CN115845606A - Regeneration method of waste zinc oxide desulfurizer - Google Patents
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Abstract
The invention belongs to the technical field of regeneration of waste zinc oxide desulfurizer, and provides a regeneration method of waste zinc oxide desulfurizer, which comprises the following steps: s1, crushing and sieving the waste zinc oxide desulfurizer, adding the crushed and sieved waste zinc oxide desulfurizer into a reaction kettle, and adding ammonia water for stirring; s2, introducing ammonia gas, and continuing stirring; s3, adding soluble ferric salt, and dropwise adding a hydrogen peroxide solution; s4, introducing carbon dioxide gas into the reaction kettle for carbonization, adjusting the pH value of the solution, and filtering to obtain a filter cake and a filtrate; s5, removing the filter cake from a sulfur melting kettle for recycling, removing the filtrate from an ammonia still, and cooling and filtering the kettle liquid to obtain a basic zinc carbonate filter cake; s6, drying, roasting and crushing the basic zinc carbonate filter cake to obtain active zinc oxide powder; s7, kneading the active zinc oxide powder, a binder, a pore-forming agent basic zinc carbonate and water uniformly, extruding into strips, drying and roasting to obtain a zinc oxide desulfurizer product. The method can realize green recovery of the zinc oxide desulfurizer, does not generate waste gas and waste liquid, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of regeneration of waste zinc oxide desulfurizer, and particularly relates to a regeneration method of waste zinc oxide desulfurizer.
Background
Ecological environmental protection is a current focus problem. Hydrogen sulfide is a toxic gas with extremely strong harm, is a main component of malodorous gas, and is derived from industrial production of petrochemical industry, wastewater treatment, metallurgy, minerals and the like. In the presence of hydrogen sulphide, it can deactivate catalysts, corrode equipment in industrial production, and also poison people, even endangering life when the content is high. Currently, the main method for removing hydrogen sulfide gas is to use a desulfurizing agent. Among them, the zinc oxide desulfurizer is a normal temperature to medium-high temperature desulfurizer with excellent desulfurization performance, and has the advantages of high desulfurization precision, simple use, high sulfur capacity, wide use temperature range and the like, so that the zinc oxide desulfurizer is in a critical position in an industrial desulfurization system, is widely applied to industrial desulfurization of coal chemical industry, hydrogen production, synthetic ammonia and the like, and is the most widely applied desulfurizer at present.
The active component of the zinc oxide desulfurizer is zinc oxide, and after the zinc oxide reacts with hydrogen sulfide, most of the zinc oxide can be converted into zinc sulfide, so that the hydrogen sulfide in the raw materials is removed. When the sulfur of the desulfurizer is saturated, the desulfurizer no longer has the function of desulfurization. The zinc oxide desulfurizer product consumption can reach tens of thousands of tons every year in coal chemical industry and petrochemical industry. The zinc content in the waste desulfurizer is still more than 50 percent, if the waste desulfurizer is recycled, the pollution of three wastes can be greatly reduced, the recycling of resources is realized, the construction and the development of a resource-saving and environment-friendly society are facilitated, and the economic value and the social benefit are higher.
At present, the research on the regeneration problem of the zinc oxide desulfurizer is less, the waste zinc oxide desulfurizer is recovered by a dry process, the waste zinc oxide desulfurizer is firstly crushed, roasted in the air, zinc sulfide is converted into zinc oxide, and then the zinc salt is obtained after the impurities are removed by the processes of acidolysis, oxidation deslagging, zinc powder replacement, acid radical ion precipitation and the like. However, this method produces zinc salts instead of zinc oxide, and the recovery process is energy intensive, producing large amounts of waste residues and sulfur dioxide-containing waste gases.
Or a wet process is adopted, and a document reports that the waste zinc oxide desulfurizer and sulfuric acid react in a closed container at room temperature to 220 ℃, zinc in the waste desulfurizer is converted into zinc sulfate, and sulfur is converted into elemental sulfur. However, acid-containing waste liquid is generated in the process, which is not environment-friendly. In another wet process, the waste zinc oxide desulfurizer and pure water or ammonia water are subjected to hydrothermal reaction at 150-220 ℃ for 12-48 hours to convert zinc sulfide into zinc oxide, but the method is difficult to perform through judgment of reaction thermodynamics, and the hydrothermal reaction needs high temperature and high pressure, so that the requirement on production equipment is high, and the method is not beneficial to industrialization.
