CN110643368A - Method for synthesizing organic high-sulfur stabilizer based on industrial waste sulfur slag - Google Patents
Method for synthesizing organic high-sulfur stabilizer based on industrial waste sulfur slag Download PDFInfo
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- CN110643368A CN110643368A CN201910918549.1A CN201910918549A CN110643368A CN 110643368 A CN110643368 A CN 110643368A CN 201910918549 A CN201910918549 A CN 201910918549A CN 110643368 A CN110643368 A CN 110643368A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
Abstract
The invention discloses a method for synthesizing an organic high-sulfur stabilizer based on industrial waste sulfur slag. The method has low cost of raw materials and mild reaction conditions, and realizes resource utilization of the waste sulfur slag. The prepared organic high-sulfur stabilizer is applied to the remediation of heavy metal contaminated soil, can efficiently reduce high-valence heavy metals in the soil, particularly has good reductive stabilization effect on hexavalent chromium, greatly reduces the dosage of a vulcanizing agent and reduces the remediation cost of the heavy metal contaminated soil under the condition of obtaining the same stabilization effect compared with common sulfur-series medicaments such as calcium polysulfide, sodium sulfide and the like in the prior art.
Description
Technical Field
The invention relates to a high-sulfur reagent, in particular to a method for synthesizing an organic high-sulfur stabilizer by utilizing industrial waste sulfur slag and industrial sodium sulfide under a mild condition, and belongs to the technical field of heavy metal contaminated soil remediation.
Background
The ethyl chloride is an intermediate for synthesizing part of organophosphorus pesticides, and the production process of the ethyl chloride is characterized in that phosphorus pentasulfide and absolute ethyl alcohol react under the catalysis of pyridine to generate sulfide, and then chlorine is introduced for chlorination to obtain the chloride since the 20 th century. And (3) carrying out alkaline hydrolysis reaction on the chloride and sodium sulfide generated in the vulcanization reaction to remove sulfur. Then washing and refining to obtain a finished product. A large amount of waste sulfur slag is generated in the process. Although many pesticide factories are stopped due to environmental protection problems at present, the waste sulfur slag as a discarded chemical waste material cannot be timely processed and stockpiled in warehouse of factory due to huge reserves. The accumulation of a large amount of waste sulfur residues not only occupies a large amount of land, but also seriously pollutes the soil environment, the random stacking of the waste sulfur residues and the volatile pungent smell also cause the pollution of the air environment, and the life of people is seriously influenced. Therefore, the method has the practical significance for resource utilization of the waste sulfur slag, not only can solve the problem of environmental protection, but also can bring good economic benefit.
The waste sulfur slag contains a large amount of mineral elements and has the characteristics of reutilization, easy recovery, high sulfur content and the like. The sulfur content in the product reaches about 73%. Sulfur is utilized in various fields as a chemical substance having a relatively wide range of applications. In the field of soil remediation, the sulfur-series medicament serving as a heavy metal stabilizer is quite prominent in the aspect of engineering application, for example, calcium polysulfide and sodium sulfide are used for reducing and stabilizing hexavalent chromium polluted soil, and the technology is quite high in the remediation project of a hexavalent chromium polluted site.
Therefore, the reduction stabilizer for repairing the heavy metal field is prepared by resource utilization of the waste sulfur slag, not only can effectively treat the stockpiled waste sulfur slag, reduce the occupation of space resources and the influence on the surrounding environment, but also provides help for the heavy metal polluted soil stabilizer industry in the aspect of raw materials, changes waste into valuable and creates economic value. The invention has application prospect and popularization value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an organic high-sulfur stabilizer which is prepared by using chemical waste sulfur slag and industrial sodium sulfide and has high unit sulfur content and good stability, the organic high-sulfur stabilizer can replace the conventional vulcanizing agents such as sodium sulfide, calcium polysulfide and the like, has good reduction effect on high-valence heavy metals in heavy metal polluted soil, particularly has good reduction and stabilization effects on hexavalent chromium, greatly reduces the consumption of vulcanizing agents under the condition of obtaining the same stabilization effect compared with the common sulfur series agents such as calcium polysulfide, sodium sulfide and the like in the prior art, reduces the repair cost of heavy metal polluted soil, achieves the aim of treating waste by waste, has low raw material cost of the organic high-sulfur stabilizer, has mild reaction conditions, and is beneficial to industrial production.
