CN106512677B - Zinc oxide desulfurizer and preparation method thereof - Google Patents
Zinc oxide desulfurizer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a zinc oxide desulfurizer and a preparation method thereof, wherein the zinc oxide desulfurizer comprises the following raw materials in parts by mass: 70-80 parts of active zinc oxide, 10-30 parts of basic zinc carbonate and 5-8 parts of binder. The molding material is prepared by mixing and molding the raw materials in sequence; and then drying and roasting the molding material in sequence to obtain the zinc oxide desulfurizer. The zinc oxide desulfurizer has high content of active component zinc oxide, which reaches more than 90 percent, and the sulfur capacity is more than 30 percent.
Description
Technical Field
The invention belongs to the technical field of a desulfurizer, and particularly relates to a zinc oxide desulfurizer and a preparation method thereof.
Background
The zinc oxide desulfurizer is a medium-temperature desulfurizer and a high-temperature desulfurizer which are widely applied to the industries of ammonia synthesis, hydrogen production, methanol synthesis, coal chemical industry, petroleum refining and the like, has the advantages of high desulfurization precision, simple and convenient use, stable and reliable performance and the like, and occupies an important position in the field of industrial fine desulfurization. At present, the chemical industry at home and abroad is developing towards large-scale and environment-friendly direction, so that higher requirements are put forward for the desulfurization performance of the desulfurizer.
In the prior art, zinc oxide desulfurizer is mostly prepared by coprecipitation method, i.e. a solution containing soluble zinc salt is provided, coprecipitation reaction is carried out by adding coprecipitator, and generated precipitate is separated, washed, dried and roasted in sequence, finally zinc oxide desulfurizer with excellent performance is prepared. In the process of preparing the desulfurizer, the added precipitating agents are different, the reaction mechanisms are different, and the compositions and the structures of the obtained precipitates are greatly different, so that the performance and the desulfurization effect of the zinc oxide desulfurizer obtained after roasting are obviously different. For example, chinese patent document CN 105692685a discloses a zinc oxide desulfurizing agent and a preparation method thereof, the preparation method comprises the following steps: (1) adding ammonia water into the ammonium bicarbonate solution to prepare a mixed solution of ammonium bicarbonate and ammonium carbonate for later use; (2) putting a metal zinc raw material into a sulfuric acid solution for reaction to obtain a zinc salt solution; (3) mixing a zinc salt solution with the mixed solution prepared in the step (1), stirring at 55-60 ℃ for coprecipitation reaction, and controlling the pH value of the reaction to be 5.5-8.0 to obtain a basic zinc carbonate precursor; (4) centrifuging the basic zinc carbonate precursor, collecting precipitates, and washing and drying the precipitates in sequence to obtain a dried product; (5) roasting the dried product at the temperature of 250-550 ℃ to obtain zinc oxide; (6) and mixing the zinc oxide, the binder, the pore-forming agent and water to form a mixture, and kneading, molding, drying and roasting the mixture in sequence to obtain the zinc oxide desulfurizer. The technology adopts the mixed liquid of ammonium bicarbonate and ammonium carbonate as the precipitator, so that the desulfurization performance of the desulfurizer is improved.
However, in the preparation process of the zinc oxide desulfurizer, in order to form the desulfurizer and maintain a certain pore structure, components such as a binder and a pore-forming agent are necessarily added, and the components have corresponding beneficial effects and bring about some defects, for example, the existence of the binder and the pore-forming agent can reduce the proportion of active components in the zinc oxide desulfurizer, and further reduce the sulfur capacity of the desulfurizer. For example, when the pore-forming agent is ammonium bicarbonate, toxic ammonia gas is generated in the preparation process, and the method is not environment-friendly. . Moreover, the zinc oxide can be prepared only by directly adopting metal zinc as a raw material and carrying out a series of chemical reactions such as replacement, precipitation, double decomposition and the like, which undoubtedly increases the acquisition cost of the zinc oxide and further increases the preparation cost of the zinc oxide desulfurizer.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of high production cost and low sulfur capacity of the desulfurizer in the existing preparation process of the zinc oxide desulfurizer, and further provides the zinc oxide desulfurizer with high active ingredient content, high sulfur capacity and low cost and the preparation method thereof.