The treatment method of the rest waste zinc oxide desulfurizer also comprises the following steps: incineration, deep burial, chemical treatment (including chemical inhibition, acid washing, high pH cleaning solvent, lime neutralization, etc.), which all bring high cost to the enterprise and secondary pollution caused by sulfur dioxide gas emission. Because of the defects of the treatment methods and the non-wide application, the development of an environment-friendly and high-added-value waste zinc oxide desulfurizer recovery method is urgent.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a regeneration method of a waste zinc oxide desulfurizer, which can realize green recovery of the desulfurizer, wherein ammonia is recycled, sulfur is recovered in a sulfur form, no waste gas or waste liquid is generated, and the method is environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme: a regeneration method of a waste zinc oxide desulfurizer comprises the following steps:
s1, crushing and sieving a waste zinc oxide desulfurizer to obtain powder, adding the powder into a reaction kettle, adding ammonia water, and stirring;
s2, introducing ammonia gas into the reaction kettle in the S1 through a liquid ammonia storage tank, and continuously stirring; in the invention, the components of the waste zinc oxide desulfurizer can be analyzed by an instrument to determine the contents of zinc and sulfur.
The waste desulfurizer is a mixture containing metal sulfide and elemental sulfur, if sulfur and metal elements can be separated, sulfur can be obtained, environmental pollution is reduced, and simultaneously, the zinc oxide which loses activity is regenerated and reused, so that waste is changed into valuable.
The waste zinc oxide desulfurizer is treated by adopting the sulfuric acid solution, a large amount of heat can be generated in the process of adding acid, and meanwhile, hydrogen sulfide is released, so that the process is dangerous and difficult to control.
Based on the purpose, the invention firstly adds ammonia water into the reaction kettle, so that the zinc oxide in the waste desulfurizer can react with the ammonia water to generate zinc tetraammine hydroxide. The reaction formula is as follows:
ZnO+4NH 3 ·H 2 O→Zn(NH 3 ) 4 (OH) 2 +3H 2 O
s3, adding soluble ferric salt into the reaction kettle in the S2, uniformly stirring, and then dropwise adding a hydrogen peroxide solution;
because the zinc sulfide is difficult to dissolve in ammonia water, after ammonia gas is introduced, the reaction liquid in the reaction kettle still contains the zinc sulfide, in order to recover the part of the zinc sulfide, a certain amount of soluble ferric salt is added, then hydrogen peroxide is dripped to dissolve the zinc sulfide in the reaction liquid, sulfur ions are oxidized into sulfur and are precipitated, at the moment, the zinc sulfide is converted into zinc oxide, and then the zinc oxide continuously reacts with the ammonia water to generate zinc tetraammine hydroxide. The reaction formula is as follows:
ZnO+4NH 3 ·H 2 O→Zn(NH 3 ) 4 (OH) 2 +3H 2 O
wherein, the soluble ferric salt is used as a catalyst, which can accelerate the oxidation of sulfur ions into sulfur and promote the conversion of zinc sulfide into zinc oxide.
S4, after the hydrogen peroxide solution is dripped in the S3, introducing carbon dioxide gas into the reaction kettle for carbonization, adjusting the pH value of the solution to 9-10, continuing to react for a period of time, and then filtering to obtain a filter cake and filtrate;
introducing carbon dioxide gas into the reaction kettle to maintain the pH of the reaction solution at about 9-10, and then reacting part of the zinc tetraammine hydroxide with the carbon dioxide to convert the zinc tetraammine carbonate. The reaction formula is as follows:
Zn(NH 3 ) 4 (OH) 2 +CO 2 →Zn(NH 3 ) 4 CO 3 +H 2 O
in this case, the reaction solution further contains solid sulfur, and filtration is performed to obtain a sulfur-containing cake and a Zn-containing filtrate.