In order to achieve the technical purpose, the invention provides a method for synthesizing an organic high-sulfur stabilizer based on industrial waste sulfur slag.
In the synthetic process of the organic high-sulfur stabilizer, abundant elemental sulfur in industrial waste sulfur slag is mainly utilized to react with sulfide to synthesize a series of polysulfide with higher sulfur content compared with the existing polysulfide compound, and the main active component of the synthesized organic high-sulfur stabilizer is NaS5And NaS6Mass fraction of>24.4 percent, and the obtained polysulfide compound has high performance stability and is not easy to decompose,the main reaction is as follows:
NaS+S→NaS2
NaS2+S→NaS3
.....
NaSx+S→NaSx+1
the organic high-sulfur stabilizer has simple synthesis process, low energy consumption and low cost, and can be synthesized at normal temperature.
In the preferred scheme, the mass ratio of each raw material component for synthesizing the organic high-sulfur stabilizer is as follows: 25-30 parts of alkali metal sulfide; 3-7 parts of a deodorant; 25-30 parts of sulfur slag; 8-12 parts of a purifying agent; 2.5-3 parts of a cosolvent; 3-7 parts of a catalyst.
In a more preferable scheme, the alkali metal sulfide is analytically pure sodium sulfide or industrial sodium sulfide; the mass percentage content of the sodium sulfide component in the industrial sodium sulfide is more than 60%. The raw material sodium sulfide of the invention can be directly industrial sodium sulfide, which greatly reduces the synthesis cost of the organic high-sulfur stabilizer.
In a more preferable scheme, the smell removing agent comprises at least one of calcium hypochlorite, activated sodium persulfate, potassium permanganate, activated carbon, diatomite and zeolite powder. The deodorant mainly functions to remove pungent odor emitted from the preparation process of the waste sulfur slag.
In a more preferred embodiment, the scavenger comprises at least one of polyacrylamide, aluminum sulfate, polyaluminum chloride and polyferric sulfate. The purifying agent adopted by the invention mainly has the function of removing impurities introduced by industrial sodium sulfide and sulfur slag, and is mainly used for precipitating the impurities and then filtering the impurities. The mechanism of purifying impurities by the purifying agent is mainly that under the action of colloidal substances or electrolytes, impurity particles and tiny flocculent gel particles in a solution neutralize the surface charges of the particles, reduce or eliminate repulsive force among the particles, so that the impurity particles are combined into a whole and aggregated into a coarse flocculent body to be separated from water. When the purifying agent is a macromolecular compound, impurity particles in the solution react with polar groups or charged groups of the macromolecular compound, and the impurity particles are combined with the macromolecular compound to form coarse flocculent precipitates which are separated from water. The purifying agent is metered and added in the form of a solution with the concentration of 0.5-1.5 g/L.
In a more preferred embodiment, the catalyst comprises at least one of carboxylic acid sugar, hydroxyl sugar, polysaccharide and xylo-oligosaccharide. The catalyst is mainly used for promoting the reaction of elemental sulfur and sulfide to be accelerated, shortening the preparation time of the organic high-sulfur stabilizer, reducing the reaction temperature and improving the sulfur content of the organic high-sulfur stabilizer. The carbohydrate catalysts selected by the invention have high activity and selectivity, and promote the synthetic reaction of elemental sulfur and sulfide. The catalyst can be added directly or after being dissolved by a small amount of solvent.
In a more preferred embodiment, the cosolvent comprises at least one of ethanol, ethylene glycol, propanol, and propylene glycol. The cosolvent has the main functions of improving the reaction rate with sulfide and shortening the preparation time of the organic high-sulfur stabilizer by changing the state of elemental sulfur in a solution, and the dissolution assisting mechanism is mainly that the cosolvent changes the surface polarity of the elemental sulfur so as to change the state of the elemental sulfur in a nonpolar sulfide alkali solution, and the cosolvent can form a soluble complex with the elemental sulfur and accelerate the reaction rate of the elemental sulfur and the alkali sulfide.
In a more preferred embodiment, the solvent is water.
The effective content of the industrial waste sulfur slag is more than 70 percent.
The elemental sulfur is sublimed sulfur, is one of main raw materials for synthesizing the organic high-sulfur stabilizer, and has the effective sulfur content of more than 99 percent.
