenation reaction etc.Above-mentioned catalyst in use, active material copper is all mainly with elemental copper form, to exist greatly, elemental copper be easy to reaction environment in sulphur, halogen etc. react, thereby there is the problems such as the sulfur poisoning of catalyst, halogen are poisoning, heat ageing, cause catalysqt deactivation, reduced the service life of catalyst.Copper zinc dead catalyst regeneration difficulty after inactivation, cannot recycle, and a large amount of decaying catalysts is piled up, and is difficult to process.But the Cu in copper zinc dead catalyst and Zn are the very important raw materials of industry, if these dead catalyst of disposal and utilization preferably just can make full use of resource, to turn waste into wealth, economic and social benefit is remarkable.
In prior art, for the recycling of copper zinc dead catalyst, in " spent catalyst recovery " write (Chemical Industry Press, calendar year 2001 version), following several method is disclosed: the first, produce copper sulphate and copper zinc fertilizer material at Sun Jinyi etc.; The second, produce zinc oxide and anhydrous cupric sulfate; Three, produce stannous chloride and zinc oxide; Four, directly produce desulfurizing agent, carry out the preparation again of copper zinc catalyst etc.; Five, thereby high-temperature roasting washing acid-hatching of young eggs recovery copper zinc dead catalyst is prepared recycling catalyst.
Wherein, utilizing copper zinc dead catalyst directly to produce desulfurizing agent, is directly as desulfurizing agent, to use after dead catalyst is crushed to certain particle diameter; But, said method be take dead catalyst as direct material, only it has been carried out to pulverization process, do not carry out any activation step, so it just makes part " release " that copper zinc dead catalyst inside do not carry out fully reaction out as the surface of catalyst by fragmentation, thereby obtains further operable catalytic activity; But the copper zinc dead catalyst in integral body after pulverization process is processed and have been absorbed a part of sulphur and taken its Sulfur capacity because it has passed through desulfurization, can be very low thereby show as the desulfurization Sulfur capacity of the copper zinc dead catalyst after pulverization process.
In addition, the high-temperature roasting washing acid-hatching of young eggs reclaims copper zinc dead catalyst, the greasy dirt that first it need to adopt roasting technique to remove and adhere on dead catalyst and inner sulfide etc., and form and be insoluble in sour Al
2o
3, the molten rear filtration washing of acid, at PH>and precipitate and separate in 7 environment, finally calcining forms CuO/ZnO catalyst; The defect of this recovery method is that roasting formation is insoluble in sour Al
2o
3cause the waste of raw material, also do not brought into play Al
2o
3carrier and crosslinked effect, meanwhile, gained CuO/ZnO catalyst desulfurizing precision is low, remaining sulfur content reaches 0.26%.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the problem that desulfurizing agent Sulfur capacity is little, desulfurization precision is low prepared by existing copper zinc dead catalyst, and the molten rear flocculation filtration of a kind of acid, reppd desulfurizing agent preparation method are provided, and gained desulfurizing agent desulfurization precision is high, and Sulfur capacity is large.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
A method of preparing ambient temperature desulfuration agent with copper zinc dead catalyst, comprises the steps:
(1) copper zinc dead catalyst is dissolved in acid solution, obtain lysate; (2) in step (1) gained lysate, add flocculant, after flocculation, filter, obtain the solution of cupric zinc ion; (3) in the solution of step (2) gained cupric zinc ion, add the precipitating reagent that can produce carbonate or bicarbonate ion, obtain the coprecipitate of copper zinc; (4) step (3) gained coprecipitate is mixed with adhesive, then carry out moulding, dry make described ambient temperature desulfuration agent;
Described copper zinc dead catalyst refers to inactivation and contains A and the catalyst of B, and A is selected from one of simple substance Cu and CuO or combination, and B is selected from one of simple substance Zn and ZnO or combination; Described acid is the inorganic acid of the above-mentioned A of solubilized and B; Described flocculant is polyacrylamide, or the mixture of polyacrylamide and inorganic polymer flocculant or organic polymer coargulator.
