CN113332756A - Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof - Google Patents
Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN113332756A CN113332756A CN202110620529.3A CN202110620529A CN113332756A CN 113332756 A CN113332756 A CN 113332756A CN 202110620529 A CN202110620529 A CN 202110620529A CN 113332756 A CN113332756 A CN 113332756A
- Authority
- CN
- China
- Prior art keywords
- calcium sulfide
- vulcanizing agent
- release
- based slow
- slow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a calcium sulfide-based slow-release vulcanizing agent, and a preparation method and application thereof. Uniformly mixing molten paraffin, zeolite particles and calcium sulfide particles, carrying out cooling molding through assistance of a mold to obtain solid particles, spraying a coating liquid containing ethyl cellulose and stearic acid on the surfaces of the solid particles, and volatilizing a solvent at room temperature to obtain the calcium sulfide-based slow-release vulcanizing agent. The calcium sulfide-based slow-release vulcanizing agent can stably and slowly release heavy metal ions deeply precipitated during vulcanization in an acid solution system, has high vulcanizing agent utilization rate, and can avoid H2The escape of S causes secondary pollution, is particularly suitable for purifying heavy metal ions in an acidic solution, and the calcium sulfide-based slow-release vulcanizing agent has the advantages of simple and efficient preparation process, low raw material cost and contribution to large-scale production and application.
Description
Technical Field
The invention relates to a slow-release vulcanizing agent, in particular to a calcium sulfide-based slow-release vulcanizing agent, a preparation method of the calcium sulfide-based slow-release vulcanizing agent, and application of the calcium sulfide-based slow-release vulcanizing agent in the aspect of heavy metal ion vulcanization and precipitation in an acid solution system, and belongs to the technical field of non-ferrous metal smelting.
Background
In 2019, the capacity of the ten major nonferrous metals such as copper, aluminum, lead, zinc, nickel, antimony, magnesium and the like in China is as high as 5841.6 ten thousand tons, and the yield of the nonferrous metals is the first in the world. Meanwhile, a large amount of acidic wastewater (i.e., waste acid) containing toxic heavy metal ions such as arsenic, copper, cadmium, zinc and the like is generated in the non-ferrous metal smelting process. The sewage containing heavy nonferrous metals and compounds thereof can be accumulated and enriched in the bodies of aquatic organisms and cells of plants, and can cause serious harm to the health of human bodies and animals and plants through the actions of biological concentration, biological accumulation, biological amplification and the like in the food chain circulation. The non-ferrous metal smelting waste acid is mainly produced in the acid preparation stage and the electrolytic immersion stage by flue gas recovery, and because of the characteristics of high arsenic and heavy metal content and high residual acid content in the waste acid, a large amount of researches on the treatment of the waste acid are carried out in China.
Common methods for treating waste acid in modern nonferrous metal smelting plants include chemical methods (including lime neutralization, chemical flocculation and sulfide precipitation), physical methods (including membrane separation and adsorption), biological methods and the like. The single method is difficult to meet the current environmental protection requirement, and the two methods are combined and applied, such as a lime neutralization-iron salt method, a lime neutralization-vulcanization method and the like.
The sulfuration method can convert heavy metal ions in the waste acid into sulfides to realize high-efficiency separation of the heavy metals, and has been widely applied. Commonly used Na in the prior art2S and NaHS are taken as vulcanizing agents, and have the technical problem of easily releasing a large amount of H2S gas, sodium salt (Na) contained in the sulfurated return water and causing secondary pollution2SO4) The heat transfer wall is easy to form crust to form mirabilite (Na)2SO4·10H2O) causes an increase in equipment load, deteriorating working conditions. For firewood, standing yuan, etc. H2S gas is used as a vulcanizing agent, a gas-liquid reinforced vulcanization technology is invented, and the problem is that a vulcanizing agent H of the technology2S gas is prepared by a metal sulfide concentrated acid acidification method (such as the reaction of pyrite and hydrochloric acid) in advance, and H is prepared in large quantity in industry2S gas is extremely dangerous and operationalThe difficulty is made, a special gas-liquid reactor needs to be customized for obtaining a better vulcanization effect, and the equipment investment cost is higher. In order to fully utilize rich calcium and sulfur resources in gypsum slag, the calcium sulfide prepared by reducing the gypsum slag is reported to be used as a vulcanizing agent for polluted acid treatment at present, but the calcium sulfide used as the vulcanizing agent has the advantages of high reaction rate and H2Low utilization of S gas, part H2The escape of S gas causes secondary pollution and the like.