The preparation method of the organic high-sulfur stabilizer comprises the following specific steps:
the invention provides a method for preparing an organic high-sulfur stabilizer by utilizing chemical waste sulfur slag, which comprises the following steps:
1. fully grinding the waste sulfur slag, and screening the waste sulfur slag through a 20-mesh sieve for later use after uniform grinding;
2. adding a deodorant into the waste sulfur slag according to a proportion, and uniformly mixing;
3. adding a cosolvent into the treated waste sulfur slag according to a proportion, and uniformly mixing;
4. adding alkali metal sulfide in a certain proportion, mixing with the pretreated sublimed sulfur, grinding, and stirring uniformly;
5. adding solvent water and catalyst, and continuously stirring until the solid solute is completely dissolved;
6. adding a purifying agent, flocculating and precipitating impurities, and filtering and removing impurities to obtain the prepared organic high-sulfur stabilizer.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the organic high-sulfur stabilizer with high utilization value can be prepared by recycling the waste sulfur slag, all sulfur elements in the waste sulfur slag are fully utilized in the preparation process, the utilization rate of the sulfur elements can reach 100%, the amount of the residual waste slag after preparation is reduced by 70% compared with the waste sulfur slag, and the resource utilization of waste resources is realized.
2. The method takes the waste sulfur slag as a raw material for preparing the organic high-sulfur stabilizer, solves the problem that the existing waste sulfur slag pollutes the environment, and has high environmental friendliness and obviously lower pollutant risk than the risk control value.
3. The organic high-sulfur stabilizer has simple preparation process, completes reaction at room temperature, has low energy consumption, does not need additional energy consumption such as heating and the like, and avoids the influence of irritant gas in waste sulfur slag on the surrounding environment to a great extent in the preparation process;
4. the method is suitable for the waste sulfur slag in the production of the ethyl chloride, the sulfur waste slag with high sulfur content is suitable, and the addition proportion of the prepared related medicament is adjusted according to the actual condition of the sulfur waste slag.
5. The organic high-sulfur stabilizer prepared by the invention has the same compound structure stability and reduction stabilization effect as the organic high-sulfur stabilizer prepared by taking sublimed sulfur as a raw material.
6. The sulfur content of the organic high-sulfur stabilizer prepared by the invention is higher than that of common sodium sulfide and calcium polysulfide, and the effective component of the calcium polysulfide product on the market is mainly CaS5In mass fraction of>18 percent of industrial sodium sulfide product, and the effective component of Na2S, containing 60% of impurities and water of crystallization, andthe organic high-sulfur stabilizer of the invention contains NaS as an effective component5And NaS6In mass fraction of>24.4 percent, and when the organic high-sulfur stabilizer is used for repairing heavy metal polluted soil and achieves the same repairing effect, the using amount of the organic high-sulfur stabilizer is far lower than that of sodium sulfide and calcium polysulfide.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Taking waste sulfur slag (the effective sulfur content is 72%) stockpiled in certain pesticide plant in Shandong to prepare the organic high-sulfur stabilizer. The preparation method comprises the following steps:
weighing 250g of waste sulfur slag, fully grinding, sieving by a 20-mesh sieve, adding 30g of calcium hypochlorite, fully and uniformly stirring, adding 50L of aqueous solvent while stirring, and standing for later use; and then adding 20g of ethanol solution and 10g of ethylene glycol solution, quickly stirring, adding 300g of sodium sulfide solid after uniformly stirring, continuously stirring, adding 500g of water, mechanically stirring at a rotating speed of 100r/min, adding 40L of polysaccharide solution with the concentration of 10g/L during stirring, continuously stirring, observing full reaction of yellow elemental sulfur in the liquid, adding 100L of PAM solution with the concentration of 1g/L, slowly stirring, and standing for one hour. And after the liquid is obviously layered, slowly pouring the upper-layer liquid into a suction filter for suction filtration to obtain a ruby-colored clear organic high-sulfur stabilizer finished product, wherein the content of effective sulfides is about 25.6%, and the preparation time is two hours and ten minutes in the whole process.