The zinc oxide desulfurizer provided by the invention is composed of the following raw materials in parts by weight:
70-80 parts of active zinc oxide
10-30 parts of basic zinc carbonate
5-8 parts of a binder.
Preferably, the particle size of the active zinc oxide is 10-15 nm;
the specific surface area of the active zinc oxide is 40-60m2/g。
Preferably, the binder is sodium metaaluminate.
The invention also provides a preparation method of the zinc oxide desulfurizer, which comprises the following steps:
sequentially carrying out molding, primary drying and primary roasting treatment on the mixture of the active zinc oxide, the basic zinc carbonate and the binder to prepare the zinc oxide desulfurizer;
the preparation process of the active zinc oxide comprises the following steps:
s1, carrying out aerobic roasting on the zinc oxide desulfurization waste agent, and collecting inactive zinc oxide materials and waste gas;
s2, washing the waste gas with sulfuric acid, and collecting washing liquid;
s3, mixing the inactive zinc oxide material with the washing liquid to perform double decomposition reaction, and performing first solid-liquid separation after the reaction is completed to obtain a first liquid phase;
s4, reacting the first liquid phase with ammonium carbonate and/or ammonium bicarbonate, and controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s5, keeping the pH value of the solution after the reaction in the step S4 is finished, heating the solution to 60-70 ℃, preserving heat and aging, and performing solid-liquid separation for the second time after aging to obtain a second solid phase;
and S6, sequentially carrying out secondary drying and secondary roasting on the second solid phase to obtain the active zinc oxide.
Preferably, the temperature of the first drying is 100-120 ℃;
the temperature of the first roasting is 350-380 ℃.
Preferably, in step S1, the temperature in the aerobic baking step is 750 to 950 ℃.
Preferably, in step S2, 25 to 35wt% of aqueous sulfuric acid solution and 3 to 5wt% of aqueous sulfuric acid solution are sequentially contacted with the waste gas in a counter-current manner.
Preferably, in step S3, the molar ratio of zinc ions in the inactive zinc oxide material to sulfuric acid in the washing liquid is (0.8-0.9): 1;
the reaction temperature of the double decomposition reaction is 20-30 ℃.
Preferably, in step S4, the molar ratio of the zinc ions in the first liquid phase to the ammonium bicarbonate is 1: (2.1-2.4); or the molar ratio of the zinc ions to the ammonium carbonate in the first liquid phase is 1: (1.05-1.2);
the reaction temperature of the reaction step is 45-50 ℃.
Preferably, in step S6, the temperature of the second drying step is 100-120 ℃;
the temperature of the second roasting step is 350-380 ℃;
in step S1, before the aerobic roasting step, the method further comprises the step of crushing the zinc oxide desulfurization waste agent to 150-200 meshes at a temperature of less than 50 ℃;
controlling the water content of the zinc oxide desulfurization waste agent to be 6-8 wt%.
Preferably, step S2, prior to the washing step, further comprises recovering heat from the exhaust gas for drying the second solid phase; and the number of the first and second groups,
collecting dust in the exhaust gas and mixing the dust with the inactive zinc oxide material in the step S3;
step S3 further includes collecting a first solid phase obtained by the first solid-liquid separation.
Preferably, in step S5, the method further includes collecting a second liquid phase obtained by the second solid-liquid separation, and evaporating the second liquid phase to dryness to obtain an ammonium sulfate solid.
Compared with the prior art, the invention has the following beneficial effects:
1) the zinc oxide desulfurizer disclosed by the embodiment of the invention adopts active zinc oxide and basic zinc carbonate, wherein the active zinc oxide has small particle size and large specific surface area, the sulfur capacity of the zinc oxide desulfurizer can be effectively improved by the property, the basic zinc carbonate can be decomposed into zinc oxide, carbon dioxide and water in the roasting process, the carbon dioxide and the water are volatilized outside, and the volatilized carbon dioxide and water enable pore channels to be formed in the zinc oxide desulfurizer, so that the bulk density of the zinc oxide desulfurizer is reduced, finally, the basic zinc carbonate is not occupied in the zinc oxide desulfurizer, and the generated zinc oxide further increases the content of active ingredients in the zinc oxide desulfurizer, and the sulfur capacity of the zinc oxide desulfurizer is improved.