Disclosure of Invention
Aiming at the problems that in the prior art, the release rate of sulfur negative ions is not easy to control, the utilization rate of the vulcanizing agent is low, and part of H is not easy to control in the process of purifying the polluted acid heavy metal ions by using calcium sulfide as the vulcanizing agent through a vulcanization method2The invention aims to provide a calcium sulfide-based slow-release vulcanizing agent which is obtained by coating and modifying active substance calcium sulfide by zeolite and paraffin, can realize slow release of sulfur negative ions under an acidic condition and can realize deep purification of polluted acid heavy metal ions.
The second purpose of the invention is to provide a preparation method of the calcium sulfide-based slow-release vulcanizing agent, which has the advantages of low cost and simple operation and is beneficial to large-scale production.
The third purpose of the invention is to provide the application of the calcium sulfide-based slow-release vulcanizing agent in the aspect of heavy metal ion vulcanization and precipitation in an acid solution system, the calcium sulfide-based slow-release vulcanizing agent can slowly release sulfur negative ions in the acid solution system, the utilization rate of the vulcanizing agent is improved, the deep purification of the heavy metal ions can be realized, the pollution of hydrogen sulfide escape to the environment is reduced, and the large-scale popularization and application are facilitated.
In order to achieve the technical purpose, the invention provides a preparation method of a calcium sulfide-based slow-release vulcanizing agent, which comprises the steps of uniformly mixing molten paraffin, zeolite particles and calcium sulfide particles, carrying out mold-assisted cooling molding to obtain solid particles, spraying a coating liquid containing ethyl cellulose and stearic acid on the surfaces of the solid particles, and volatilizing a solvent at room temperature to obtain the calcium sulfide-based slow-release vulcanizing agent.
When traditional calcium sulfide is used as a vulcanizing agent, the reactivity is high, slow-release burst release exists, namely, the release rate is high in the early stage of investment, the utilization rate of the vulcanizing agent is low, resource waste and environmental pollution are caused, and after the calcium sulfide is wrapped by paraffin, the contact reaction of the active component of the calcium sulfide and an acid solution system can be completely isolated to form slow-release wrapping, namely, the active component of the calcium sulfide is excessively wrapped, and sulfur anions can not be released. The key point of the technical scheme is that the calcium sulfide is modified by the cooperation of paraffin and zeolite particles, on the basis of the calcium sulfide coated by the paraffin, a proper amount of zeolite particles are doped in the paraffin coating layer, the zeolite particles are stable in structure and good in acid resistance, the surfaces of the zeolite particles have porous structures and can be used as effective channels of liquid and sulfur negative ions, an acid solution can react with active ingredients of calcium sulfide in a calcium sulfide-based slow-release vulcanizing agent through zeolite pores, and the generated sulfur negative ions can escape from the zeolite pores to perform a vulcanization reaction on heavy metal ions entering an acid solution system, so that the aim of slow-release vulcanization is fulfilled.
