阅读说明：本技术 湿法磷酸工业副产物无害化资源化再生利用的方法 (Method for harmless resource recycling of wet-process phosphoric acid industrial by-products ) 是由 罗海波 王钧 欧阳春 周向东 冯宗林 于 2020-06-19 设计创作，主要内容包括：本发明公开湿法磷酸工业副产物无害化资源化再生利用的方法,湿法磷酸工艺生产线尾端增加磷石膏无害化工艺措施,将湿法磷酸工艺中产生的磷石膏废渣直接进入改性处理工艺环节,实现湿法磷酸工艺生产线延伸后,对磷石膏直接进行无害化资源化利用,彻底解决湿法磷酸工艺环节中大宗工业固体废弃物磷石膏的环保处置问题；同时,改性处理的磷石膏作为建材原料,与普通硅酸盐水泥发生作用,生产水泥基磷石膏混凝土建材制品。磷石膏无害化处置原料配方按重量计数如下：磷石膏70-90份、钙粉5-10份、改性调理剂1-5份,水10-12份;本发明实现磷石膏工艺线上的无害化资源化利用；为磷化工行业可持续发展奠基基础,解决湿法磷酸工业废物磷石膏中的环境污染风险问题,同时可生产优质的、硬质的水泥基磷石膏混凝土建材。(The invention discloses a method for harmless resource recycling of byproducts in wet-process phosphoric acid industry, wherein a phosphogypsum harmless process measure is added at the tail end of a production line of the wet-process phosphoric acid process, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after the extension of the production line of the wet-process phosphoric acid process is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; meanwhile, the modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product. The formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, wherein the invention realizes the harmless resource utilization on the phosphogypsum process line; the method lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and can produce high-quality and hard cement-based phosphogypsum concrete building materials.)

1. The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; simultaneously, modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product, and the formulation of the raw material for the harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry;

s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material;

and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

2. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1, characterized in that: the raw material formula of the formula also comprises 3-10 parts of silicon powder by weight, and the silicon powder is gradually added in the process of continuously stirring after the calcium powder is added in the step S2.

3. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: the conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent;

the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate;

the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

4. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in the step s1, the water content of the phosphogypsum raw slag is 35-45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45-55 parts.

5. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S1, pH value is pH 6-9.

6. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S2, the calcium powder is nano calcium carbonate, nano silica powder or a combination of the two.

7. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: in step S3, the aging time is 5-8 hours, and the drying temperature is 300 °.

8. The method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct according to claim 1 or 2, characterized in that: the product obtained in the step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete building material products.

Technical Field

The invention relates to a method for recycling phosphogypsum raw slag through baking-free, washing-free conditioning, harmless recycling and recycling, and belongs to the technical field of resource utilization of phosphogypsum industrial waste.

Background

The main process by-product of the wet-process phosphoric acid production line is phosphogypsum, and the phosphogypsum treated on the process production line has strong acidity and also has partial environmental pollutants such as phosphorus, fluorine and the like. The prior art can not carry out resource utilization after timely harmless disposal. Only the phosphogypsum slag can be discharged to a phosphogypsum slag yard for stacking, the acid strength is reduced and the impurity content is reduced through natural placement or a slow process in the stacking process of the slag yard, and the resource is recycled through calcination and water washing. In the process, the investment of environmental protection management of the slag field is extremely large, and meanwhile, certain environmental protection risks exist, and in fact, the by-products are naturally stockpiled in the slag field, so that the pollution elements are slowly released to the nature. With the strict environmental protection supervision, the discharge of the slag yard is strictly supervised, so that enterprises are forced to perform the seepage prevention of the slag yard and the treatment of wastewater, and the environmental protection cost of the enterprises is greatly increased.

The harmless recycling of the phosphogypsum becomes a necessary way of the industry, and the phosphogypsum raw slag on a wet-process phosphoric acid process line cannot be directly conditioned to realize the harmless recycling. The technology takes the phosphogypsum raw slag discharged from the tail end of the wet-process phosphoric acid process as a starting point, directly enters the phosphogypsum discharged from the tail end of the original process into a large-scale high-speed stirrer, gradually adds a conditioner into the stirrer, realizes extension of the original wet-process phosphoric acid process line, adjusts the pH value of the phosphogypsum through modification treatment, synchronously solidifies pollutants in the phosphogypsum, and realizes harmless resource utilization on the phosphogypsum process line. The method lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and can produce high-quality and hard cement-based phosphogypsum concrete building materials. Thoroughly solves the defects of the prior phosphogypsum resource utilization technology.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry, so as to realize the harmless resource recycling on a phosphogypsum process line; the method lays a foundation for sustainable development of the phosphorus chemical industry, solves the problem of environmental pollution risk in the phosphogypsum which is a waste in the wet-process phosphoric acid industry, can produce high-quality and hard cement-based phosphogypsum concrete building materials, and can overcome the defects of the existing phosphogypsum resource utilization technology.