2) The preparation method of the zinc oxide desulfurizer provided by the embodiment of the invention adopts active zinc oxide, basic zinc carbonate and a binder to mix, form, dry and roast to prepare the zinc oxide desulfurizer, and the zinc oxide desulfurizer has high content of active component zinc oxide, up to more than 90%, and has a sulfur capacity of more than 30%.
3) According to the preparation method of the zinc oxide desulfurizer, both the active zinc oxide and the basic zinc carbonate can come from the zinc oxide desulfurization waste agent, so that the cost of the active zinc oxide and the basic zinc carbonate is reduced, the zinc oxide desulfurization waste agent is treated, and the resource waste and the environmental pollution are avoided. The sodium metaaluminate is easy to absorb moisture, and can play a good role in bonding when being matched with zinc oxide and basic zinc carbonate.
4) In the preparation method of the zinc oxide desulfurizer disclosed by the embodiment of the invention, active zinc oxide is prepared by the following steps: firstly, roasting the zinc oxide desulfurization waste agent under an aerobic condition to remove sulfur in the zinc oxide desulfurization waste agent, so that zinc sulfide in the zinc oxide desulfurization waste agent is completely oxidized into inactive zinc oxide. Then, the waste gas generated in the roasting process is washed by sulfuric acid, so that the desulfurization waste agent mixed in the waste gas is eluted into the washing liquid, and the reduction of the regeneration rate of the desulfurization waste agent caused by the loss of the desulfurization waste agent is avoided; on the other hand, the sulfuric acid can react with the zinc volatilized from the waste desulfurization agent to generate zinc sulfate, and the zinc sulfate enters the washing liquid, so that the loss of the zinc is reduced, and the regeneration rate of the waste desulfurization agent is improved. Then, mixing the inactive zinc oxide material and the washing liquid to generate double decomposition reaction, and carrying out first solid-liquid separation after the reaction is finished to obtain a first liquid phase-zinc sulfate. And the first liquid phase reacts with the solid ammonium carbonate and/or ammonium bicarbonate, the pH value of a reaction system is controlled to be 7 in the reaction process, the leaching of zinc is facilitated under the specific reaction condition, the zinc in the solution can be completely converted into basic zinc carbonate, the loss of zinc is avoided, the recovery utilization rate of zinc is improved, and the pH value of the solution can be conveniently controlled to be 7 by adopting the reaction of the solid ammonium carbonate and/or ammonium bicarbonate and zinc sulfate, so that the loss of zinc ions is avoided. After the reaction is finished, the temperature is kept at 60-70 ℃ for aging at the pH value of 7, and when the temperature is kept at the pH value and the temperature for aging, zinc and ammonium carbonate and/or ammonium bicarbonate can be further prevented from continuously reacting to generate zinc ammonia complex ions, so that the recovery rate of zinc is further improved; and finally, drying and roasting the second solid phase in sequence to obtain the active zinc oxide. The regeneration method of the zinc oxide desulfurization waste agent has the characteristics of high regeneration rate of the desulfurization waste agent and high penetrating sulfur capacity of the regenerated active zinc oxide, and tests show that the regeneration rate of the desulfurization waste agent is up to 99.8 percent and the penetrating sulfur capacity is up to 38 percent by weight.
5) The preparation method of the zinc oxide desulfurizer in the embodiment of the invention limits the molar ratio of zinc ions in the inactive zinc oxide material to sulfuric acid in the washing liquid to be (0.8-0.9): 1, an acid environment is provided for the inactive zinc oxide material, the inactive zinc oxide material is favorably and completely converted into zinc sulfate, and the recovery rate of zinc is improved.