As a preferable scheme, the mass ratio of the molten paraffin, the zeolite particles and the calcium sulfide particles is (1-3) to (2-4) to (3-7). The most preferred mass ratio of molten paraffin, zeolite particles and calcium sulfide particles is 1.5:3: 5.5. The paraffin is mainly used for coating active substances of calcium sulfide particles, can effectively isolate contact reaction of calcium sulfide and an acidic solution, and the zeolite particles are introduced to change the structure of the paraffin coating layer, so that an effective channel for contacting a calcium sulfide active component in the paraffin coating layer with the acidic solution is formed by utilizing the porous structure of the zeolite particles, the acidic solution can enter the slow-release agent through the porous structure of the zeolite and react with the calcium sulfide in the slow-release agent, thereby causing the concentration difference of sulfur negative ions in the internal solution and the external solution of the slow-release agent, and promoting the release of the sulfur negative ions in the slow-release agent into an acidic solution system under the action of concentration gradient. Therefore, the rate of the slow release agent for releasing sulfur negative ions into the acidic solution can be regulated and controlled by controlling the dosage ratio of the zeolite particles to the paraffin wax to the calcium sulfide. The addition amount of the paraffin affects the thickness of a coating layer on the surface of the calcium sulfide particle, when the addition proportion of the paraffin is too high, for example, the paraffin accounts for more than 30% of the mass of the sustained release agent, the calcium sulfide surface is uniformly coated with a complete paraffin layer, but the release amount of the calcium sulfide is small, the calcium sulfide is slowly released, when the addition proportion of the paraffin is moderate, for example, the addition proportion accounts for 10-20% of the mass of the sustained release agent, the sustained release agent is well formed, a small amount of cracks or active components (calcium sulfide) exist on the surface of the sustained release agent, the sustained release state can be achieved, the release is thorough, when the addition proportion of the paraffin is too low, for example, the paraffin accounts for less than 6% of the mass of the sustained release agent, the particle is not tightly bonded and is difficult to form, and the phenomenon of sustained release burst release occurs due to the too low paraffin content and the large early release rate. The contact reaction area of the acid solution and the calcium sulfide is mainly influenced by the addition amount of the zeolite particles, the higher the zeolite addition amount is, the more favorable the contact reaction of the calcium sulfide and the acid solution is, and the lower the dosage is, the slower the contact reaction rate of the calcium sulfide and the acid solution is. Therefore, the calcium sulfide-based slow-release vulcanizing agent can achieve a good effect of slowly releasing sulfur anions by controlling the paraffin, the zeolite particles and the calcium sulfide particles in an optimal proportion range.
As a preferable scheme, the molten paraffin, the zeolite particles and the calcium sulfide particles are uniformly mixed by adopting a mechanical stirring mode, the stirring speed is 100 r/min-180 r/min, and the stirring time is 15 min-25 min. The molten paraffin, the zeolite particles and the calcium sulfide particles can be uniformly mixed by controlling the mechanical stirring condition, and a uniform coating structure is formed. The stirring speed is most preferably 150r/min and the stirring time is most preferably 20 min.
As a preferable scheme, in the coating liquid, the mass of the ethyl cellulose accounts for 8-10% of that of the calcium sulfide-based slow-release vulcanizing agent; the mass of the stearic acid accounts for 3 to 5 percent of that of the calcium sulfide-based slow-release vulcanizing agent. The main raw material of the calcium sulfide slow release agent is easily oxidized in air, is easily hydrolyzed in humid air, and is sealed and moisture-proof during storage. Therefore, the technical problem is solved by spraying the coating liquid (namely the coating agent) on the surface of the slow-release vulcanizing agent in the technical scheme of the invention. The main components of the coating liquid are ethyl cellulose and stearic acid, the ethyl cellulose is an organic matter which has the characteristics of adhesion, filling, film forming and the like and can be used for coating sustained-release pellets, and the stearic acid is a surface active substance and can be mixed with the ethyl cellulose to form uniform and stable emulsion. The addition amounts of the ethyl cellulose and the stearic acid are respectively measured according to 8-10% and 3-5% of the mass of the calcium sulfide-based slow-release vulcanizing agent, if the ethyl cellulose with high proportion is added, the cost is increased, and the calcium sulfide slow-release agent is excessively wrapped, so that the early-stage slow-release speed is slow, the covering effect of the coating liquid added with the ethyl cellulose with low proportion is poor, and the surface of the slow-release agent can still contact with the air. And stearic acid as surfactant additive amount is less, excessive addition can form micelle and floccule, and too little addition is difficult to form emulsion, which causes poor spraying effect. The solvent in the coating liquid is an organic solvent which can dissolve the ethyl cellulose and the stearic acid and is volatile at room temperature. Preferred organic solvents are alcohol solvents such as ethanol, glycerol, etc., and the amount of the solvent is not limited, as long as ethyl cellulose and stearic acid are sufficiently dissolved, as will be understood by those skilled in the art.