Example 2
Taking waste sulfur slag (the effective sulfur content is 72%) stockpiled in certain pesticide plant in Shandong to prepare the organic high-sulfur stabilizer. The preparation method comprises the following steps:
weighing 280g of waste sulfur slag, fully grinding, sieving with a 20-mesh sieve, adding 10g of potassium permanganate, fully and uniformly stirring, adding 50L of aqueous solvent while stirring, standing for 10min, adding 20g of diatomite, and standing for later use; then 20g of ethylene glycol solution and 10g of propanol solution are added and rapidly stirred, 300g of sodium sulfide solid is added after uniform stirring, continuous stirring is carried out, 500g of water is added, mechanical stirring is utilized, the rotating speed is set at 100r/min, 40L of carboxylic acid sugar solution with the concentration of 10g/L is added in the stirring process, then continuous stirring is carried out, after the yellow elemental sulfur in the liquid is observed to fully react, 100L of aluminum sulfate solution with the concentration of 1g/L is added, slow stirring is carried out, and standing is carried out for one hour. And after the liquid is obviously layered, slowly pouring the upper-layer liquid into a suction filter for suction filtration to obtain a ruby-colored clear organic high-sulfur stabilizer finished product, wherein the content of the effective sulfide is about 27.4%, and the preparation time is two hours and thirty minutes in the whole process.
Example 3
Taking waste sulfur slag (the effective sulfur content is 72%) stockpiled in certain pesticide plant in Shandong to prepare the organic high-sulfur stabilizer. The preparation method comprises the following steps:
weighing 300g of waste sulfur slag, fully grinding, sieving by a 20-mesh sieve, adding 20g of 30% activated sodium persulfate, fully and uniformly stirring, standing for 10min, adding 10g of diatomite, stirring while adding 50L of water solvent, and standing for later use; then 20g of ethanol solution and 10g of ethylene glycol solution are added and then rapidly stirred, 300g of sodium sulfide solid is added after uniform stirring, continuous stirring is carried out, 500g of water is added, mechanical stirring is utilized, the rotating speed is set at 100r/min, 20L of 10g/L carboxylic acid sugar solution and 20L of 10g/L polysaccharide solution are added in the stirring process, then continuous stirring is carried out, after the yellow elemental sulfur in the liquid is observed to fully react, 20L of 1g/L PAM solution and 80L of 1g/L aluminum sulfate solution are added, slow stirring is carried out, and the mixture is kept stand for one hour. After the liquid is observed to be obviously layered, the upper layer liquid is slowly poured into a suction filter for suction filtration to obtain a ruby clear organic high-sulfur stabilizer finished product, the content of the effective sulfide is about 29.4 percent, and the preparation time is two hours.
Example 4
The organic high-sulfur stabilizer prepared according to the example 1 is used for repairing polluted soil of a certain polluted site of the sand in comparison with the organic high-sulfur stabilizer prepared by sublimed sulfur.
Taking soil polluted by some chromium-polluted site of the Changsha, naturally airing the soil for 48 hours, mechanically crushing the soil, and sieving the crushed soil with a 20-mesh sieve for later use. The total amount of hexavalent chromium in the soil is measured, the soil is divided into 300g groups according to the measurement result, two organic high-sulfur stabilizers (named as FS-stabilizers prepared in example 1 and named as DS-stabilizers prepared by sublimed sulfur) which are organic high-sulfur stabilizers and 15 times, 28 times and 30 times of the total mass multiple of the hexavalent chromium are respectively added into the soil, the soil and the polluted soil are stirred and mixed uniformly, and meanwhile, a proper amount of water is sprayed to keep the water content of the soil at 30%. After three days of maintenance, the restored soil is sampled, a toxicity (hexavalent chromium) leaching test is carried out on the stabilized soil by referring to HJ 557-. The leaching concentration and repair efficiency of hexavalent chromium are shown in table 1.
TABLE 1 hexavalent chromium leach concentration and remediation efficiency
As can be seen from the table, the stabilizing effects of the FS-stabilizer and the DS-stabilizer are compared, the difference between the FS-stabilizer and the DS-stabilizer is small, when the adding proportion reaches 28 times of the total mass multiple of hexavalent chromium, the leaching concentration of the hexavalent chromium can be as low as about 0.05, the hexavalent chromium can basically reach the hexavalent chromium content standards of three types of underground water in the underground water quality standard, and the hexavalent chromium content standards can meet the acceptance standards and requirements of most soil remediation projects.
Example 5
Taking waste sulfur slag stockpiled in certain pesticide plant in Shandong to prepare the organic high-sulfur stabilizer.