Further, described copper zinc dead catalyst refers to inactivation and contains CuO and the co-precipitated catalyst of ZnO.Preferably, described copper scrap zinc catalyst is containing the component of following mass percent, and CuO 25～65%, and ZnO 15～60%, Al
2o
31～10%, all the other are impurity.Most preferably, described copper zinc dead catalyst is that methyl alcohol is synthetic by copper zinc dead catalyst, low-temperature conversion copper zinc dead catalyst, one or more in copper zinc dead catalyst of aldehyde Hydrogenation alcohol.
Preferably, in described step (1), described acid is that concentration is the sulfuric acid of 40～55wt% or the nitric acid that concentration is 18～25wt%.
Preferably, described inorganic polymer flocculant is one or more in aluminium polychloride, poly-ferric chloride, PAFC and PFAS; Described organic polymer coargulator is Sodium Polyacrylate.Preferably, the concentration of aqueous solution of described polyacrylamide is 0.1～0.5wt%, and the concentration of aqueous solution of other flocculants is 3～5wt%; While using polyacrylamide separately, in every liter of lysate, its aqueous solution use amount is 4～10mg; When polyacrylamide and other flocculants are used in conjunction, in every liter of lysate, its aqueous solution use amount is than being (1～3 mg): (30～70 mg).
Preferably, described precipitating reagent is one or more of carbonic hydroammonium, sodium acid carbonate and sodium carbonate.
Preferably, in step (3), gained coprecipitate is washed, filters, is dried; Described baking temperature is 70～110 ℃.
Preferably, in step poly-(4), described adhesive is one or more of molecular sieve, kaolin, concave convex rod, sesbania powder and alumina cement; The coprecipitate of described copper zinc and the mass ratio of adhesive are (75～85): (15～25).In step (4), described dry temperature is 70～110 ℃, and be 2～10 hours drying time.
To sum up, compared with prior art, the present invention has the following advantages:
1, the method of preparing ambient temperature desulfuration agent with copper zinc dead catalyst of the present invention, with high-temperature roasting of the prior art, the washing acidleach again method of co-precipitation is compared, adopt acid molten, flocculation filtration is the method for co-precipitation again, the desulfurization performance of gained desulfurizing agent is obviously better than high-temperature roasting dead catalyst impurity removal method gained desulfurizing agent, this is mainly because adopt the mode that adds flocculant after acid is dissolved, can a step remove graphite, greasy dirt and S, than high-temperature roasting dead catalyst impurity removal method, not only can save the energy, reduce costs, can also retain the Al in dead catalyst, and performance bonds and the function that strengthens adsorptivity in end product, particularly, the existence of aluminium salt is played good peptizaiton to copper zinc active component, has taken on the role of carrier, and the subcarbonate eutectic growth of itself and copper zinc, meanwhile, under the acting in conjunction with other auxiliary agents, reclaim the easier moulding of copper zinc carbonate of gained, shaping strength also obviously improves.
Simultaneously, the desulfurizing agent heap that method of the present invention makes is than be also significantly less than the desulfurizing agent heap ratio of preparing as raw material merely in prior art after copper zinc dead catalyst is pulverized, this is to be mainly that the copper zinc carbonate that reclaims preparation is again raw material because the present invention adopts, this raw material self heap, than little, possesses the ability that multi-pore channel is provided.Reduced so on the one hand the weight of desulfurizing agent in same volume, greatly reduced cost, in desulfurizing agent, loose duct provides advantage for effective absorbing hydrogen sulphide on the other hand.
2, the Cu(OH in the copper zinc carbonate structure that prepared by the inventive method)
2and Zn(OH)
2unit plays a part very important to the high Sulfur capacity of desulfurizing agent and high desulfurization precision, and the two in solution due to effect cocrystallization growth of co-precipitation, this makes Cu(OH)
2and Zn(OH)
2these two unit can close contact, better brings into play the synergy of the two, thereby realizes the object that increases Sulfur capacity and improve desulfurization precision.Simultaneously, the present invention has adopted liquid phase and liquid phase reactor to generate the method for the carbonate deposition of copper zinc, react rapider, the copper zinc carbonate high degree of dispersion making, make can form in end product homogeneous, reasonably pore passage structure (the present invention can form the duct between molecule, rather than simple particle and the duct between particle), further improved the Sulfur capacity of desulfurizing agent; In addition, the also working condition requirement of more realistic production of liquid-liquid coprecipitation method of the present invention.