6) According to the preparation method of the zinc oxide desulfurizer, 25-35 wt% and 3-5 wt% of sulfuric acid aqueous solution are sequentially adopted to be in countercurrent contact with the waste gas, so that the waste gas is washed, zinc oxide desulfurization waste agent mixed in the waste gas can be effectively eluted, meanwhile, the sulfuric acid can be ensured to fully react with zinc volatilized from the desulfurization waste agent in the waste gas, the recovery rate of zinc is improved, and the regeneration rate of the desulfurization waste agent is high.
7) The preparation method of the zinc oxide desulfurizer provided by the embodiment of the invention comprises the steps of crushing the zinc oxide desulfurization waste agent to 150-200 meshes at the temperature of less than 50 ℃; the water content of the zinc oxide desulfurization waste agent is controlled to be 6-8%, the mesh number and the water content are beneficial to fully removing sulfur in the zinc oxide desulfurization waste agent in the roasting process, so that the zinc oxide desulfurization waste agent is fully converted into an inactive zinc oxide material, and the regeneration rate of the zinc oxide desulfurization waste agent is finally improved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific embodiments. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The compositions of the zinc oxide desulfurization waste agents used in the following examples and comparative examples are shown in the following table 1:
TABLE 1
| Composition of | S | O | Zn | Cl | Ca | Si | Na |
| wt% | 18～20 | 22～36 | 40～50 | Micro-scale | Micro-scale | Micro-scale | Micro-scale |
The physical properties of the ammonium bicarbonate used in each of the following examples and comparative examples are shown in table 2 below:
TABLE 2
| Name of material | Chemical formula (II) | Molecular weight | Bulk Density (g/ml) | Appearance of the product | Content (wt.) |
| Ammonium bicarbonate | NH4HCO3 | 79 | 0.773 | White powder | The nitrogen content is more than or equal to 17.1 percent |
The regeneration rates described in the following examples and comparative examples were calculated as follows: regeneration rate = moles of regenerated active zinc oxide/moles of zinc ions in spent desulfurization agent.
The breakthrough sulfur capacity of the regenerated active zinc oxide described in each of the following examples and comparative examples was measured by the following test method: taking 4g of regenerated active zinc oxide, at 350 ℃ and normal pressure (ambient pressure, usually 1 atm), and mixing the following components in volume ratio: h272%、N224%、H2The S4% (i.e. hydrogen sulfide content 40000 ppm) simulated synthesis gas was subjected to an evaluation test. Wherein, qualitative detection can be carried out by self-preparing 1wt% silver nitrate solution to carry out sulfur inlet on the outletThe minimum detection quantity of the instrument is 0.2 ppm.
The sulfur capacity of the zinc oxide desulfurizing agent described in each of the following examples and comparative examples was measured in accordance with "HG/T2513-2006 sulfur capacity test method for zinc oxide desulfurizing agent".
Example 1
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 70 parts of active zinc oxide, 30 parts of basic zinc carbonate and 5 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 10nm, and the specific surface area is 60m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 10 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 200 meshes at the temperature of 40 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 6 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 750 ℃ for 5 hours, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, sequentially carrying out countercurrent contact on the waste gas by using 25wt% and 5wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 30 ℃ for 2h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.8: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 45 ℃ for 2 hours, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.1, controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 70 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 120 ℃ for 1h, and then roasting the basic zinc carbonate filter cake at 380 ℃ for 1h to obtain active zinc oxide;
tests show that the regeneration rate of the active zinc oxide is 99.8 percent, the penetrating sulfur capacity is 38 percent, the particle size is 10nm, and the specific surface area is 60m2/g；
(2) And drying the strip material at 150 ℃ for 2h, and roasting at 560 ℃ for 4h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 0.95kg/L, the content of zinc oxide is 94.8wt%, and the sulfur capacity is 36%.
Example 2
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 80 parts of active zinc oxide, 10 parts of basic zinc carbonate and 8 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 15nm, and the specific surface area is 50m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 8 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 150 meshes at the temperature of 30 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 8 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 800 ℃ for 3 hours, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, then sequentially carrying out countercurrent contact on the waste gas by using 35wt% and 3wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 20 ℃ for 3h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.85: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 50 ℃ for 1h, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.2, controlling the pH value of the reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 60 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 120 ℃ for 0.5h, and then roasting the basic zinc carbonate filter cake at 370 ℃ for 1.5h to obtain the activated zinc oxide.