S5, removing the filter cake obtained in the S4 from a sulfur melting kettle for recycling, removing the filtrate from an ammonia still, heating the ammonia still for deamination, and cooling and filtering the kettle liquid after deamination to obtain a basic zinc carbonate filter cake;
and heating the Zn-containing filtrate in an ammonia still for deamination. The reaction formula is as follows:
when the filtrate is heated in the ammonia still, the zinc tetraammine carbonate in the filtrate reacts with the zinc tetraammine hydroxide to generate basic zinc carbonate precipitate and ammonia gas, and the ammonia gas escapes from the ammonia still along with water vapor. And after the deamination is finished, cooling and filtering the kettle liquid containing the basic zinc carbonate precipitate to obtain a basic zinc carbonate filter cake.
The steam volatilized from the ammonia still is mixed gas containing ammonia, and can be firstly cooled and then absorbed, and the obtained ammonia water can be used as a raw material for regenerating the waste desulfurizer, so that waste gas is avoided. And filtrate obtained by filtering the kettle liquid can be sent to an absorption tower to be used as non-condensable gas absorption liquid, so that the reutilization of raw materials can be fully realized.
S6, drying, roasting and crushing the basic zinc carbonate filter cake obtained in the S5 to obtain active zinc oxide powder;
heating and decomposing the basic zinc carbonate at high temperature to obtain active zinc oxide powder, wherein the reaction formula is as follows:
s7, uniformly kneading the active zinc oxide powder obtained in the step S6 with a binder, a pore-forming agent basic zinc carbonate and water, feeding the kneaded active zinc oxide powder into a strip extruding machine for strip extruding and forming to obtain a formed strip-shaped object, and then drying and roasting the formed strip-shaped object to obtain a zinc oxide desulfurizer product.
The regenerated zinc oxide desulfurizer prepared by the method has the characteristics of environmental protection and high efficiency, and the overall zinc recovery rate is more than 95 percent.
Based on the method, the invention can also be improved as follows:
preferably, in S1, the sieving is 200-mesh sieving, and the molar ratio of zinc to ammonia in the reaction kettle is 1:4 to 6 percent of ammonia water, and the mass fraction of ammonia water is 5 to 35 percent.
Preferably, in S1, the stirring temperature is 30-80 ℃ and the stirring time is 0.5-2 h.
Preferably, in S2, the concentration of ammonia in the reaction solution in the reaction vessel after the introduction of ammonia is 5 to 35 wt%.
Preferably, in the S3, the soluble iron salt is 1 to 10% (wt) ferrous chloride solution, and after the ferrous chloride is added, the molar ratio of sulfur to iron in the reaction kettle is 100:0.1 to 1 percent, the stirring temperature is 30 to 100 ℃, and the mass fraction of the hydrogen peroxide solution is 5 to 30 percent; the molar ratio of the hydrogen peroxide to the sulfur in the powder is 1:1 to 2.
Preferably, in the S4, the reaction is carried out at a temperature of 20-100 ℃ for 1-4 h.
Preferably, in S5, the deamination temperature of the ammonia still is 100-150 ℃.
Preferably, in S5, the filtrate obtained by the still filtration is sent to an absorption tower to be used as an absorption liquid, and the vapor volatilized from the ammonia still is sent to the absorption tower to be condensed and absorbed.
Preferably, in S6, the drying temperature of the basic zinc carbonate filter cake is 100-140 ℃, and the roasting temperature is 250-450 ℃.
Preferably, in S7, the pore-forming agent is basic zinc carbonate, the drying temperature of the formed strip is 100-140 ℃, and the roasting temperature is 350-450 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the regeneration method of the waste zinc oxide desulfurizer, provided by the invention, the zinc oxide desulfurizer is recovered by using a wet method, the method is green and efficient, the overall zinc recovery efficiency is higher than 95%, ammonia is recycled, water is recycled, sulfur is recovered in a sulfur form, and the defect of more waste gas in dry recovery is overcome. The method does not generate waste gas and waste liquid, and is environment-friendly.
2. The invention provides a regeneration method of a waste zinc oxide desulfurizer, which takes hydrogen peroxide as an oxidant and ferric salt as a catalyst to quickly dissolve insoluble zinc sulfide and S in the zinc sulfide 2- The iron salt can accelerate the reaction speed and improve the yield at the same time when being converted into sulfur.