3, the copper zinc dead catalyst of the inventive method is preferably containing CuO and ZnO's but separate out etc. former thereby cause the co-precipitated catalyst of inactivation because of sulfur sensitive (as synthetic in methyl alcohol with, low-temperature conversion dead catalyst), pore structure destruction (as aldehyde Hydrogenation alcohol dead catalyst) or part elemental copper.The copper zinc catalyst why preferably prepared by coprecipitation is because catalyst copper zinc content prepared by the method is relatively high.Further, institute's copper zinc dead catalyst can also contain a certain amount of Al simple substance or oxide, as synthetic in methyl alcohol with, the oxidizing cyclohexanone Cu-Zn-Al catalyst etc. that gives up for cyclohexanol processed for, aldehyde Hydrogenation alcohol for, low-temperature conversion.Most preferably, described copper scrap zinc catalyst is containing the component of following mass percent, and CuO 25～65%, and ZnO 15～60%, Al
2o
31～10%, in all the other impurity, be mainly graphite, also have a small amount of sulphur and organic greasy dirt.Particularly, in useless catalst for synthesis of methanol, the percentage by weight of each component is CuO 60～65%, and ZnO 15～20%, Al
2o
35～10%; In useless low temperature conversion catalyst, the percentage by weight of each component is CuO 35～40%, and ZnO 38～45%, Al
2o
36～8%; In useless preparing alcohol catalyst through adding hydrogen to aldehyde, the percentage by weight of each component is CuO 25～35%, and ZnO 50～60%, Al
2o
31～2%.
4, because the consumption of copper zinc dead catalyst is large, the life-span is relatively short, all can produce a large amount of copper zinc dead catalyst every year, and the present invention adopts copper zinc dead catalyst to prepare copper zinc ambient temperature desulfuration agent as raw material, at a low price by its recovery and be used, and remarkable in economical benefits; And the cost of copper zinc dead catalyst is significantly less than soluble copper salt, advantage has been created in this cost control to desulfurizing agent.Take waste methanol catalyst as example, and by current market price estimation, waste methanol catalyst is 1.8w/t, and basic copper carbonate is 3.2w/t, and alkali formula is zinc carbonate 0.7w/t.1t waste methanol catalyst is after processing of the present invention, can obtain the copper zinc carbonate powder (aluminium hydroxide) of 1.1～1.2t, and the copper zinc carbonate powder of preparing isodose need consume basic copper carbonate 0.66～0.78t(cost 2.1～2.5w), basic zinc carbonate 0.17～0.24t(cost 0.12～0.17w), totle drilling cost is 2.22～2.67w, directly saves cost 0.42～0.87w.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is preparation technology's flow chart of copper zinc ambient temperature desulfuration agent;
Fig. 2 is the XRD spectra of the carbonate mixture of the copper zinc that makes in embodiment 1.
The specific embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein, only for description and interpretation the present invention, is not intended to limit the present invention.
embodiment 1
As shown in Figure 1, copper zinc synthesizing methanol dead catalyst is crushed to 80～100 orders, and gets 1500g sulfuric acid for 450g (mass concentration of sulfuric acid is 45%) by its dissolving; Under the state stirring, according to the polyacrylamide solution that concentration is 0.1wt% that is metered into of polyacrylamide 6mg/L, after there is alumen ustum, sedimentation is 30 minutes, filters and obtains settled solution; And then slowly adding wherein 2300g ammonium bicarbonate soln (mass concentration of carbonic hydroammonium is 18%), after precipitation is complete, washing press filtration is also dried 7 hours at 80 ℃, makes the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of the copper zinc-aluminium of above-mentioned preparation and 20g sesbania powder, 80g alumina cement and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 80 ℃ dry did Sulfur capacity evaluation after 7 hours.
In Fig. 2 XRD spectra, "●" represents the characteristic peak of basic zinc carbonate, and " ■ " represents the characteristic peak of aluminium hydroxide, other characteristic peaks that are basic copper carbonate.Fig. 2 shows, in this mixture, is mainly basic copper carbonate, and has a small amount of basic zinc carbonate and aluminium hydroxide to exist, and the component that this explanation the inventive method reclaims conforms to quality requirements.
