CN110550959B - Treatment method and application of salt-containing organic wastewater crystallization residual salt - Google Patents

Treatment method and application of salt-containing organic wastewater crystallization residual salt Download PDF

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CN110550959B
CN110550959B CN201910843851.5A CN201910843851A CN110550959B CN 110550959 B CN110550959 B CN 110550959B CN 201910843851 A CN201910843851 A CN 201910843851A CN 110550959 B CN110550959 B CN 110550959B
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salt
crystallization
organic wastewater
containing organic
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CN110550959A (en
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徐红彬
陈辉霞
唐海燕
张笛
徐世红
孙继远
张红玲
曹宏斌
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Institute of Process Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
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    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/027—Lightweight materials
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite

Abstract

The invention relates to a treatment method of salt-containing organic wastewater crystallization residual salt and application thereof. The processing method comprises the following steps: (1) mixing and heating salt-containing organic wastewater crystallization residual salt and sulfuric acid to convert inorganic salt in the crystallization residual salt into sulfate, so as to obtain mixed salt containing sulfate; (2) and (2) mixing the sulfate-containing mixed salt obtained in the step (1) with a curing agent, and carrying out pyrolysis curing to obtain a mineral composite compound. The mineral state compound obtained by the treatment method can be comprehensively utilized as general industrial solid waste. The treatment method has the advantages of cheap and easily-obtained raw materials, simple process and lower cost, can realize the efficient removal of organic matters in the crystallized residual salt and the safe fixation of water-soluble salt, realizes the resource utilization of the crystallized residual salt, and is beneficial to industrial implementation.