3. The invention provides a regeneration method of a waste zinc oxide desulfurizer, which is characterized in that carbon dioxide is introduced in the reaction process for carbonization, part of zinc tetraammine hydroxide is converted into zinc tetraammine carbonate, and a precipitate product basic zinc carbonate is obtained after ammonia evaporation, wherein the basic zinc carbonate can be used for preparing active zinc oxide. The activity of the zinc oxide desulfurizer prepared by the method is better than that of the zinc oxide desulfurizer prepared by the zinc hydroxide.
4. The regeneration method of the waste zinc oxide desulfurizer provided by the invention takes basic zinc carbonate as a pore-forming agent, avoids other useless components from being mixed into the desulfurizer, improves the zinc oxide content of the desulfurizer, and increases the sulfur capacity of the desulfurizer.
Drawings
FIG. 1 is a schematic flow chart of a method for regenerating a waste zinc oxide desulfurizer, which is provided by an embodiment of the present invention;
FIG. 2 is a process schematic diagram of a method for regenerating a waste zinc oxide desulfurizer provided by an embodiment of the present invention.
Detailed Description
The present invention is further described in detail below with reference to specific examples so that those skilled in the art can more clearly understand the present invention.
Example 1
A regeneration method of a waste zinc oxide desulfurizer comprises the following steps:
s1, crushing a waste zinc oxide desulfurizer (the zinc content is about 65.4 percent and the sulfur content is about 11 percent), sieving to obtain powder with the particle size less than 200 meshes, adding 100kg of the powder into a reaction kettle, then adding 1360kg of 5 percent (wt) ammonia water, and stirring and reacting for 2 hours at 30 ℃;
s2, introducing 90Nm ammonia gas into the reaction kettle in the S1 through a liquid ammonia storage tank 3 Keeping the concentration of ammonia in the reaction liquid at 5% (wt), and continuing stirring after the ammonia gas is introduced;
s3, heating the reaction kettle in the S2 to 30 ℃, and adding the sulfur and the iron into the reaction kettle according to a molar ratio of 100:0.1 percent (wt) of ferrous chloride solution is added, the mixture is stirred evenly, then 76kg of hydrogen peroxide solution with the concentration of 5 percent (wt) is dripped into the reaction kettle until the zinc sulfide in the kettle is completely reacted;
s4, introducing carbon dioxide gas into the reaction kettle in the step S3, adjusting the pH value of the solution to enable the pH value of the solution in the reaction kettle to be 9, controlling the temperature of the reaction kettle to be 100 ℃, continuing to react for 1 hour, and then filtering to obtain a filter cake and filtrate, wherein the filter cake is sulfur;
s5, removing the filter cake obtained in the step S4 to a sulfur melting kettle for recycling, removing filtrate to an ammonia still, heating the ammonia still to 100 ℃, evaporating ammonia in the still liquid, cooling ammonia-containing steam through a cooler to obtain ammonia water, removing non-condensable gas to an absorption tower for recycling ammonia, wherein the recycled ammonia water can be used for a zinc oxide recycling process, then cooling and filtering the still liquid to obtain a basic zinc carbonate filter cake, and removing the filtrate to the absorption tower for use as absorption liquid;
wherein, the absorption tower is a packed tower and divided into two sections, clear water and filtrate of the ammonia still are used as absorbents, the upper section is a clear water absorption section, and the lower section is a filtrate absorption section of the ammonia still.
Condensing ammonia-containing steam from the ammonia still through a cooler, then discharging a gas-water mixture to the lower part of the absorption tower, discharging the gas from the top of the tower after absorption, and discharging tower bottom liquid to an ammonia water storage tank.
The volume ratio of clear water to filtrate in the ammonia still is 0.5:1.
s6, drying the basic zinc carbonate filter cake obtained in the S5 at 100 ℃, roasting at 250 ℃, crushing and sieving to obtain 78.2kg of active zinc oxide powder, wherein the recovery rate of zinc oxide is 96%;
and S7, uniformly kneading the active zinc oxide powder obtained in the step S6 with a binder and basic zinc carbonate by adding water, feeding the kneaded mixture into a strip extruding machine for strip extruding and forming, drying the formed strip at 100 ℃, and roasting the dried strip at 350 ℃ to obtain a zinc oxide desulfurizer product.