Copper zinc synthesizing methanol dead catalyst is crushed to 100～120 orders, and gets 3500g nitric acid for 450g (mass concentration of nitric acid is 25%) by its dissolving; The mixed solution that contains according to being metered into of polyacrylamide 2mg/L and aluminium polychloride 40mg/L the aluminium polychloride aqueous solution that polyacrylamide solution that concentration is 0.2wt% and concentration are 4wt% under the state stirring, after there is alumen ustum, sedimentation is 50 minutes, filters and obtains settled solution; And then slowly adding wherein 4500g sodium bicarbonate solution (mass concentration of sodium acid carbonate is 10%), after precipitation is complete, washing press filtration is also dried 5 hours at 100 ℃, makes the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of whole copper zinc-aluminiums of above-mentioned preparation and 100g alumina cement and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 100 ℃ dry did Sulfur capacity evaluation after 5 hours.
embodiment 3
Copper zinc aldehyde hydrogenation dead catalyst is crushed to 100～120 orders, and gets 4500g nitric acid for 450g (mass concentration of nitric acid is 20%) by its dissolving; Under the state stirring, according to the polyacrylamide solution that concentration is 0.15wt% that is metered into of polyacrylamide 8mg/L, after there is alumen ustum, sedimentation is 35 minutes, filters and obtains settled solution; And then slowly adding wherein 1900g sodium carbonate liquor (mass concentration of sodium carbonate is 30%), after precipitation is complete, washing press filtration is also dried 3 hours at 110 ℃, makes the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of whole copper zinc-aluminiums of above-mentioned preparation and 100g concave convex rod and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 110 ℃ dry did Sulfur capacity evaluation after 3 hours.
embodiment 4
Copper zinc aldehyde hydrogenation dead catalyst is crushed to 80～100 orders, and gets 1350g sulfuric acid for 450g (mass concentration of sulfuric acid is 50%) by its dissolving; The mixed solution that contains according to being metered into of polyacrylamide 3mg/L and poly-ferric chloride 50mg/L the aluminium polychloride aqueous solution that polyacrylamide solution that concentration is 0.3wt% and concentration are 5wt% under the state stirring, after there is alumen ustum, sedimentation is 70 minutes, filters and obtains settled solution; And then slowly add wherein the mixed solution (containing sodium acid carbonate 10%, carbonic hydroammonium 18%) of 2000g sodium acid carbonate and carbonic hydroammonium, precipitation completely after, washing press filtration also 90 ℃ dry 6 hours, make the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of whole copper zinc-aluminiums of above-mentioned preparation and 100g kaolin and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 90 ℃ dry did Sulfur capacity evaluation after 6 hours.
embodiment 5
Copper zinc low-temperature conversion dead catalyst is crushed to 100～120 orders, and gets 4000g nitric acid for 450g (mass concentration of nitric acid is 22%) by its dissolving; The mixed solution that contains according to being metered into of polyacrylamide 0.1mg/L and PAFS 50mg/L the PAFS aqueous solution that polyacrylamide solution that concentration is 0.1wt% and concentration are 5wt% under the state stirring, after there is alumen ustum, sedimentation is 60 minutes, filters and obtains settled solution; And then slowly add wherein the mixed solution (containing sodium carbonate 30%, carbonic hydroammonium 18%) of 1600g sodium acid carbonate and carbonic hydroammonium, precipitation completely after, washing press filtration also 70 ℃ dry 10 hours, make the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of whole copper zinc-aluminiums of above-mentioned preparation and 20g sesbania powder, 80g molecular sieve and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 70 ℃ dry did Sulfur capacity evaluation after 10 hours.
embodiment 6
Copper zinc low-temperature conversion dead catalyst is crushed to 80～100 orders, and gets 4000g nitric acid for 450g (mass concentration of nitric acid is 22%) by its dissolving; The mixed solution that contains according to being metered into of polyacrylamide 0.1mg/L and PAFS 50mg/L the PAFS aqueous solution that polyacrylamide solution that concentration is 0.1wt% and concentration are 5wt% under the state stirring, after there is alumen ustum, sedimentation is 65 minutes, filters and obtains settled solution; And then slowly adding wherein 1900g sodium carbonate liquor (mass concentration containing sodium carbonate is 30%), after precipitation is complete, washing press filtration is also dried 6 hours at 100 ℃, makes the carbonate mixture of copper zinc-aluminium; By the carbonate mixture powder of whole copper zinc-aluminiums of above-mentioned preparation and 20g sesbania powder, 80g concave convex rod and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 100 ℃ dry did Sulfur capacity evaluation after 6 hours.