Preferably, the mass ratio of stearic acid to ethyl cellulose is (0.5-1): 2-3. The mass ratio of stearic acid to ethylcellulose is most preferably 1: 2.5.
Preferably, the paraffin wax is melted at a temperature of 60 to 80 ℃.
The mould is a conventional mould, and is mainly used for cooling and forming paraffin to cool a mixture of molten paraffin, zeolite particles and calcium sulfide particles to form a solid particle material.
The invention also provides a calcium sulfide-based slow-release vulcanizing agent, which is prepared by the preparation method.
As a preferable scheme, the method is applied to the sulfide precipitation of heavy metal ions in an acid solution system.
As a preferable scheme, the temperature condition of the sulfide precipitation is 30-50 ℃.
As a preferable scheme, the dosage of the calcium sulfide-based slow-release vulcanizing agent is 1.1-1.5 times of the theoretical molar quantity of the calcium sulfide-based slow-release vulcanizing agent required for generating corresponding sulfides by heavy metal ions in an acidic solution system.
As a preferred scheme, the acidic solution system is at least one of waste acid, zinc leachate, copper leachate, industrial waste acid and electrolyte.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the calcium sulfide-based slow-release vulcanizing agent provided by the invention has the advantages of stable slow-release process, good slow-release effect and the like in an acid solution system, can improve the utilization rate of the vulcanizing agent, and can avoid H2The generation of S causes secondary pollution, and is particularly suitable for purifying heavy metal ions in acidic solution.
The preparation method of the calcium sulfide-based slow-release vulcanizing agent provided by the invention adopts calcium sulfide, zeolite and paraffin as raw materials, has low cost and simple and efficient preparation process, and is beneficial to large-scale production.
The calcium sulfide-based slow-release vulcanizing agent provided by the invention is applied to the vulcanization precipitation of heavy metal ions in an acid solution system, not only can deeply remove the heavy metal ions in the acid solution system, but also has high utilization rate of the vulcanizing agent, avoids the generation of harmful gas of hydrogen sulfide, is simple to operate, has a controllable process, and meets the requirements of industrial application.
Drawings
FIG. 1 is a process flow chart of the preparation of calcium sulfide-based slow-release vulcanizing agent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings and embodiments, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The arsenic concentration in the waste acid of a certain lead-zinc smelting plant in Hunan is 2g/L, the zinc ion concentration is 0.7g/L, the lead ion concentration is 100mg/L, and the copper ion concentration is 60 mg/L.
Firstly, melting paraffin at 70 ℃, adding calcium sulfide and zeolite according to the mass ratio of the paraffin to the zeolite to the calcium sulfide of 1.5:3:5.5, stirring for 20min, pouring into a mold and condensing. And (2) fully dissolving the ethyl cellulose and the stearic acid in a small amount of ethanol according to the addition amounts of 8% and 3% by mass respectively to prepare a uniform coating solution. And uniformly spraying the coating liquid on the surface of the condensed solid particles to obtain the calcium sulfide slow-release agent. Adding calcium sulfide slow release agent into acid solution, wherein the theoretical dosage of the calcium sulfide slow release agent is 1.1 times, stirring and reacting for 40min, controlling the reaction temperature at 45 ℃, adding flocculating agent to accelerate sedimentation after reaction, and finally performing solid-liquid separation. From the table 1, it can be seen that the arsenic precipitation rate of the contaminated acid after being purified by the calcium sulfide slow-release agent can reach 97.65%, the zinc ion precipitation rate can reach 92.71%, the lead ion precipitation rate can reach 92%, and the copper ion precipitation rate can reach 93.3%.