The technical scheme of the invention is as follows: the method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; simultaneously, modified phosphogypsum is used as a building material raw material to react with ordinary portland cement to produce a cement-based phosphogypsum concrete building material product, and the formulation of the raw material for the harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70-90 parts of phosphogypsum, 5-10 parts of calcium powder, 1-5 parts of modified conditioner and 10-12 parts of water, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, a belt scale is used as a weighing device, the raw phosphogypsum slag is added into a large-scale high-speed stirrer, and a modified conditioner of the phosphogypsum is added according to the weight proportion of the phosphogypsum to obtain mixed slurry with the pH value of 6-9; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The raw material formula of the formula also comprises 3-10 parts of silicon powder by weight, and the silicon powder is gradually added in the process of continuously stirring after the calcium powder is added in the step S2.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent;

the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content of the phosphogypsum raw slag is 35-45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45-55 parts.

In step S2, the calcium powder is nano calcium carbonate, nano silica powder or a combination of the two.

In step S3, the aging time is 5-8 hours, and the drying temperature is 300 °.

The product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Compared with the prior art, the method for harmless resource recycling of the wet-process phosphoric acid industrial byproduct has the beneficial effects that:

(1) realizing the harmless resource utilization on the phosphogypsum process line; lays a foundation for the sustainable development of the industry of the phosphorization industry, solves the problem of environmental pollution risk in the phosphogypsum which is the waste of the wet-process phosphoric acid industry, and lays a foundation for the harmless resource utilization of the by-products of the wet-process phosphoric acid process;

(2) the phosphogypsum harmless recycling process measures are added in the process links, the phosphogypsum process production line is extended and then is directly treated, so that the phosphogypsum is treated in time without entering a storage yard to generate the risk of environmental pollution;

(3) the calcium powder and the silicon powder are added according to the proportion through conditioning of a conditioner, and the mixture is dried to be used as a building material raw material to replace common sandstone materials to produce building material products;

(4) through conditioning of the conditioner, the problem of acid pollution caused by acid radical ions such as phosphorus, sulfur, fluorine and the like in the phosphogypsum raw material can be solved, and through a plurality of tests, the PH value of the produced hard concrete block is more than 7, so that the problem of acidity of the phosphogypsum raw material is thoroughly solved;

(5) the conditioning of the phosphogypsum, specifically, adding a certain proportion of penetrant for homogenization treatment according to the quality of the phosphogypsum raw slag, then adding a sealing agent to form a phosphogypsum sealing crystal, permanently sealing harmful substances in the phosphogypsum raw slag, thoroughly solving the problem of permeation and leakage of the harmful substances of the phosphogypsum, aging the phosphogypsum sealing crystal at a certain temperature and within a certain time to ensure the complete formation and stability of the sealing crystal, further adding a propping agent which can be selectively combined with the sealing crystal to ensure the integrity and the certain strength of the formed sealing crystal, realizing the stable sealing of the harmful substances fixed in crystal lattices, solving the condition that the phosphogypsum is damp and acid-returning, simultaneously solving the secondary pollution problem of the phosphogypsum product, finally adding a curing agent to improve the bonding and curing performance of the phosphogypsum sealing crystal, and realizing the finished product index of a novel product of the phosphogypsum, after the phosphogypsum raw slag is conditioned, harmful substances are sealed, and the conditioned phosphogypsum raw material has extremely low solubility of phosphorus, fluorine and heavy metals and no pollution risk to the environment;

(6) after the phosphogypsum is subjected to harmless treatment, the phosphogypsum is used as a sandstone substitute material and directly enters a production link, and the phosphogypsum is stockpiled without a special field, so that the field occupation and the environmental pollution are saved;

(7) after the phosphogypsum is modified, the physical and chemical properties are stable, the PH is maintained neutral, and repeated water absorption, moisture regain and caking can not be caused in the natural storage process; the stacking and the subsequent utilization are convenient;

(8) after the ardealite is modified, the ardealite can be directly blended with ordinary portland cement for use. The produced cement-based phosphogypsum concrete building material product has the advantages that harmful substances are completely sealed, the seepage is avoided, and the secondary pollution risk of the building material product is thoroughly solved.

Drawings

None.

Detailed Description

Example 1.

A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70 parts of phosphogypsum, 5 parts of calcium powder, 1 part of modified conditioner and 10 parts of water, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content of the phosphogypsum raw slag is 35 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Example 2.

A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 80 parts of phosphogypsum, 8 parts of calcium powder, 3 parts of modified conditioner and 11 parts of water, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content ratio of the phosphogypsum raw slag is 40 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 50 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Example 3.