Example 2
A regeneration method of a waste zinc oxide desulfurizer comprises the following steps:
s1, crushing a waste zinc oxide desulfurizer (the zinc content is about 65.4 percent and the sulfur content is about 11 percent), sieving to obtain powder with the particle size of less than 200 meshes, adding 100kg of the powder into a reaction kettle, then adding 510kg of 20 percent (wt) ammonia water, and stirring and reacting for 1.3 hours at 55 ℃;
s2, introducing 40Nm ammonia gas into the reaction kettle in the S1 through a liquid ammonia storage tank 3 Keeping the concentration of ammonia in the reaction liquid at 10% (wt), and continuing stirring after the ammonia gas is introduced;
s3, heating the reaction kettle in the S2 to 65 ℃, and adding the sulfur and the iron into the reaction kettle according to a molar ratio of 100:0.5, adding a ferrous chloride solution with the concentration of 5 percent (wt), uniformly stirring, and then dropwise adding 12.7kg of 20 percent (wt) hydrogen peroxide solution into the reaction kettle until the zinc sulfide in the kettle is completely reacted;
s4, introducing carbon dioxide gas into the reaction kettle in the step S3, adjusting the pH value of the solution to enable the pH value of the solution in the reaction kettle to be 9, controlling the temperature of the reaction kettle to be 60 ℃, continuing to react for 2 hours, and filtering to obtain a filter cake and filtrate;
s5, removing the filter cake obtained in the step S4 to a sulfur melting kettle for recycling, removing filtrate to an ammonia still, heating the ammonia still to 125 ℃, evaporating ammonia in the still liquid, cooling ammonia-containing steam through a cooler to obtain ammonia water, removing non-condensable gas to an absorption tower for recycling ammonia, wherein the recycled ammonia water can be used for a zinc oxide recycling process, cooling and filtering the still liquid to obtain a basic zinc carbonate filter cake, and removing the filtrate to the absorption tower for use as absorption liquid;
wherein, the absorption tower is a packed tower and divided into two sections, clear water and filtrate of the ammonia still are used as absorbents, the upper section is a clear water absorption section, and the lower section is a filtrate absorption section of the ammonia still.
Condensing ammonia-containing steam from the ammonia still in a cooler, introducing the gas-water mixture to the lower part of an absorption tower, discharging the gas from the top of the tower after absorption, and introducing the tower bottom liquid into an ammonia water storage tank.
The volume ratio of clear water to filtrate in the ammonia still is 1:1.
s6, drying the basic zinc carbonate filter cake obtained in the step S5 at 120 ℃, roasting at 350 ℃, crushing and sieving to obtain 79.5kg of active zinc oxide powder, wherein the recovery rate of the zinc oxide is 97.7%; (ii) a
And S7, uniformly kneading the active zinc oxide powder obtained in the step S6 with a binder and basic zinc carbonate by adding water, feeding the kneaded mixture into a strip extruding machine for strip extruding and forming, drying the formed strip at 120 ℃, and roasting at 400 ℃ to obtain a zinc oxide desulfurizer product.