Table 1: lead-zinc smeltery contaminated acid purification filtrate of example 1 main component and ion precipitation rate (paraffin: zeolite: calcium sulfide ═ 1.5:3:5.5)
| Name (R) | AS | Zn2+ | Pb2+ | Cu2+ |
| concentration/mg/L | 47 | 51 | 8 | 4.02 |
| Precipitation rate/%) | 97.65 | 92.71 | 92.00 | 93.33 |
Comparative example 1
The dirty acid source is the same as that of the example 1, except that no zeolite is added, and the comparison between the tables 1 and 2 shows that the vulcanization effect of the calcium sulfide slow-release agent without the added zeolite is obviously lower than that of the example 1, and the waste of calcium sulfide resources is large.
Table 2: comparative example 1 contaminated acid purification filtrate of lead-zinc smeltery Main component and ion precipitation Rate (without added Zeolite)
| Name (R) | AS | Zn2+ | Pb2+ | Cu2+ |
| concentration/mg/L | 656.8 | 242.2 | 68.9 | 16.7 |
| Precipitation rate/%) | 67.16 | 65.40 | 68.90 | 72.17 |
Comparative example 2
The source of the waste acid is the same as that of the example 1, except that no ethyl cellulose is added into the coating liquid, and the comparison between the table 1 and the table 3 shows that the vulcanization effect of the calcium sulfide slow-release agent without adding the ethyl cellulose in the coating liquid is obviously lower than that of the example 1, and most of calcium sulfide in the slow-release agent is hydrolyzed or oxidized and deteriorated.
Table 3: comparative example 2 Main component and ion precipitation ratio of contaminated acid purification filtrate from lead-Zinc smelting plant (without addition of Ethyl cellulose)
| Name (R) | AS | Zn2+ | Pb2+ | Cu2+ |
| concentration/mg/L | 1593.2 | 559.02 | 75.00 | 43.68 |
| Precipitation rate/%) | 23.04 | 20.14 | 25.00 | 27.20 |
Example 2
The arsenic concentration in the waste acid of certain zinc smelting plant in Hunan is 30.3mg/L, the zinc ion concentration is 450mg/L, the cadmium ion concentration is 30.6mg/L and the copper ion concentration is 4.7 mg/L.
First of all. Melting paraffin at 70 deg.C, adding calcium sulfide and zeolite at a mass ratio of paraffin to zeolite to calcium sulfide of 1.5:3.5:5, stirring for 20min, and pouring into a mold for condensation. And dissolving ethyl cellulose and stearic acid in ethanol according to the addition of 10% and 4% by mass respectively to prepare a uniform coating solution. And uniformly spraying the coating liquid on the surface of the condensed solid particles to obtain the calcium sulfide slow-release agent. Adding a calcium sulfide slow-release agent into the contaminated acid, wherein the theoretical dosage of the calcium sulfide slow-release agent is 1.15 times, stirring and reacting for 40min, controlling the reaction temperature at 40 ℃, adding a flocculating agent to accelerate sedimentation after the reaction, and finally performing solid-liquid separation. From table 4, it can be seen that the precipitation rate of zinc ions, arsenic, cadmium ions and copper ions of the contaminated acid after being purified by the calcium sulfide slow-release agent can reach 93.78%, 92.82%, 93.20% and 95.74%.