The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 90 parts of phosphogypsum, 10 parts of calcium powder, 5 parts of modified conditioner and 12 parts of water, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, adding calcium powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content ratio of the phosphogypsum raw slag is 45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 55 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

The raw material formula of the formula also comprises 3-10 parts of silicon powder by weight,

example 4.

A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 70 parts of phosphogypsum, 5 parts of calcium powder, 1 part of modified conditioner, 10 parts of water and 3 parts of silicon powder, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content of the phosphogypsum raw slag is 35 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 45 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Example 5.

A method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, the phosphogypsum is directly subjected to harmless resource recycling after the extension of the wet-process phosphoric acid process production line is realized, and the problem of environment-friendly disposal of a large amount of industrial solid waste phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 80 parts of phosphogypsum, 8 parts of calcium powder, 3 parts of modified conditioner, 11 parts of water and 7 parts of silicon powder, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2 and S2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content ratio of the phosphogypsum raw slag is 40 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 50 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Example 6.

The method for harmless resource recycling of byproducts in the wet-process phosphoric acid industry is characterized in that a phosphogypsum harmless process measure is added at the tail end of a wet-process phosphoric acid process production line, phosphogypsum waste residues generated in the wet-process phosphoric acid process directly enter a modification treatment process link, after extension of the wet-process phosphoric acid process production line is realized, phosphogypsum is directly subjected to harmless resource recycling, and the problem of environment-friendly disposal of a large amount of industrial solid wastes phosphogypsum in the wet-process phosphoric acid process link is thoroughly solved; the formula of the raw materials for harmless treatment of the phosphogypsum comprises the following components in percentage by weight: 90 parts of phosphogypsum, 10 parts of calcium powder, 5 parts of modified conditioner, 12 parts of water and 10 parts of silicon powder, and the production steps are as follows:

s1, at the tail end of a wet-process phosphoric acid process production line, taking a belt scale as a weighing device, adding the raw phosphogypsum slag into a large-scale high-speed stirrer, and adding a modified conditioner of the phosphogypsum according to the weight proportion of the phosphogypsum to obtain mixed slurry; s2, sequentially adding calcium powder, silicon powder and water into the mixed slurry, and stirring to obtain a mixed material; and S3, feeding the mixed materials into a temporary storage warehouse for an aging reaction, feeding the aged materials into a dryer for dehydration and drying, and obtaining a powdery product after dehydration and drying.

The conditioning agent comprises a penetrating agent, a sealing agent, a propping agent and a curing agent; the mixing ratio of the phosphogypsum raw slag to the sealing agent is 1: 0.05-0.15; the sealing medicament comprises the following raw materials in parts by weight: active lime milk, 35 parts of calcium powder, silicon powder, 25 parts of sodium metasilicate pentahydrate, calcium silicate, sodium oleoyloxy ethanesulfonate and 10 parts of sodium dodecyl benzene sulfonate; the mixing ratio of the phosphogypsum raw slag to the penetrating agent is 1: 0.01-0.05; the penetrating agent is an anionic penetrating agent and a nonionic surfactant which are sequentially added into the phosphogypsum raw slag; or the penetrating agent is an organic solvent and an inorganic solvent which are sequentially added into the phosphogypsum raw slag; the anion penetrating agent is alkyl phosphate mono-or diester salt; the nonionic surfactant is fatty alcohol-polyoxyethylene ether, oleoyloxy sodium ethanesulfonate or a combination of the fatty alcohol-polyoxyethylene ether and the oleoyloxy sodium ethanesulfonate; the mixing ratio of the phosphogypsum raw slag to the propping agent is 1:0.05, and the curing time is at least 1 hour; the proppant is one or a mixture of gas-phase titanium dioxide and gas-phase aluminum oxide, and is used for strengthening the previously formed inclusion or crystal and improving the strength and stability of the inclusion or crystal; the mixing ratio of the phosphogypsum raw slag to the curing agent is 1: 0: 005-0.02; the curing time is 1-2 hours.

In the step s1, the water content ratio of the phosphogypsum raw slag is 45 parts, and a certain amount of water is added to control the water content of the raw slag entering the stirrer to be 55 parts; in step S1, pH value of PH 6-9; in step S2, the calcium powder is nano calcium carbonate, nano silicon dioxide powder or a combination of the two; in step S3, the aging time is 5-8 hours, and the drying temperature is 300 degrees; the product obtained in step S3 can be directly used with ordinary portland cement to produce phosphogypsum-based cement concrete products.

Through multiple tests, in examples 1-6, the modified phosphogypsum does not have self-adhesiveness any more, the pH value of the phosphogypsum is maintained at about 7, the content of soluble P is not higher than 5ppm, the content of soluble F is not higher than 2ppm, the modified phosphogypsum is used as a building material raw material and can be directly blended with common silicate cement, and the blending ratio of the phosphogypsum reaches more than 70 parts, so that a phosphogypsum-based cement concrete product is obtained.

Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.