Example 3
A regeneration method of a waste zinc oxide desulfurizer comprises the following steps:
s1, crushing a waste zinc oxide desulfurizer (the zinc content is about 65.4 percent and the sulfur content is about 13 percent), sieving to obtain powder with the particle size less than 200 meshes, adding 100kg of the powder into a reaction kettle, adding 290kg of 35 percent (wt) ammonia water, and stirring and reacting for 0.5 hour at 80 ℃;
s2, introducing 100Nm ammonia gas into the reaction kettle in the S1 through a liquid ammonia storage tank 3 Keeping the concentration of ammonia in the reaction liquid at 35% (wt), and continuing stirring after the ammonia gas is introduced;
s3, heating the reaction kettle in the S2 to 100 ℃, and adding the sulfur and the iron into the reaction kettle according to the molar ratio of 100:1 adding 10 percent (wt) ferrous chloride solution, stirring uniformly, then dropwise adding 6.4kg of 30 percent (wt) hydrogen peroxide solution into the reaction kettle until the zinc sulfide in the kettle is completely reacted;
s4, introducing carbon dioxide gas into the reaction kettle in the step S3, adjusting the pH value of the solution to 10, controlling the temperature of the reaction kettle at 20 ℃, continuing to react for 4 hours, and filtering to obtain a filter cake and a filtrate;
s5, removing the filter cake obtained in the step S4 to a sulfur melting kettle for recycling, removing filtrate to an ammonia still, heating the ammonia still to 150 ℃, evaporating ammonia in the still liquid, cooling ammonia-containing steam through a cooler to obtain ammonia water, removing non-condensable gas to an absorption tower for recycling ammonia, wherein the recycled ammonia water can be used for a zinc oxide recycling process, cooling and filtering the still liquid to obtain a basic zinc carbonate filter cake, and removing the filtrate to the absorption tower for use as absorption liquid;
wherein, the absorption tower is a packed tower and divided into two sections, clear water and filtrate of the ammonia still are used as absorbents, the upper section is a clear water absorption section, and the lower section is a filtrate absorption section of the ammonia still.
Condensing ammonia-containing steam from the ammonia still in a cooler, introducing the gas-water mixture to the lower part of an absorption tower, discharging the gas from the top of the tower after absorption, and introducing the tower bottom liquid into an ammonia water storage tank.
The volume ratio of clear water to filtrate in the ammonia still is 1:1.
s6, drying the basic zinc carbonate filter cake obtained in the step S5 at 140 ℃, roasting at 450 ℃, crushing and sieving to obtain 78.9kg of active zinc oxide powder, wherein the recovery rate of zinc oxide is 96.9%;
s7, uniformly kneading the active zinc oxide powder obtained in the step S6 with a binder and basic zinc carbonate by adding water, feeding the mixture into a strip extruding machine for strip extruding and forming, drying the formed strip at 140 ℃, and roasting at 450 ℃ to obtain a zinc oxide desulfurizer product.
Comparative example 1
Zinc sulfide is oxidized without adding ferrous chloride solution and hydrogen peroxide and zinc oxide is recovered by a hydrothermal method without using a carbonization process as distinguishing conditions.
S1, crushing a waste zinc oxide desulfurizer (the zinc content is about 65.4 percent and the sulfur content is about 11 percent), sieving to obtain powder with the particle size less than 200 meshes, adding 10g of the powder into a hydrothermal reaction kettle, adding 100g of 20 percent (wt) ammonia water, and reacting for 48 hours at 200 ℃;
and S2, cooling the reaction kettle in the S1 to 35 ℃, filtering and washing, and collecting filter residues and filtrate.
And S3, evaporating ammonia from the filtrate obtained in the S2 at 100 ℃ to obtain zinc hydroxide precipitate.
And S4, filtering and washing the zinc hydroxide precipitate obtained in the S3, drying a filter cake at 120 ℃, and roasting at 450 ℃ to obtain 5.51g of zinc oxide powder, wherein the recovery rate of the zinc oxide is 67.6%.
And S5, uniformly kneading the zinc oxide powder obtained in the step S4, a binder and basic zinc carbonate by adding water, feeding the mixture into a strip extruding machine for strip extruding and forming, drying the formed strip at 120 ℃, and roasting at 400 ℃ to obtain the zinc oxide desulfurizer.
Experimental verification
The zinc oxide desulfurizing agent products prepared in examples 1 to 3 and comparative example 1 were tested.
The desulfurization performance of the regenerated zinc oxide desulfurizer is evaluated according to the method in the industry standard HG/T2513-2014, and the specific results are shown in Table 1:
TABLE 1 Sulfur Capacity test results for Zinc oxide desulfurizer products prepared in examples 1-3 and comparative example 1
The results in Table 1 show that the products of the regenerated zinc oxide desulfurizing agents prepared in examples 1 to 3 have high sulfur capacity, which is more than 20%, and can be reused. The sulfur capacity of the zinc oxide desulfurizing agent in the comparative example was significantly lower than that of examples 1 to 3 because the zinc oxide prepared from zinc hydroxide had a lower desulfurizing activity than that of zinc oxide prepared from basic zinc carbonate.