comparative example 1
Commercially available copper carbonate 200g mixes with commercially available zinc carbonate 200g, and with 20g sesbania powder, 80g concave convex rod and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 100 ℃ dry did Sulfur capacity evaluation after 3 hours.
comparative example 2
Copper zinc synthesizing methanol dead catalyst is crushed to 80～100 orders, get 400g and 20g sesbania powder, 80g concave convex rod and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 100 ℃ are dried 3 hours, and Sulfur capacity evaluation is done in 300 ℃ of roastings after 2 hours.
comparative example 3
Copper zinc synthesizing methanol dead catalyst is crushed to 80～100 orders, 850 ℃ of calcinings 3 hours, and get 1500g sulfuric acid 450g for (mass concentration of sulfuric acid is 45%) and dissolved, filtration obtains settled solution; And then slowly adding wherein 2300g ammonium bicarbonate soln (mass concentration of carbonic hydroammonium is 18%), after precipitation is complete, washing press filtration is also dried 7 hours at 80 ℃, makes the carbonate mixture of copper zinc; By the carbonate mixture powder of whole copper zinc of above-mentioned preparation and 20g sesbania powder, 80g alumina cement and appropriate water kneading, extruded moulding, extruding diameter is the column bar shaped desulfurizing agent of 4mm, 80 ℃ dry did Sulfur capacity evaluation after 7 hours.
test case
Desulfurizing agent Sulfur capacity is analyzed
Utilize the Sulfur capacity of normal temperature and pressure Sulfur capacity evaluating apparatus test desulfurizing agent.
Appreciation condition: desulfurizing agent loading amount 0.8g; Pressure is normal pressure; Air speed 200～400h
-1; Temperature is room temperature; Unstripped gas forms, H
2s 3.5～4.0%(v/v); Remaining is nitrogen.
Desulfurizing agent Sulfur capacity computational methods are shown below:
The Sulfur capacity of S---desulfurizing agent, %
V---gas is by the volume of desulfurizing agent, L;
The mass fraction of C---hydrogen sulfide standard gas, %;
The filling quality of m---desulfurizing agent, g.
The Sulfur capacity contrast of several desulfurizing agents of table 1
| Catalyst | Sulfur capacity % | Intensity N/cm | Heap compares Kg/L |
| Embodiment 1 | 34 | 175 | 0.77 |
| | 33 | 169 | 0.77 |
| Embodiment 3 | 30 | 163 | 0.76 |
| Embodiment 4 | 31 | 158 | 0.75 |
| Embodiment 5 | 27 | 165 | 0.75 |
| Embodiment 6 | 26 | 172 | 0.76 |
| Comparative example 1 | 25 | 185 | 0.75 |
| Comparative example 2 | 22 | 89 | 1.21 |
| Comparative example 3 | 26 | 162 | 0.77 |
From above embodiment, can see, the highest Sulfur capacity of the obtained desulfurizing agent of the present invention can be up to 34%, removes in rear tail gas sulfide hydrogen amount lower than 0.05ppm; Heap is than the minimum 0.75Kg/L that reaches.Particularly:
Comparative example 1 and 2 gained desulfurizing agent Sulfur capacity are all lower than embodiment gained desulfurizing agent Sulfur capacity, illustrate that it is raw material that the carbonate of copper zinc waste catalyst recovery copper zinc is take in the present invention, the Sulfur capacity of the desulfurizing agent making by kneading method (embodiment 1-6), higher than with commercially available copper carbonate and zinc carbonate being desulfurizing agent (comparative example 1) prepared by raw material, also higher than the desulfurizing agent (comparative example 2) of preparing as raw material after copper zinc dead catalyst is pulverized merely.
Comparative example 3 gained desulfurizing agent Sulfur capacity are less than embodiment 1 and 2, and embodiment 1,2 and comparative example 3 all adopt copper zinc synthesizing methanol dead catalyst to make raw material, therefore illustrate that flocculence gained desulfurizing agent Sulfur capacity of the present invention reclaims gained desulfurizing agent higher than the high-temperature roasting washing acid-hatching of young eggs.