Table 4: zinc smeltery waste acid purification filtrate of example 2 main component and ion precipitation rate (paraffin: zeolite: calcium sulfide ═ 1.5:3.5:5)
| Name (R) | As | Zn2+ | Cd2+ | Cu2+ |
| concentration/mg/L | 2.18 | 27.99 | 2.08 | 0.20 |
| Precipitation rate/%) | 92.81 | 93.78 | 93.20 | 95.74 |
Comparative example 3
The dirty acid source of comparative example 3 is the same as example 2, except that no zeolite is added. By comparing table 4 and table 5, it is found that the vulcanization precipitation rate of the calcium sulfide slow release agent without added zeolite is significantly lower than that of the example 2 of the present invention, and the waste of calcium sulfide resource is large, and the industrial application is not suitable.
Table 5: comparative example 3 Zinc smeltery contaminated acid purification filtrate Main component and ion precipitation Rate (without added Zeolite)
| Name (R) | As | Zn2+ | Cd2+ | Cu2+ |
| concentration/mg/L | 10.36 | 159.75 | 10.12 | 1.54 |
| Precipitation rate/%) | 65.81 | 64.50 | 66.92 | 67.23 |
Comparative example 4
The source of the waste acid is the same as that of the example 2, except that no ethyl cellulose is added into the coating liquid, and the comparison between tables 4 and 6 shows that the vulcanization effect of the calcium sulfide slow-release agent without the ethyl cellulose in the coating liquid is obviously lower than that of the example 2, and most of calcium sulfide in the slow-release agent is hydrolyzed or oxidized and deteriorated.
Table 6: comparative example 4 effluent acid purification filtrate of lead-zinc smeltery Main component and ion precipitation Rate (without addition of Ethyl cellulose)
Example 3
The arsenic concentration in the waste acid of certain zinc smelting plant in Hunan province is 45.3mg/L, the zinc ion concentration is 330mg/L, the lead ion concentration is 22mg/L, and the copper ion concentration is 8.0 mg/L.
First of all. Melting paraffin at 70 deg.C, adding calcium sulfide and zeolite at a mass ratio of paraffin to zeolite to calcium sulfide of 1:3:6, stirring for 25min, and pouring into a mold for condensation. And dissolving ethyl cellulose and stearic acid in ethanol according to the addition of 10% and 4% by mass respectively to prepare a uniform coating solution. And uniformly spraying the coating liquid on the surface of the condensed solid particles to obtain the calcium sulfide slow-release agent. Adding a calcium sulfide slow-release agent into the contaminated acid, wherein the theoretical dosage of the calcium sulfide slow-release agent is 1.2 times, stirring and reacting for 45min, controlling the reaction temperature at 40 ℃, adding a flocculating agent to accelerate sedimentation after the reaction, and finally performing solid-liquid separation. From table 7, it can be seen that the precipitation rate of zinc ions, arsenic and copper ions of the contaminated acid after being purified by the calcium sulfide slow-release agent can reach 95.20%, 93.50%, 95.00% and 97.40%, respectively.
Table 7: zinc smeltery contaminated acid purification filtrate of example 3 main component and ion precipitation rate (paraffin: zeolite: calcium sulfide ═ 1:3:6)
| Name (R) | AS | Zn2+ | Pb2+ | Cu2+ |
| concentration/mg/L | 2.95 | 15.84 | 1.21 | 0.21 |
| Precipitation rate/%) | 93.50 | 95.20 | 95.00 | 97.40 |
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of calcium sulfide-based slow-release vulcanizing agent is characterized by comprising the following steps: uniformly mixing molten paraffin, zeolite particles and calcium sulfide particles, carrying out cooling molding with the assistance of a mold to obtain solid particles, spraying a coating liquid containing ethyl cellulose and stearic acid on the surfaces of the solid particles, and volatilizing a solvent at room temperature to obtain the catalyst.
