CN110950789A - Regeneration method of nickel-removing chelating agent in aluminum sulfate production process - Google Patents
Regeneration method of nickel-removing chelating agent in aluminum sulfate production process Download PDFInfo
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- CN110950789A CN110950789A CN201911271632.0A CN201911271632A CN110950789A CN 110950789 A CN110950789 A CN 110950789A CN 201911271632 A CN201911271632 A CN 201911271632A CN 110950789 A CN110950789 A CN 110950789A
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- nickel
- chelating agent
- aluminum sulfate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
Abstract
The invention discloses a regeneration method of a nickel-removing chelating agent in the production process of aluminum sulfate, which mainly comprises the following steps: (1) chelating agent and heavy metal ions Ni2+Removing impurities from soluble salt by combining the generated heavy metal salt nickel thiram precipitate; (2) and (3) placing the nickel-thiram precipitate after impurity removal into a rotary roasting furnace, introducing reducing gas, and controlling the reaction temperature to obtain nickel sulfide, dimethylamine and carbon disulfide. (3) The dimethylamine and the carbon disulfide obtained in the step (2) generate thiram acid in the condensation process, and then sodium thiram is obtained by absorption reaction of liquid alkali; (4) and (3) packaging and storing the nickel sulfide obtained in the step (2) under the drive of protective gas. The invention has the technical advantages that the dry method is adopted to realize the regeneration and recycling of the heavy metal chelating agent sodium fermet, the production cost of the aluminum sulfate is reduced, the metal separation is realized, andthe nickel separation and drying are realized in the same equipment, the equipment utilization rate is high, and the investment is small.
Description
Technical Field
The invention belongs to the technical field of recycling, and relates to a regeneration method of a nickel-removing chelating agent in an aluminum sulfate production process.
Background
In the process of preparing aluminum sulfate by using a catalytic cracking waste catalyst, the waste catalyst contains heavy metals such as nickel, so that the prepared aluminum sulfate product is poor in quality, and in order to obtain a pure aluminum sulfate product without heavy metals, a chelating agent sodium ferbamate is adopted in the production to remove the heavy metals in the waste catalyst, two problems exist in the whole process, namely the sodium ferbamate is high in price, and the nickel ferbamate waste residue is generated, so that the conversion treatment of the nickel ferbamate waste residue is realized while the sodium ferbamate is recycled, and the method becomes a key point for improving the technical level of the process and reducing the production cost of aluminum sulfate.
The sodium ferbamate is an important heavy metal remover and is widely applied to wastewater treatment and heavy metal impurity removal. At present, the recovery report is mainly wet recovery, and chinese patent CN104528819A discloses a method for recovering precipitant in titanium dioxide production process, which is mainly to add metal precipitation solid into sodium hydroxide solution to make metal generate hydroxide and make precipitant reduce. Chinese patent application No. CN103304462A
A process for recovering sodium diethyldithiocarbamate is disclosed, which comprises adding sodium hydroxide solution to iron diethyldithiocarbamate solution, wherein the weight ratio of iron diethyldithiocarbamate to sodium hydroxide is 1:3, controlling the reaction condition while stirring, and filtering the resultant reaction solution to obtain sodium diethyldithiocarbamate solution. Generally, the existing recovery method is mainly wet conversion recovery, no report of dry decomposition conversion recovery exists, and the nickel fermat is relatively stable in property, almost insoluble in water and difficult to realize conversion and recovery of the nickel fermat in the solution.
The invention has the following technical advantages:
1) according to the characteristic that the thiram is easy to decompose under an acidic condition, the thiram is placed in an acidic gas at a high temperature, can be subjected to acidolysis to form carbon disulfide and dimethylamine under the synchronous condition of reducibility and acidity, and sequentially escapes in a high-temperature environment, the thiram is immediately generated in the escaping process, the thiram is condensed and then is changed into thiram sodium through sodium hydroxide absorption reaction, so that the recovery of the thiram sodium is realized, and heavy metals can be changed into heavy metal inorganic salts to realize separation.
2) The invention innovatively adopts a dry decomposition technology to realize the recovery of sodium ferulate.
3) The method can realize the recovery of sodium ferulate and the separation of metal salt in one step, and has the advantages of simple process, strong operability, high equipment utilization rate and small investment.
Disclosure of Invention
The invention aims to provide a method for recovering a nickel-removing chelating agent in the production process of aluminum sulfate, and in order to realize the purpose, the technical scheme of the invention is as follows:
1. a method for regenerating a nickel-removing chelating agent used in the production process of aluminum sulfate is characterized in that: (1) chelating agent and heavy metal ions Ni2+Removing impurities from soluble salt by combining the generated heavy metal salt nickel thiram precipitate; (2) putting the nickel precipitate after impurity removal into a rotary roasting furnace, and introducing H2S and N2Mixing the gases, and controlling the reaction temperature and the reaction time to obtain the nickel sulfide, the dimethylamine and the carbon disulfide. (3) And (3) condensing the dimethylamine and the carbon disulfide in the step (2) to form the thiram acid, and absorbing and reacting the thiram acid with liquid alkali to obtain the thiram sodium. (4) And (3) packaging and storing the nickel sulfide obtained in the step (2) under the drive of protective gas.
2. Wherein the chelating agent in the regeneration method of the nickel-removing chelating agent in the production process of the aluminum sulfate is sodium dimethyl dithiocarbamate;
3. the soluble salt in the step (1) is mainly aluminum sulfate and a small amount of sodium sulfate;
4. the nickel thiram precipitate in the step (2) is wet or pretreated by water vapor in advance, and the water content is required to be more than or equal to 10 percent, preferably 30 to 50 percent;
5. the reducing gas in the step (2) is H2S and N2Mixed gas of (2), H2S and Ar2Mixed gas of (2) or H2S and He2And H is one of the mixed gases of2The gas partial pressure of S is 5-50%, preferably 25-30%;
6. the reaction temperature in the step (2) is 150-250 ℃, and preferably 200-220 ℃;
7. the reaction time in the step (2) is 10-60 min, preferably 25-35 min;
8. the condensation temperature in the step (3) is 0-10 ℃, and is preferably 5-10 ℃;
9. the mass concentration of the liquid caustic soda in the step (3) is 8-15%, and preferably 10-12%;
10. the reaction temperature of the liquid caustic soda in the step (3) is controlled to be 5-20 ℃, and preferably 10-15 ℃;
11. the protective gas in the step (4) is N2、Ar2Or He2One kind of (1).
The method has the technical advantages that the recovery of sodium ferulate and the separation of metal salt can be realized in one step under the non-solution state according to the characteristic that thiram is easy to decompose under the reducing atmosphere and acidic condition, the production cost of aluminum sulfate can be effectively reduced, the process is simple, and the operation is easy. The reactions involved in the present invention are shown below:
Detailed Description
In order to better and more particularly illustrate the details of the present invention, reference is made to the following examples:
example 1
(1) Chelating agent and heavy metal ions Ni2+Pulping and washing the generated heavy metal salt thiram precipitate to obtain pure thiram precipitate; (2) putting the nickel precipitate with the water content of 23 percent after impurity removal into a rotary roasting furnace, and introducing H2S and N2Mixing gas, control H2The partial pressure of S is 20%, and nickel sulfide, dimethylamine and carbon disulfide are obtained after reaction for 30min at 200 ℃; (3) and (3) carrying out condensation reaction on dimethylamine and carbon disulfide in the step (2) at the temperature of 5 ℃ to generate fulvic acid, and absorbing the fulvic acid by using liquid alkali with the mass fraction of 12% to obtain sodium ferulate. (4) The nickel sulfide obtained in the step (2) is added in N2Packaging and storing under the drive of protective gas.
Example 2
(1) By separating chelating agents and heavy metalsSeed Ni2+Pulping and washing the generated heavy metal salt thiram precipitate to obtain pure thiram precipitate; (2) putting the nickel precipitate with water content of 27% after impurity removal into a rotary roasting furnace, and introducing H2Mixed gas of S and He, control of H2The partial pressure of S is 22 percent, and nickel sulfide, dimethylamine and carbon disulfide are obtained after reaction is carried out for 30min at the temperature of 200 ℃; (3) and (3) carrying out condensation reaction on dimethylamine and carbon disulfide in the step (2) at 7 ℃ to generate fulvic acid, and absorbing the fulvic acid by using 11% liquid alkali by mass fraction to obtain sodium ferulate. (4) The nickel sulfide obtained in the step (2) is added in N2Packaging and storing under the drive of protective gas.
Example 3
(1) Chelating agent and heavy metal ions Ni2+Washing the precipitate with the generated heavy metal salt thiram to obtain pure thiram precipitate; (2) putting the nickel precipitate with the water content of 30 percent after impurity removal into a rotary roasting furnace, and introducing H2Mixed gas of S and He, control of H2The partial pressure of S is 22 percent, and nickel sulfide, dimethylamine and carbon disulfide are obtained after reaction for 20min at 200 ℃; (3) and (3) carrying out condensation reaction on dimethylamine and carbon disulfide in the step (2) at the temperature of 3 ℃ to generate fulvic acid, and absorbing the fulvic acid by using 11% liquid alkali by mass fraction to obtain sodium ferulate. (4) The nickel sulfide obtained in the step (2) is added in N2Packaging and storing under the drive of protective gas.
Example 4
(1) Chelating agent and heavy metal ions Ni2+Pulping and washing the generated heavy metal salt thiram precipitate to obtain pure thiram precipitate; (2) putting the nickel precipitate with water content of 27% after impurity removal into a rotary roasting furnace, and introducing H2Mixed gas of S and He, control of H2The partial pressure of S is 22 percent, and nickel sulfide, dimethylamine and carbon disulfide are obtained after reaction for 40min at 200 ℃; (3) and (3) carrying out condensation reaction on dimethylamine and carbon disulfide in the step (2) at the temperature of 5 ℃ to generate fulvic acid, and absorbing the fulvic acid by using liquid alkali with the mass fraction of 12% to obtain sodium ferulate. (4) The nickel sulfide obtained in the step (2) is added in N2Packaging and storing under the drive of protective gas.
Comparative example a sodium thiram sample from a company was purchased.
In order to verify the using effect of the recovered sodium ferulate, the recovered sodium ferulate was reused in the impurity removal process of nickel-containing aluminum sulfate, and the using effect was compared with that of a comparative example (purchased sodium ferulate sample), and the results are shown in the following table:
the use effect of the recovered sodium dimethyl dithiocarbamate can be seen, the removal effect of the recovered sodium dimethyl dithiocarbamate on heavy metal nickel is equivalent to that of the recycled sodium dimethyl dithiocarbamate, and thus the technical advancement of the invention is verified. The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (11)
1. A method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate is characterized in that: (1) chelating agent and heavy metal ions Ni2+Removing impurities from soluble salt by combining the generated heavy metal salt nickel thiram precipitate; (2) putting the nickel precipitate after impurity removal into a rotary roasting furnace, and introducing H2And (3) controlling the reaction temperature and the reaction time by using mixed gas of S and inert gas to obtain nickel sulfide, dimethylamine and carbon disulfide. (3) And (3) forming the thiram acid in the condensation process of the dimethylamine and the carbon disulfide in the step (2), and absorbing and reacting by using liquid alkali to obtain the thiram sodium. (4) And (3) packaging and storing the nickel sulfide obtained in the step (2) under the drive of protective gas.
2. The method for regenerating a chelating agent for removing nickel in the production process of aluminum sulfate as set forth in claim 1, wherein said chelating agent is sodium fermet.
3. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the soluble salt in the step (1) is mainly aluminum sulfate and a small amount of sodium sulfate.
4. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the nickel thiram precipitate in the step (2) is wet or pretreated by water vapor in advance, and the water content is required to be more than or equal to 10%, and is preferably 30-50%.
5. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the reducing gas in the step (2) is H2S and N2Mixed gas of (2), H2Mixed gas of S and Ar or H2One of mixed gases of S and He, and H2The gas partial pressure of S is 5 to 50%, preferably 25 to 30%.
6. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the reaction temperature in the step (2) is 150-250 ℃, and preferably 200-220 ℃.
7. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the reaction time in the step (2) is 10-60 min, preferably 25-35 min.
8. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the condensation temperature in the step (3) is 0-10 ℃, and preferably 5-10 ℃.
9. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the mass concentration of the liquid caustic soda (calculated by NaOH) in the step (3) is 8-15%, and preferably 10-12%.
10. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the reaction temperature of the step (3) and the liquid caustic soda is controlled to be 5-20 ℃, and preferably 10-15 ℃.
11. The method for regenerating a nickel-removing chelating agent in the production process of aluminum sulfate according to claim 1, wherein the method comprises the following steps: the protective gas in the step (4) is N2Ar or He.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113562877A (en) * | 2021-07-26 | 2021-10-29 | 中南大学 | Treatment method of EDTA-Ni-containing wastewater |
| CN113802008A (en) * | 2021-09-16 | 2021-12-17 | 兰州大学 | Method for treating waste liquid containing platinum group noble metal |
| CN113845455A (en) * | 2021-10-12 | 2021-12-28 | 兰州大学 | Method for recycling Fumei slag |
| CN113930616A (en) * | 2021-10-12 | 2022-01-14 | 兰州大学 | Recovery method of Fumei slag in wet metallurgy |
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| CN113802008A (en) * | 2021-09-16 | 2021-12-17 | 兰州大学 | Method for treating waste liquid containing platinum group noble metal |
| CN113845455A (en) * | 2021-10-12 | 2021-12-28 | 兰州大学 | Method for recycling Fumei slag |
| CN113930616A (en) * | 2021-10-12 | 2022-01-14 | 兰州大学 | Recovery method of Fumei slag in wet metallurgy |
| CN113845455B (en) * | 2021-10-12 | 2022-06-14 | 兰州大学 | Recycling method of Fumei slag |
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