Further analyze, we are divided into 3 groups by embodiment 1-6, be respectively embodiment 1-2 group, embodiment 3-4 group, embodiment 5-6 group, these 3 groups of embodiment adopt respectively useless catalst for synthesis of methanol (CuO 60～65%), useless preparing alcohol catalyst through adding hydrogen to aldehyde (CuO 25～35%), useless low temperature conversion catalyst (CuO 35～40%), from Sulfur capacity data analysis, along with the increase of copper content in dead catalyst, the Sulfur capacity of products obtained therefrom increases thereupon; Therefore, this inventive method is particularly useful for the dead catalyst that copper content is higher.
Finally it should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (11)
1. with copper zinc dead catalyst, prepare a method for ambient temperature desulfuration agent, comprise the steps:
(1) copper zinc dead catalyst is dissolved in acid solution, obtain lysate;
(2) in step (1) gained lysate, add flocculant, after flocculation, filter, obtain the solution of cupric zinc ion;
(3) in the solution of step (2) gained cupric zinc ion, add the precipitating reagent that can produce carbonate or bicarbonate ion, obtain the coprecipitate of copper zinc;
(4) step (3) gained coprecipitate is mixed with adhesive, then carry out moulding, dry make described ambient temperature desulfuration agent;
Described copper zinc dead catalyst refers to inactivation and contains A and the catalyst of B, and A is selected from one of simple substance Cu and CuO or combination, and B is selected from one of simple substance Zn and ZnO or combination; Described acid is the inorganic acid of the above-mentioned A of solubilized and B; Described flocculant is polyacrylamide, or the mixture of polyacrylamide and inorganic polymer flocculant or organic polymer coargulator.
2. the method for preparing ambient temperature desulfuration agent with copper zinc dead catalyst according to claim 1, is characterized in that, described copper zinc dead catalyst refers to inactivation and contains CuO and the co-precipitated catalyst of ZnO.
3. the method for preparing ambient temperature desulfuration agent with copper zinc dead catalyst according to claim 1, is characterized in that, described copper scrap zinc catalyst is containing the component of following mass percent, and CuO 25～65%, and ZnO 15～60%, Al
2o
31～10%, all the other are impurity.
4. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in claim 1-3 any one, it is characterized in that, described copper zinc dead catalyst is that methyl alcohol is synthetic by copper zinc dead catalyst, low-temperature conversion copper zinc dead catalyst, one or more in copper zinc dead catalyst of aldehyde Hydrogenation alcohol.
5. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-4, it is characterized in that, in described step (1), described acid is that concentration is the sulfuric acid of 40～55wt% or the nitric acid that concentration is 18～25wt%.
6. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-5, it is characterized in that, described inorganic polymer flocculant is one or more in aluminium polychloride, poly-ferric chloride, PAFC and PFAS; Described organic polymer coargulator is Sodium Polyacrylate.
7. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-6, it is characterized in that, the concentration of aqueous solution of described polyacrylamide is 0.1～0.5wt%, and the concentration of aqueous solution of other flocculants is 3～5wt%; While using polyacrylamide separately, in every liter of lysate, its aqueous solution use amount is 4～10mg; When polyacrylamide and other flocculants are used in conjunction, in every liter of lysate, its aqueous solution use amount is than being (1～3 mg): (30～70 mg).
8. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-7, it is characterized in that, described precipitating reagent is one or more of carbonic hydroammonium, sodium acid carbonate and sodium carbonate.
9. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-8, it is characterized in that, in step (3), to gained coprecipitate wash, filter, dry; Described baking temperature is 70～110 ℃.
10. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-9, it is characterized in that, in step poly-(4), described adhesive is one or more of molecular sieve, kaolin, concave convex rod, sesbania powder and alumina cement; The coprecipitate of described copper zinc and the mass ratio of adhesive are (75～85): (15～25).
11. according to preparing the method for ambient temperature desulfuration agent with copper zinc dead catalyst described in any one in claim 1-10, it is characterized in that, in step (4), described dry temperature is 70～110 ℃, and be 2～10 hours drying time.