The test shows that the regeneration rate of the active zinc oxide is 99.7 percent, the penetrating sulfur capacity is 37 percent, the particle size is 15nm, and the specific surface area is 50m2/g；
(2) And drying the strip material at 200 ℃ for 1h, and roasting at 600 ℃ for 3h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.0kg/L, the content of zinc oxide is 92wt%, and the sulfur capacity is 33%.
Example 3
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 75 parts of active zinc oxide, 25 parts of basic zinc carbonate and 7 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 12nm, and the specific surface area is 58m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 12 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 180 meshes at the temperature of 40 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 7 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 850 ℃ for 2h, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, sequentially carrying out countercurrent contact on the waste gas by using 30wt% and 4wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 30 ℃ for 2h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.9: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 48 ℃ for 2 hours, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.4, controlling the pH value of the reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 70 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 110 ℃ for 0.6h, and then roasting the basic zinc carbonate filter cake at 360 ℃ for 1h to obtain the active zinc oxide.
Tests show that the regeneration rate of the active zinc oxide is 98.7%, the penetrating sulfur capacity is 35%, the particle size is 12nm, and the specific surface area is 58m2/g；
(2) And drying the strip material at 180 ℃ for 2h, and roasting at 650 ℃ for 2h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.2kg/L, the content of zinc oxide is 93wt%, and the sulfur capacity is 34%.
Example 4
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 78 parts of active zinc oxide, 18 parts of basic zinc carbonate and 6 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 13nm, and the specific surface area is 57m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 8 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 200 meshes at the temperature of 50 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 6 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 900 ℃ for 1.5h, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, sequentially carrying out countercurrent contact on the waste gas by using 25wt% and 5wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 25 ℃ for 2.5h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.8: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 46 ℃ for 2.6 hours, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.4, controlling the pH value of the reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 70 ℃, preserving heat and aging for 1.8h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
and S7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 100 ℃ for 0.7h, and roasting the basic zinc carbonate filter cake at 350 ℃ for 1.3h to obtain the activated zinc oxide.
The test shows that the regeneration rate of the active zinc oxide is 98.5 percent, the penetrating sulfur capacity is 33 percent, the particle size is 13nm, and the specific surface area is 57m2/g；
(2) And drying the strip material at 170 ℃ for 1.5h, and roasting at 560 ℃ for 4h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.1kg/L, the content of zinc oxide is 94wt%, and the sulfur capacity is 35%.
Example 5
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 74 parts of active zinc oxide, 30 parts of basic zinc carbonate and 7 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 11nm, and the specific surface area is 59m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 10 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 150 meshes at the temperature of 30 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 8 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 950 ℃ for 1h, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, then sequentially carrying out countercurrent contact on the waste gas by using 35wt% and 3wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 30 ℃ for 2h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.9: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium carbonate into the zinc sulfate filtrate, and reacting the zinc sulfate filtrate and the solid ammonium carbonate at 45 ℃ for 2h, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 1.1, controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 60 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 115 ℃ for 1h, and then roasting the basic zinc carbonate filter cake at 5350 ℃ for 1.5h to obtain the active zinc oxide.
The test shows that the regeneration rate of the active zinc oxide is 98.6 percent, the penetrating sulfur capacity is 34 percent, the particle size is 11nm, and the specific surface area is 59m2/g；
(2) And drying the strip material at 160 ℃ for 1.8h, and roasting at 600 ℃ for 2.5h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 0.98kg/L, the content of zinc oxide is 93wt%, and the sulfur capacity is 34%.
Example 6
The embodiment provides a zinc oxide desulfurizer, which comprises the following raw materials in parts by mass: 80 parts of active zinc oxide, 30 parts of basic zinc carbonate and 5 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 13nm, and the specific surface area is 57m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 10 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 180 meshes at the temperature of 40 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 7 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 850 ℃ for 2h, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, then carrying out countercurrent contact on the waste gas by using a 40wt% sulfuric acid aqueous solution, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 25 ℃ for 2h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.8: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 50 ℃ for 1h, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.4, controlling the pH value of the reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 70 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 100 ℃ for 0.9h, and then roasting the basic zinc carbonate filter cake at 370 ℃ for 1h to obtain the active zinc oxide.