Taking soil polluted by some chromium-polluted site of Changsha (same as in example 4), naturally airing the soil for 48 hours, mechanically crushing the soil, and sieving the crushed soil with a 20-mesh sieve for later use. The total amount of hexavalent chromium in the soil is measured, according to the measurement result, the soil is divided into 300g groups, organic high-sulfur stabilizer (prepared in example 1) which is 15 times, 20 times and 28 times of the total amount of hexavalent chromium by mass, sodium sulfide and calcium polysulfide are respectively added, the mixture is uniformly stirred and mixed with the polluted soil, and meanwhile, a proper amount of water is sprayed, so that the water content of the soil is kept at 30%. After three days of maintenance, the restored soil is sampled, and toxicity (hexavalent chromium) leaching test is carried out on the stabilized soil by referring to HJ 557-. The remediation efficiency of hexavalent chromium-contaminated soil is shown in table 2.
As can be seen from the table, the reduction stabilizing effect of the organic high-sulfur stabilizer on hexavalent chromium can reach more than 99.9%, and the reduction stabilizing effect on hexavalent chromium can be equal to that of the commercially mature heavy metal stabilizer under the condition of the same addition proportion.
TABLE 2 comparison of organic high-sulfur stabilizer to commercial agent remediation efficiency
Claims (8)
1. A method for synthesizing an organic high-sulfur stabilizer based on industrial waste sulfur slag is characterized by comprising the following steps: uniformly mixing the sulfur slag with a deodorant, a cosolvent, an alkali metal sulfide, a catalyst and a solvent, stirring for reaction, adding a purifying agent for precipitation and impurity removal, and thus obtaining the organic high-sulfur stabilizer.
2. The method for synthesizing the organic high-sulfur stabilizer based on the industrial waste sulfur slag according to claim 1, which is characterized in that: the organic high-sulfur stabilizer is synthesized from the following raw material components in percentage by mass:
25-30 parts of alkali metal sulfide;
3-7 parts of a deodorant;
25-30 parts of sulfur slag;
8-12 parts of a purifying agent;
2.5-3 parts of a cosolvent;
3-7 parts of a catalyst.
3. The method for synthesizing the organic high-sulfur stabilizer based on the industrial waste sulfur slag according to claim 1 or 2, characterized in that: the alkali metal sulfide is analytically pure sodium sulfide or industrial sodium sulfide; the mass percentage content of the sodium sulfide in the industrial sodium sulfide is more than 60%.
4. The method for synthesizing the organic high-sulfur stabilizer based on the industrial waste sulfur slag according to claim 1 or 2, characterized in that: the smell removing agent comprises at least one of calcium hypochlorite, activated sodium persulfate, potassium permanganate, activated carbon, diatomite and zeolite powder.
5. The method for synthesizing the organic high-sulfur stabilizer based on the industrial waste sulfur slag according to claim 1 or 2, characterized in that: the purifying agent comprises at least one of polyacrylamide, aluminum sulfate, polyaluminum chloride and polyferric sulfate.
6. The method for synthesizing an organic high sulfur stabilizer based on industrial waste sulfur slag according to claim 1 or 2, characterized in that: the catalyst comprises at least one of carboxylic acid sugar, hydroxyl sugar, polysaccharide and xylo-oligosaccharide.
7. The method for synthesizing an organic high sulfur stabilizer based on industrial waste sulfur slag according to claim 1 or 2, characterized in that: the cosolvent comprises at least one of ethanol, ethylene glycol, propanol and propylene glycol.
8. The method for synthesizing an organic high sulfur stabilizer based on industrial waste sulfur slag according to claim 1 or 2, characterized in that: the solvent is water.
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| CN101628750A (en) * | 2009-09-10 | 2010-01-20 | 南京师范大学 | Sulfide heavy metal chelating agent and preparation method thereof |
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| CN101628750A (en) * | 2009-09-10 | 2010-01-20 | 南京师范大学 | Sulfide heavy metal chelating agent and preparation method thereof |
| CN104841693A (en) * | 2015-05-29 | 2015-08-19 | 北京大学 | Hexavalent chromium contaminated soil in-situ remediation method |
| CN108160684A (en) * | 2017-12-27 | 2018-06-15 | 辽宁工程技术大学 | A kind of combined remediation method of pollution of chromium soil |
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Application publication date: 20200103 |