2. The method for preparing a calcium sulfide-based slow-release vulcanizing agent according to claim 1, wherein the calcium sulfide-based slow-release vulcanizing agent comprises the following steps: the mass ratio of the molten paraffin, the zeolite particles and the calcium sulfide particles is (1-3) to (2-4) to (3-7).
3. The method for preparing a calcium sulfide-based slow-release vulcanizing agent according to claim 1, wherein the calcium sulfide-based slow-release vulcanizing agent comprises the following steps: the molten paraffin, the zeolite particles and the calcium sulfide particles are uniformly mixed by adopting a mechanical stirring mode, the stirring speed is 100 r/min-180 r/min, and the stirring time is 15 min-25 min.
4. The method for preparing a calcium sulfide-based slow-release vulcanizing agent according to claim 1, wherein the calcium sulfide-based slow-release vulcanizing agent comprises the following steps: the mass of the ethyl cellulose in the coating liquid accounts for 8-10% of the mass of the calcium sulfide-based slow-release vulcanizing agent, and the mass of the stearic acid accounts for 3-5% of the mass of the calcium sulfide-based slow-release vulcanizing agent; the solvent in the coating liquid is an organic solvent which can dissolve the ethyl cellulose and the stearic acid and is volatile at room temperature.
5. The method for preparing a calcium sulfide-based slow-release vulcanizing agent according to claim 1 or 4, wherein: the mass ratio of stearic acid to ethyl cellulose is (0.5-1) to (2-3).
6. A calcium sulfide-based slow-release vulcanizing agent is characterized in that: the preparation method of any one of claims 1 to 5.
7. The use of a calcium sulfide-based slow-release vulcanizing agent according to claim 6, wherein: the method is applied to the sulfide precipitation of heavy metal ions in an acid solution system.
8. The use of a calcium sulfide-based slow-release vulcanizing agent according to claim 7, wherein: the temperature condition of the sulfuration precipitation is 30-50 ℃.
9. The use of a calcium sulfide-based slow-release vulcanizing agent according to claim 7, wherein: the dosage of the calcium sulfide-based slow-release vulcanizing agent is 1.1-1.5 times of the theoretical molar quantity of the calcium sulfide-based slow-release vulcanizing agent required for generating corresponding sulfides by heavy metal ions in an acidic solution system.
10. The use of a calcium sulfide-based slow-release vulcanizing agent according to claim 7, wherein: the acidic solution system is at least one of waste acid, zinc leachate, copper leachate, industrial waste acid and electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110620529.3A CN113332756B (en) | 2021-06-03 | 2021-06-03 | Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110620529.3A CN113332756B (en) | 2021-06-03 | 2021-06-03 | Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113332756A true CN113332756A (en) | 2021-09-03 |
| CN113332756B CN113332756B (en) | 2022-06-28 |
Family
ID=77473379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110620529.3A Active CN113332756B (en) | 2021-06-03 | 2021-06-03 | Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113332756B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180703A (en) * | 2021-12-30 | 2022-03-15 | 北京师范大学 | Persulfate slow-release material for in-situ remediation of underground water chlorinated hydrocarbon pollution |
| CN115572827A (en) * | 2022-10-10 | 2023-01-06 | 江西理工大学 | Method for selectively precipitating and recovering copper and arsenic from copper ash in steps |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131688A1 (en) * | 1998-05-21 | 2004-07-08 | Ingman Dov | Multi-action particle for structuring biological media |
| CN105540973A (en) * | 2015-12-28 | 2016-05-04 | 中南大学 | Method for purifying and recycling high arsenic polluted acid wastewater |
| CN107188361A (en) * | 2017-06-16 | 2017-09-22 | 中南大学 | A kind of method for being sustained vulcanizing agent and preparation method thereof and sustained release vulcanizing agent for purifying heavy metal and arsenic in acid solution |