The test shows that the regeneration rate of the active zinc oxide is 98.1 percent, the penetrating sulfur capacity is 31 percent, the particle size is 13nm, and the specific surface area is 5m2/g；
(2) And drying the strip material at 150 ℃ for 2h, and roasting at 650 ℃ for 3h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.0kg/L, the content of zinc oxide is 95wt%, and the sulfur capacity is 37%.
Comparative example 1
The comparative example provides a zinc oxide desulfurizer which comprises the following raw materials in parts by mass: 70 parts of active zinc oxide, 30 parts of active carbon powder and 5 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 10nm, and the specific surface area is 60m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 10 mm;
the preparation method of the active zinc oxide comprises the following steps:
s1, crushing the zinc oxide desulfurization waste agent to 200 meshes at the temperature of 40 ℃, and drying the crushed zinc oxide desulfurization waste agent to control the water content to be 6 wt%;
s2, roasting the zinc oxide desulfurization waste agent at 750 ℃ for 5 hours, and collecting inactive zinc oxide materials and waste gas;
s3, recovering heat in the waste gas, collecting dust in the waste gas, sequentially carrying out countercurrent contact on the waste gas by using 25wt% and 5wt% sulfuric acid aqueous solutions, washing the waste gas, and collecting washing liquid;
s4, adding the washing liquid collected in the step S3 into the inactive zinc oxide material collected in the step S2 and the dust collected in the step S3, carrying out double decomposition reaction on the zinc oxide and sulfuric acid at 30 ℃ for 2h, and controlling the molar ratio of zinc ions in the inactive zinc oxide material and the dust to the sulfuric acid in the washing liquid to be 0.8: 1, filtering after the double decomposition reaction is finished to obtain filter residue and zinc sulfate filtrate, wherein the filter residue can be used as a raw material of a downstream procedure;
s5, adding solid ammonium bicarbonate into the zinc sulfate filtrate, and reacting the solid ammonium bicarbonate and the zinc sulfate filtrate at 45 ℃ for 2 hours, wherein the molar ratio of zinc ions to the solid ammonium bicarbonate in the zinc sulfate filtrate is 1: 2.1, controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s6, keeping the pH value of the solution after the reaction in the step S5 unchanged, heating the solution to 70 ℃, preserving heat and aging for 1.5h, filtering after aging to obtain a basic zinc carbonate filter cake and an ammonium sulfate solution, wherein the ammonium sulfate solution can be recovered by evaporation to dryness;
s7, drying the basic zinc carbonate filter cake by utilizing the heat in the waste gas recovered in the step S3, drying the basic zinc carbonate filter cake at 120 ℃ for 1h, and then roasting the basic zinc carbonate filter cake at 380 ℃ for 1h to obtain active zinc oxide;
tests show that the regeneration rate of the active zinc oxide is 99.8 percent, the penetrating sulfur capacity is 38 percent, the particle size is 10nm, and the specific surface area is 60m2/g；
(2) And drying the strip material at 150 ℃ for 2h, and roasting at 560 ℃ for 4h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.8kg/L, the content of zinc oxide is 66wt%, and the sulfur capacity is 23%.
Comparative example 2
The comparative example provides a zinc oxide desulfurizer which comprises the following raw materials in parts by mass: 80 parts of active zinc oxide, 10 parts of basic zinc carbonate and 8 parts of sodium metaaluminate, wherein the particle size of the active zinc oxide is 15nm, and the specific surface area is 50m2/g。
The preparation method of the zinc oxide desulfurizer in the embodiment comprises the following steps:
(1) mixing active zinc oxide and basic zinc carbonate, adding sodium metaaluminate, mixing, extruding to obtain the final product
A strip material with the length of 8 mm;
(2) and drying the strip material at 200 ℃ for 1h, and roasting at 600 ℃ for 3h to obtain the zinc oxide desulfurizer.