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| CN107029545A (en) * | 2017-04-14 | 2017-08-11 | 山东科技大学 | A kind of copper-plated zinc steel wire drawing sludge-based desulfurizer and preparation method thereof |
| CN107511057A (en) * | 2017-08-03 | 2017-12-26 | 山东科技大学 | A kind of method for preparing multiple active components desulfurizing agent using cupric zinc organic sludge and pickling sludge |
| CN108854476A (en) * | 2017-05-10 | 2018-11-23 | 神华集团有限责任公司 | Protective agent of methanol synthesis catalyst and its preparation method and application |
| CN111333102A (en) * | 2020-04-22 | 2020-06-26 | 安徽锦华氧化锌有限公司 | Preparation method of zinc oxide for sulfur removal agent |
| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
| CN114471577A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | Scrap Cu/ZnO/Al2O3Method for preparing new catalyst precursor by using catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237471A (en) * | 1998-06-02 | 1999-12-08 | 中国科学院山西煤炭化学研究所 | Application of chrome-contained waste catalyst as desulfurizing agent |
| US20100111787A1 (en) * | 2007-03-13 | 2010-05-06 | Man Joo Kim | Method of recovering valuable metals from the vrds spent catalyst |
| CN102212694A (en) * | 2011-04-21 | 2011-10-12 | 江苏科创石化有限公司 | Method for extracting valuable metal from waste hydrogenation catalyst |
-
2012
- 2012-07-04 CN CN201210229565.8A patent/CN103521046B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237471A (en) * | 1998-06-02 | 1999-12-08 | 中国科学院山西煤炭化学研究所 | Application of chrome-contained waste catalyst as desulfurizing agent |
| US20100111787A1 (en) * | 2007-03-13 | 2010-05-06 | Man Joo Kim | Method of recovering valuable metals from the vrds spent catalyst |
| CN102212694A (en) * | 2011-04-21 | 2011-10-12 | 江苏科创石化有限公司 | Method for extracting valuable metal from waste hydrogenation catalyst |
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| CN105478001A (en) * | 2015-12-30 | 2016-04-13 | 北京三聚环保新材料股份有限公司 | Method for preparing desulfurizing agent from copper-zinc dead catalyst |
| CN107029545A (en) * | 2017-04-14 | 2017-08-11 | 山东科技大学 | A kind of copper-plated zinc steel wire drawing sludge-based desulfurizer and preparation method thereof |
| CN107029545B (en) * | 2017-04-14 | 2019-09-10 | 山东科技大学 | A kind of copper-plated zinc steel wire drawing sludge-based desulfurizer and preparation method thereof |
| CN108854476A (en) * | 2017-05-10 | 2018-11-23 | 神华集团有限责任公司 | Protective agent of methanol synthesis catalyst and its preparation method and application |
| CN108854476B (en) * | 2017-05-10 | 2021-04-27 | 神华集团有限责任公司 | Protective agent for methanol synthesis catalyst, and preparation method and application thereof |
| CN107511057A (en) * | 2017-08-03 | 2017-12-26 | 山东科技大学 | A kind of method for preparing multiple active components desulfurizing agent using cupric zinc organic sludge and pickling sludge |
| CN107511057B (en) * | 2017-08-03 | 2019-06-28 | 山东科技大学 | A method of multiple active components desulfurizing agent is prepared using cupric zinc organic sludge and pickling sludge |
| CN111333102A (en) * | 2020-04-22 | 2020-06-26 | 安徽锦华氧化锌有限公司 | Preparation method of zinc oxide for sulfur removal agent |
| CN114471577A (en) * | 2020-10-27 | 2022-05-13 | 中石化南京化工研究院有限公司 | Scrap Cu/ZnO/Al2O3Method for preparing new catalyst precursor by using catalyst |
| CN114471577B (en) * | 2020-10-27 | 2024-02-09 | 中石化南京化工研究院有限公司 | Waste Cu/ZnO/Al 2 O 3 Method for preparing new catalyst precursor by using catalyst |
| CN112604651A (en) * | 2020-12-18 | 2021-04-06 | 湖北润驰环保科技有限公司 | Method for preparing high-efficiency desulfurizer by using waste molecular sieve catalyst and waste zinc oxide desulfurizer as raw materials |
| CN112604651B (en) * | 2020-12-18 | 2023-06-09 | 湖北润驰环保科技有限公司 | Method for preparing efficient desulfurizing agent by using waste molecular sieve catalyst and waste zinc oxide desulfurizing agent as raw materials |
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