We show from the comparative example that the recovery of zinc oxide directly by ammonia process is significantly lower than this process, since ferrous chloride can be used as catalyst to rapidly dissolve insoluble zinc sulfide and S in zinc sulfide 2- The zinc oxide is converted into sulfur, so that the yield of the zinc oxide is improved; meanwhile, the active zinc oxide prepared by thermal decomposition of the basic zinc carbonate obtained by carbonization has good desulfurization activity.
The mechanisms, components and parts of the present invention which are not described in detail are all the existing structures which exist in the prior art. Can be purchased directly from the market.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A regeneration method of a waste zinc oxide desulfurizer is characterized by comprising the following steps:
s1, crushing the waste zinc oxide desulfurizer, sieving to obtain powder, adding the powder into a reaction kettle, adding ammonia water, and stirring;
s2, introducing ammonia gas into the reaction kettle in the S1, and continuously stirring;
s3, adding soluble ferric salt into the reaction kettle in the S2, uniformly stirring, and then dropwise adding a hydrogen peroxide solution;
s4, after the hydrogen peroxide solution is dripped in the S3, introducing carbon dioxide gas into the reaction kettle for carbonization, adjusting the pH value of the solution to 9-10, continuing to react for a period of time, and then filtering to obtain a filter cake and filtrate;
s5, removing the filter cake obtained in the S4 from a sulfur melting kettle for recycling, removing the filtrate from an ammonia still, heating the ammonia still for deamination, and cooling and filtering the kettle liquid after deamination to obtain a basic zinc carbonate filter cake;
s6, drying the basic zinc carbonate filter cake obtained in the S5, roasting, crushing and sieving to obtain active zinc oxide powder;
s7, uniformly kneading the active zinc oxide powder obtained in the step S6 with a binder, a pore-forming agent and water, conveying the kneaded active zinc oxide powder to a strip extruding machine for strip extruding and forming to obtain a formed strip-shaped object, and then drying and roasting the formed strip-shaped object to obtain a zinc oxide desulfurizer product.
2. The regeneration method of the waste zinc oxide desulfurizer as claimed in claim 1, wherein in the S1, the sieving is 200-mesh sieving, the mass fraction of the ammonia water is 5-35%, and the molar ratio of zinc to ammonia is 1.
3. The regeneration method of a waste zinc oxide desulfurizer as claimed in claim 1, wherein the stirring temperature in S1 is 30-80 ℃, and the stirring time is 0.5-2 h.
4. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein the concentration of ammonia in the reaction solution in the reaction vessel after the introduction of ammonia gas in the S2 is 5 to 35% (wt).
5. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein in S3, the soluble ferric salt is 1-10% (wt) ferrous chloride solution, and after the ferrous chloride is added, the molar ratio of sulfur to iron in the reaction kettle is 100:0.1 to 1 percent, the stirring temperature is 30 to 100 ℃, and the mass fraction of the hydrogen peroxide solution is 5 to 30 percent; the molar ratio of hydrogen peroxide to sulfur in the powder is 1:1 to 2.
6. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein in the step S4, the reaction temperature is 20 to 100 ℃, and the reaction is carried out for 1 to 4 hours.
7. The regeneration method of the waste zinc oxide desulfurizer as claimed in claim 1, wherein in S5, the deamination temperature of the ammonia still is 100-150 ℃.
8. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein in S5, the filtrate obtained by filtering the still is sent to an absorption tower to be used as absorption liquid, and the steam volatilized from an ammonia still is condensed and absorbed.
9. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein in S6, the drying temperature of basic zinc carbonate filter cake is 100-140 ℃, and the roasting temperature is 250-450 ℃.
10. The method for regenerating a waste zinc oxide desulfurizer as claimed in claim 1, wherein in S7, the pore-forming agent is basic zinc carbonate, the drying temperature of the formed strip is 100-140 ℃, and the roasting temperature is 350-450 ℃.
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