The test shows that the bulk density of the zinc oxide desulfurizer is 1.6kg/L, the content of zinc oxide is 92wt%, and the sulfur capacity is 26%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (7)
1. A zinc oxide desulfurizer is composed of the following raw materials by weight:
70-80 parts of active zinc oxide
10-30 parts of basic zinc carbonate
5-8 parts of a binder;
the particle size of the active zinc oxide is 10-15 nm;
the specific surface area of the active zinc oxide is 40-60m2/g；
The preparation process of the active zinc oxide comprises the following steps:
s1, carrying out aerobic roasting on the zinc oxide desulfurization waste agent, and collecting inactive zinc oxide materials and waste gas;
s2, washing the waste gas with sulfuric acid, and collecting washing liquid;
s3, mixing the inactive zinc oxide material with the washing liquid to perform double decomposition reaction, and performing first solid-liquid separation after the reaction is completed to obtain a first liquid phase;
s4, reacting the first liquid phase with ammonium carbonate and/or ammonium bicarbonate, and controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s5, keeping the pH value of the solution after the reaction in the step S4 is finished, heating the solution to 60-70 ℃, preserving heat and aging, and performing solid-liquid separation for the second time after aging to obtain a second solid phase;
s6, sequentially carrying out secondary drying and secondary roasting on the second solid phase to obtain active zinc oxide;
in step S2, sequentially carrying out countercurrent contact on the waste gas by using 25-35 wt% of sulfuric acid aqueous solution and 3-5 wt% of sulfuric acid aqueous solution;
the binder is sodium metaaluminate.
2. A method for preparing the zinc oxide desulfurizing agent of claim 1, comprising the steps of:
sequentially carrying out molding, primary drying and primary roasting treatment on the mixture of the active zinc oxide, the basic zinc carbonate and the binder to prepare the zinc oxide desulfurizer;
the preparation process of the active zinc oxide comprises the following steps:
s1, carrying out aerobic roasting on the zinc oxide desulfurization waste agent, and collecting inactive zinc oxide materials and waste gas;
s2, washing the waste gas with sulfuric acid, and collecting washing liquid;
s3, mixing the inactive zinc oxide material with the washing liquid to perform double decomposition reaction, and performing first solid-liquid separation after the reaction is completed to obtain a first liquid phase;
s4, reacting the first liquid phase with ammonium carbonate and/or ammonium bicarbonate, and controlling the pH value of a reaction system to be 7 in the reaction process until the reaction is finished;
s5, keeping the pH value of the solution after the reaction in the step S4 is finished, heating the solution to 60-70 ℃, preserving heat and aging, and performing solid-liquid separation for the second time after aging to obtain a second solid phase;
and S6, sequentially carrying out secondary drying and secondary roasting on the second solid phase to obtain the active zinc oxide.
3. The method as claimed in claim 2, wherein the temperature of the first drying is 100-120 ℃;
the temperature of the first roasting is 350-380 ℃.
4. The method according to claim 2 or 3, wherein the temperature in the aerobic baking step in step S1 is 750 to 950 ℃.
5. The method according to claim 2 or 3, wherein in step S3, the molar ratio of zinc ions in the inactive zinc oxide material to sulfuric acid in the washing liquid is (0.8-0.9): 1;
the reaction temperature of the double decomposition reaction is 20-30 ℃.
6. The method according to claim 2 or 3, wherein in step S4, the molar ratio of zinc ions in the first liquid phase to the ammonium bicarbonate is 1: (2.1-2.4); or the molar ratio of the zinc ions to the ammonium carbonate in the first liquid phase is 1: (1.05-1.2);
the reaction temperature of the reaction step is 45-50 ℃.
7. The method as claimed in claim 2 or 3, wherein in step S6, the temperature of the second drying step is 100-120 ℃;
the temperature of the second roasting step is 350-380 ℃;
in step S1, before the aerobic roasting step, the method further comprises the step of crushing the zinc oxide desulfurization waste agent to 150-200 meshes at a temperature of less than 50 ℃;
controlling the water content of the zinc oxide desulfurization waste agent to be 6-8 wt%.
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