| CN110694579A (en) * | 2019-09-17 | 2020-01-17 | 青岛众昇新材料科技有限公司 | Vulcanizing agent carrier auxiliary agent with self-adsorption property and preparation method thereof |
-
2021
- 2021-06-03 CN CN202110620529.3A patent/CN113332756B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131688A1 (en) * | 1998-05-21 | 2004-07-08 | Ingman Dov | Multi-action particle for structuring biological media |
| CN105540973A (en) * | 2015-12-28 | 2016-05-04 | 中南大学 | Method for purifying and recycling high arsenic polluted acid wastewater |
| CN107188361A (en) * | 2017-06-16 | 2017-09-22 | 中南大学 | A kind of method for being sustained vulcanizing agent and preparation method thereof and sustained release vulcanizing agent for purifying heavy metal and arsenic in acid solution |
| CN110694579A (en) * | 2019-09-17 | 2020-01-17 | 青岛众昇新材料科技有限公司 | Vulcanizing agent carrier auxiliary agent with self-adsorption property and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 乔冉冉: "冶炼烟气制酸系统废酸硫化处理理论及新工艺研究", 《中国优秀硕士论文辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114180703A (en) * | 2021-12-30 | 2022-03-15 | 北京师范大学 | Persulfate slow-release material for in-situ remediation of underground water chlorinated hydrocarbon pollution |
| CN115572827A (en) * | 2022-10-10 | 2023-01-06 | 江西理工大学 | Method for selectively precipitating and recovering copper and arsenic from copper ash in steps |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113332756B (en) | 2022-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113332756B (en) | Calcium sulfide-based slow-release vulcanizing agent and preparation method and application thereof | |
| CN107522436B (en) | Sludge curing agent and preparation method and application method thereof | |
| CN101402485B (en) | Cohesive action nutrient source SRB sewage sludge immobilization particle, production and uses in treating heavy metal wastewater thereof | |
| CN107129016B (en) | Sewage treatment agent and preparation method thereof | |
| CN101074457A (en) | Method for smelting and separating refuse-combustion fly-ash heavy metal | |
| US11196107B2 (en) | Method for recycling lead paste in spent lead-acid battery | |
| CN103588240A (en) | Green utilization method of waste acid | |
| CN101973619A (en) | Method for treating waste water from copper smelting by using modified ardealite | |
| CN102897885B (en) | The method of sulfuric acid industry Two-way Cycle jet-type arsenic removal | |
| WO2014079221A1 (en) | Reagent for processing fly ash whilst incinerating waste | |
| CN109020444B (en) | Preparation method of nano desulfurization gypsum artificial board | |
| CN106430647A (en) | Treating agent for heavy metal waste water and preparation method and application thereof | |
| CN112139200B (en) | Incineration fly ash disposal process and system thereof | |
| CN108588882A (en) | A kind of industrial residue based composite fibre and preparation method thereof | |
| CN117263716A (en) | Preparation method and application of supported bi-metal oxide sludge-based mesoporous ceramsite | |
| CN101157988A (en) | Method for purifying zinc sulfate solution | |
| CN110575812A (en) | environment-friendly adsorbing material for efficient phosphorus removal of argil/pyrolusite and preparation method thereof | |
| CN107459176B (en) | Harmless treatment process for salt-containing wastewater near-zero discharge crystallization mother liquor | |
| CN114289478B (en) | Method for recycling waste salt containing organic matters | |
| CN104445715B (en) | Treatment method for removing high-concentration nickel-containing electroplating wastewater | |
| CN104355466B (en) | A kind of purification process technique of methyl-etherified waste water | |
| CN105883995A (en) | Novel magnesium-based quick-setting material and preparation method and application thereof | |
| CN113414220B (en) | Harmless treatment method for arsenic-containing slag | |
| CN110090850A (en) | It is a kind of using humic acid as the cement solidification arsenic scum method of additive | |
| CN111072206B (en) | Method for treating acidic sewage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |