CN110980655A - Method for recovering sulfur from byproduct gypsum of sulfur-containing wastewater - Google Patents
Method for recovering sulfur from byproduct gypsum of sulfur-containing wastewater Download PDFInfo
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- CN110980655A CN110980655A CN201911262784.4A CN201911262784A CN110980655A CN 110980655 A CN110980655 A CN 110980655A CN 201911262784 A CN201911262784 A CN 201911262784A CN 110980655 A CN110980655 A CN 110980655A
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- sulfur
- containing wastewater
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0253—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides
- C01B17/0259—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides by reduction of sulfates
- C01B17/0264—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides by reduction of sulfates of calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
- C01B17/44—Sulfides or polysulfides of magnesium, calcium, strontium, or barium by reduction of sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
- Removal Of Specific Substances (AREA)
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Abstract
The patent discloses a method for recovering sulfur from sulfur-containing wastewater by-product gypsum, wherein a catalyst and a reducing agent are added into the sulfur-containing wastewater by-product gypsum, and calcium sulfide is obtained through reduction reaction; adding calcium sulfide into the sulfur-containing wastewater to obtain calcium sulfate precipitate and hydrogen sulfide gas; absorbing, oxidizing and carrying out liquid-solid separation on the hydrogen sulfide gas to obtain elemental sulfur. Compared with the prior art, the method has the characteristics of low production cost, high production efficiency and good product quality.
Description
Technical Field
The invention relates to the field of industrial sulfur-containing wastewater treatment, in particular to cyclic utilization of gypsum as a byproduct in neutralization of sulfur-containing wastewater.
Background
When titanium dioxide is produced by a sulfuric acid method, limestone and calcium oxide are added to treat acidic wastewater to neutralize the acidic wastewater to produce titanium gypsum, the main components of the titanium gypsum are dihydrate gypsum and ferric hydroxide, and the titanium gypsum is weakly alkaline when the calcium oxide is added in a small excess amount to ensure thorough iron precipitation. The discharge of titanium gypsum not only occupies a large amount of land, but also pollutes the environment. The titanium gypsum on the stacking yard can be lost due to the washing of rainwater, and meanwhile, the soluble harmful substances are dissolved in water due to the washing and soaking of the titanium gypsum by the rainwater, and the surface water and the underground water can be seriously polluted due to the flowing and circulating of the water in the environment; on the other hand, after titanium gypsum is piled up and blown by sunshine and wind, a small part of titanium gypsum will fly to the atmosphere in a powdery state and sink to the surface of a foreign object which may be contacted, thus polluting the environment and threatening the health [ li nationality, zhao shuai, in ocean ] application research of titanium gypsum in the field of building materials [ J ]. tiles, 2008, (3): 58-60].
In addition, in the hydrometallurgical industry, a large amount of sulfuric acid-containing wastewater is also generated, and gypsum containing heavy metals is also obtained by adopting a lime neutralization method. The gypsum will pollute the environment if not treated. The project takes the byproduct gypsum of the sulfur-containing wastewater as a raw material, adopts a fluidized bed type decomposing furnace commonly used in cement plants as decomposing equipment, decomposes the gypsum at low temperature to prepare high-purity calcium sulfide, recycles the calcium sulfide to treat the sulfur-containing wastewater, generates hydrogen sulfide for preparing sulfur, is easy to transport, and realizes the recovery of sulfur resources and the cyclic utilization of calcium resources.
Disclosure of Invention
Compared with the prior art, the method can save the production cost, reduce the energy consumption, improve the efficiency and have obvious economic benefit and social benefit.
A method for recovering sulfur from gypsum as a byproduct of sulfur-containing wastewater comprises the following steps:
adding a catalyst and a reducing agent into the byproduct gypsum of the sulfur-containing wastewater, uniformly mixing, carrying out reduction reaction to obtain a reaction product, and sorting the reaction product to obtain calcium sulfide; adding calcium sulfide into the sulfuric acid-containing wastewater to obtain calcium sulfate precipitate and hydrogen sulfide gas; adding a trapping agent and a pH regulator into a washer, and absorbing hydrogen sulfide gas to obtain a pregnant solution; and (3) introducing the absorbed rich solution into an oxidation tank, adding a surfactant and a foaming agent, introducing air into the oxidation tank, and separating the elemental sulfur generated by oxidation of the rich solution from the solution along with the upward floating of bubbles to obtain the elemental sulfur.
The catalyst is one of hematite, waste battery anodes, chemical waste catalysts and electroplating slag, and the adding amount of the catalyst is 1-10% of the mass of the byproduct gypsum of the sulfur-containing wastewater.
The reducing agent is one of waste plastics, waste rubber and waste engine oil, and the adding amount of the reducing agent is 1-10% of the mass of the byproduct gypsum of the sulfur-containing waste water.
The trapping agent is one of manganese citrate, copper sulfate and ferric lactate, and the addition amount of the trapping agent is 0.1-5% of the mass of the byproduct gypsum of the sulfur-containing wastewater.
The pH regulator is one of calcium oxide, potassium carbonate and ammonium carbonate, and the addition amount of the pH regulator is 0.1-5% of the mass of the byproduct gypsum of the sulfur-containing wastewater.
The surfactant is one of xanthate, ethionine and nigre, and the addition amount of the surfactant is 0.01 to 0.1 percent of the mass of the gypsum as a byproduct of the sulfur-containing wastewater.
The foaming agent is one of cresol glyceryl ether, methyl isobutyl carbinol, methyl amyl alcohol and polyglycol ether, and the addition amount of the foaming agent is 0.01-0.1% of the mass of the byproduct gypsum of the sulfur-containing wastewater.
Compared with the prior art, the invention has the following advantages:
the main phase of the sulfur-containing wastewater byproduct gypsum is calcium sulfate dihydrate and also contains 21-40% of adsorption water. The gypsum containing the adsorption water directly enters the preheater of the rapid decomposer, so that the drying equipment can be reduced, the heat of the flue gas can be recovered, and the cost can be reduced. The material inlet of the preheater is provided with a scattering device to disperse the gypsum.
The hematite in the catalyst is waste residue generated by removing iron by a hematite method in a zinc hydrometallurgy plant; the waste battery anode is waste residue after lithium is recovered from the lithium ion battery anode, and mainly contains substances of cobalt, nickel or iron; the chemical waste catalyst is mainly a waste catalyst containing iron or nickel; the electroplating slag is nickel-containing electroplating slag and contains impurities such as Cu, Zn, Fe, Cr and the like. These catalysts can react with gypsum to form intermediate phase, promote the decomposition of gypsum and raise the conversion efficiency of gypsum by 5-20 times.
The reducing agent is one of waste plastics, waste rubber and waste engine oil, and the materials are cracked at high temperature to generate carbon monoxide to reduce gypsum to obtain a calcium sulfide product. The reducing agents are industrial solid wastes, are used, and have the effects of protecting the environment and saving resources.
The equipment adopted for the reduction reaction is a quick decomposer which consists of a preheater and a decomposing furnace. The number of the preheater stages is 2-6, and the preheater is designed according to the principle of a preheater commonly used in a pre-decomposition cement kiln. The decomposing furnace is a columnar spouting turbulent bed in principle and is formed by connecting 3-8 column units with necking in series, the ratio of the inner diameter of each column unit to the inner diameter of each necking is 1.1:1-1.8:1, and the ratio of the inner height of each column unit to the inner diameter of each column is 1:1-4: 1. The combustion-supporting gas used by the rapid decomposer is a carbon dioxide/oxygen mixed gas with the ratio of 3:1-0.1:1 (carbon dioxide: oxygen, volume ratio), and compared with the air, the carbon dioxide/oxygen mixed gas can avoid the generation of nitrogen oxides and the pollution of the nitrogen oxides; the main component of the flue gas is carbon dioxide, and the flue gas can be partially recycled. Each column unit has inlets for fuel and combustion supporting gas, so that the atmosphere of each column unit can be adjusted separately. The temperature of the rapid decomposer is 800-. In the flue gas ascending pipeline after the decomposed materials are separated from the flue gas, combustion-supporting gas is introduced, and unreacted carbon monoxide gas is oxidized into carbon dioxide. The catalyst is magnetic substance, which is beneficial to magnetic separation and can be recycled. By using the method, the purity of the calcium sulfide is higher than 95%. In addition, the auxiliary fuel adopted by the decomposing furnace in the patent is one of high-temperature blast furnace gas (more than or equal to 1000 ℃), combustible waste gas generated by coal chemical industry and high-sulfur coal, and the resource recycling can be realized by using the waste gas and coal which is difficult to utilize.
The trapping agent is added into the scrubber and can react with the hydrogen sulfide gas to generate new substances to enter the solution, so that the trapping of the hydrogen sulfide gas is realized, and the trapping agent has high trapping efficiency, and the trapping rate is more than 99.9 percent. The pH regulator can stabilize the pH value of the solution, and is beneficial to capture sulfur dioxide gas by the capture agent.
And introducing air into the oxidation tank, and oxidizing the trapping agent and new substances generated by hydrogen sulfide to obtain elemental sulfur and realize the regeneration of the trapping agent. The elemental sulfur has fine particle size and is difficult to separate when dispersed in a solution. And adding a surfactant and a foaming agent into the oxidation tank, so that the elemental sulfur floats upwards along with bubbles to realize the separation of the solution and the sulfur, wherein the content of the elemental sulfur in the solution after the liquid-solid separation is less than 0.05 percent. The surface active agent improves the surface property of sulfur, is easy to be adsorbed on foam generated by a foaming agent, enables elemental sulfur to float upwards, and realizes the quick separation of sulfur and solution. And returning the desulfurized solution to the scrubber for recycling.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Adding a catalyst and a reducing agent into the byproduct gypsum of the sulfur-containing wastewater, uniformly mixing, carrying out reduction reaction to obtain a reaction product, and sorting the reaction product to obtain calcium sulfide; adding calcium sulfide into the wastewater containing sulfuric acid to obtain calcium sulfate precipitate and hydrogen sulfide gas; adding a trapping agent and a pH regulator into a washer, and absorbing hydrogen sulfide gas to obtain a pregnant solution; and (3) introducing the absorbed rich solution into an oxidation tank, adding a surfactant and a foaming agent, introducing air into the oxidation tank, and separating the elemental sulfur generated by oxidation of the rich solution from the solution along with the upward floating of bubbles to obtain the elemental sulfur. The formula of the catalyst and the reducing agent in the raw materials is shown in the table 1; the formula of the trapping agent and the pH regulator is shown in the table 2; the formulations of the surfactant and the foaming agent are shown in Table 3.
TABLE 1
TABLE 2
TABLE 3
The embodiments of the invention can be implemented and achieve the aim of the invention. The present invention is not limited to these examples.
Claims (7)
1. A method for recovering sulfur from gypsum as a byproduct of sulfur-containing wastewater is characterized by sequentially comprising the following steps: adding a catalyst and a reducing agent into the byproduct gypsum of the sulfur-containing wastewater, uniformly mixing, carrying out reduction reaction to obtain a reaction product, and sorting the reaction product to obtain calcium sulfide; adding calcium sulfide into sulfur-containing wastewater to obtain calcium sulfate precipitate and hydrogen sulfide gas; adding a trapping agent and a pH regulator into a washer, and absorbing hydrogen sulfide gas to obtain a pregnant solution; and (3) introducing the absorbed rich solution into an oxidation tank, adding a surfactant and a foaming agent, introducing air into the oxidation tank, and separating the elemental sulfur generated by oxidation of the rich solution from the solution along with the upward floating of bubbles to obtain the elemental sulfur.
2. The method for recovering sulfur from the sulfur-containing wastewater byproduct gypsum according to claim 1, wherein the catalyst is one of hematite, a waste battery anode, a chemical waste catalyst and electroplating slag, and the addition amount of the catalyst is 1-10% of the mass of the sulfur-containing wastewater byproduct gypsum.
3. The method of claim 1, wherein the reducing agent is one of waste plastics, waste rubber and waste engine oil, and is added in an amount of 1-10% by mass of the gypsum as a byproduct of the sulfur-containing waste water.
4. The method as claimed in claim 1, wherein the capturing agent is one of manganese citrate, copper sulfate and iron lactate, and the amount of the capturing agent is 0.1-5% of the mass of the gypsum as the byproduct of the sulfur-containing wastewater.
5. The method for recovering sulfur from the sulfur-containing wastewater by-product gypsum according to claim 1, wherein the pH regulator is one of calcium oxide, potassium carbonate and ammonium carbonate, and the addition amount is 0.1-5% of the mass of the sulfur-containing wastewater by-product gypsum.
6. The method for recovering sulfur from the sulfur-containing wastewater by-product gypsum as claimed in claim 1, wherein the surfactant is one of xanthate, ethionamide and nigricans, and the amount of the surfactant added is 0.01 to 0.1% of the mass of the sulfur-containing wastewater by-product gypsum.
7. The method of claim 1, wherein the foaming agent is one of cresyl glyceryl ether, methyl isobutyl carbinol, methyl amyl alcohol and polyglycol ether, and the addition amount is 0.01-0.1% of the mass of the gypsum as the byproduct of the sulfur-containing wastewater.
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| CN201911262784.4A CN110980655A (en) | 2019-12-11 | 2019-12-11 | Method for recovering sulfur from byproduct gypsum of sulfur-containing wastewater |
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| CN201911262784.4A CN110980655A (en) | 2019-12-11 | 2019-12-11 | Method for recovering sulfur from byproduct gypsum of sulfur-containing wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684793A (en) * | 2022-05-20 | 2022-07-01 | 黔南民族师范学院 | Method for preparing elemental sulfur from titanium gypsum, titanium white waste acid and yellow phosphorus tail gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114684793A (en) * | 2022-05-20 | 2022-07-01 | 黔南民族师范学院 | Method for preparing elemental sulfur from titanium gypsum, titanium white waste acid and yellow phosphorus tail gas |
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