Description

Treatment method and application of salt-containing organic wastewater crystallization residual salt
Technical Field
The invention relates to the technical field of solid waste disposal, in particular to a treatment method of salt-containing organic wastewater crystallization residual salt and application thereof.
Background
In the wastewater treatment process of chemical industries such as the coal chemical industry, the fertilizer industry, the pesticide industry, the pharmaceutical industry and the like, a large amount of salt-containing organic wastewater is generated. In such wastewaters, in addition to organic contaminants, they contain a large amount of soluble inorganic salts, such as Cl-、Na+、SO4 2-、Ca2+And the like. Only by removing the organic matters in the salt-containing organic wastewater and simultaneously separating and treating the soluble salt substances, the final treatment target of the salt-containing organic wastewater is achieved. For this reason, a technique of "low-temperature heat utilization-evaporation-crystallization process of salt-containing organic wastewater" has been proposed for treating such wastewater. However, the end result is not the one that would be expected from the process technology, i.e. both industrial salt and recycled fresh water. This is due toMost of salt substances in the wastewater are halide substances, the solubility of the salt substances in the wastewater is particularly high, the salt substances cannot be efficiently separated out by adopting a concentration and cooling crystallization method, and a lot of waste salt with complex composition and high treatment difficulty is generated.
The waste salt is treated by landfill disposal or high-temperature incineration. Due to the moisture absorption of the waste salt, the risk of redissolution exists in the processes of storage, transportation and landfill, and secondary pollution is easily caused. Therefore, the landfill disposal needs to adopt extremely strict closed landfill requirements to meet the standard of safety and environmental protection. Researchers have conducted a great deal of research based on the high-temperature incineration method of waste salt, and disclosed various methods for treating waste salt by using different incineration processes, for example, CN106801874A discloses a method for treating industrial waste salt, which comprises mixing microwave absorbing medium particles and industrial waste salt particles in a microwave processor, heating and degrading pollutants in the waste salt by using microwave energy under the condition of air atmosphere and continuous stirring and mixing, elutriating the residual waste salt with water to recover NaCl, and recycling the microwave absorbing medium particles. CN105712421A discloses a method for harmlessly treating coal chemical industry organic high-salt wastewater by a two-stage heating-oxygen-enriched combustion method, which comprises the steps of putting the coal chemical industry organic high-salt wastewater into an electric furnace, carrying out two-stage heating to fully melt the wastewater, and then blowing oxidizing gas into a molten pool to carry out oxygen-enriched combustion on organic matters in the organic high-salt wastewater to obtain nontoxic molten waste salt. CN108571736A discloses a method for harmlessly treating high-salinity wastewater by using fly ash as an additive, which comprises the steps of placing the high-salinity wastewater in an electric furnace, heating materials, adding a certain amount of fly ash into the materials when the materials are in a molten state, and blowing oxidizing gas into a molten pool through a spray gun to perform oxygen-enriched combustion of organic pollutants and the like, so as to realize the harmlessness treatment of the organic pollutants and the like in the high-salinity wastewater and the complex conversion of sodium salt and potassium salt. However, these treatment methods often have the problems of waste salt melting, incomplete removal of organic matter and heavy metal impurities, mixing of various inorganic salts, and the like, so that the resource utilization after the treatment of the waste salt still cannot be realized.
The salt-containing organic wastewater crystallization residual salt is residual salt generated in the process of recycling waste salt through fractional crystallization, is solid hazardous waste containing various inorganic salts such as sodium chloride, sodium sulfate, sodium sulfite, sodium sulfide, sodium nitrate, sodium nitrite, potassium chloride, potassium sulfate, potassium sulfite, potassium sulfide, potassium nitrate, potassium nitrite and the like, contains a large amount of organic matters and various heavy metals, and has strong pungent smell. Because the components are complex, the toxicity is high, the impurity content is higher, the resource treatment is more difficult to realize, and the country manages according to the hazardous waste. Therefore, the development of a new method which has simple process, lower cost and safe disposal is of great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention relates to a method for treating salt-containing organic wastewater crystallization residual salt, and the mineral compound obtained by the treatment method can be used for comprehensive utilization of general industrial solid waste or can be directly used as a downstream industrial raw material.
One purpose of the invention is to provide a method for treating salt residue from salt-containing organic wastewater crystallization, which comprises the following steps:
(1) mixing and heating salt-containing organic wastewater crystallization residual salt and sulfuric acid to convert inorganic salt in the crystallization residual salt into sulfate, so as to obtain mixed salt containing sulfate;
(2) and (2) mixing the sulfate-containing mixed salt obtained in the step (1) with a curing agent, and carrying out pyrolysis curing to obtain a mineral composite compound.
As a preferred technical solution of the present invention, the inorganic salt in the residual crystallization salt in step (1) includes any one or a mixture of at least two of halide, sulfate, sulfite, metal sulfide, nitrate or nitrite, and typical but non-limiting examples of the mixture are: mixtures of halides and nitrates, mixtures of halides and sulfates, mixtures of sulfates, sulfites, and metal sulfides, or mixtures of halides, nitrates, and nitrites, and the like.
Preferably, the inorganic salt in the residual salt from the crystallization in step (1) includes any one or a mixture of at least two of sodium chloride, sodium sulfate, sodium sulfite, sodium sulfide, sodium nitrate, sodium nitrite, potassium chloride, potassium sulfate, potassium sulfite, potassium sulfide, potassium nitrate, or potassium nitrite, and the mixture is typically but not limited to: mixtures of sodium chloride, potassium chloride and sodium nitrate, mixtures of sodium chloride, sodium sulfate and sodium sulfite, mixtures of sodium sulfate, sodium nitrate and sodium nitrite or mixtures of sodium sulfide, potassium chloride and potassium sulfate, and the like.
Preferably, the TOC content of the residual salt crystallized in step (1) is 50-100000 mg/kg, such as 50mg/kg, 100mg/kg, 500mg/kg, 1000mg/kg, 5000mg/kg, 10000mg/kg, 50000mg/kg or 100000mg/kg, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the residual salt of the crystallization in step (1) has a heavy metal content of 0.5 to 10000mg/kg, such as 0.5mg/kg, 10mg/kg, 100mg/kg, 1000mg/kg, 5000mg/kg or 10000mg/kg, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the heavy metal comprises any one of copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium, bismuth, chromium, vanadium, thallium or manganese or a mixture of at least two of these, typical but non-limiting examples being: mixtures of copper, nickel and cobalt, mixtures of lead, antimony and mercury, mixtures of tin, cadmium and bismuth or mixtures of chromium, vanadium, thallium and manganese, etc.
The invention utilizes the principle that the acid which is difficult to volatilize can prepare the volatile acid to convert the inorganic salt in the salt residue of the salt-containing organic wastewater into sulfate, and particularly separates and treats chloride ions and nitrate ions in a gas form. Taking sodium chloride and sodium nitrate as examples, the specific equation is as follows:
2NaCl (solid) + H2SO4(concentrated) Na ═ Na2SO4+2HCl↑
2NaNO3(solid) + H2SO4(concentrated) Na ═ Na2SO4+2HNO3↑
As a preferable technical scheme of the invention, pure H in the sulfuric acid in the step (1)2SO4The mass fraction of the component (A) is more than or equal to 70 percent.
Preferably, the amount of the sulfuric acid added in the step (1) is 1 to 5 times, such as 1 time, 1.5 times, 2 times, 2.5 times, 2.7 times, 3 times, 3.5 times, 4 times or 5 times, etc., more preferably 2 to 3 times, such as 2 times, 2.1 times, 2.3 times, 2.5 times, 2.7 times, 2.9 times or 3 times, etc., of the mass of the residual salt of crystallization, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
In a preferred embodiment of the present invention, the heating time in step (1) is 1 to 5 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, and more preferably 1 to 3 hours, such as 1 hour, 1.4 hours, 1.7 hours, 1.9 hours, 2 hours, 2.3 hours, 2.6 hours, 2.8 hours or 3 hours, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the heating temperature in step (1) is 100 to 600 ℃, such as 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃ or 600 ℃, and more preferably 200 to 500 ℃, such as 200 ℃, 250 ℃, 300 ℃, 340 ℃, 400 ℃, 460 ℃ or 500 ℃, but not limited to the recited values, and other unrecited values within the above numerical range are also applicable.
As a preferable technical scheme of the invention, the curing agent in the step (2) is a mineral containing silicon and/or aluminum.
Preferably, the silicon and/or aluminium containing mineral comprises any one or a mixture of at least two of clay, kaolin, silica sand, alumina, bauxite, red mud, fly ash or mill tailings, typical but non-limiting examples of which are: a mixture of clay and kaolin, a mixture of fly ash and silica sand, a mixture of silica sand and mineral processing tailings, a mixture of silica sand, alumina and bauxite or a mixture of alumina, bauxite, red mud and fly ash, etc., and further preferably any one or a mixture of at least two of kaolin, red mud or fly ash, the typical but non-limiting examples of which are: mixtures of kaolin and red mud, mixtures of kaolin and fly ash or mixtures of red mud and fly ash, and the like.
The invention adds a certain amount of curingThe agent can pyrolyze and solidify the residual salt reacted with the sulfuric acid at high temperature, convert the water-soluble crystalline ionic compound into the water-insoluble mineral composite oxide, and realize the safe solidification of the residual salt. With sulphate and silica Sand (SiO)2) Kaolin (Al)2O3·2SiO2) The pyrolytic curing reaction of the potassium feldspar produces the potassium feldspar (K)2O·Al2O3·6SiO2) Albite (Na)2O·Al2O3·6SiO2) Leucite (KAlSi)2O6) Jadeite (NaAlSi)2O6) For example, the specific equation is as follows:
K2O·SO3+Al2O3·2SiO2+4SiO2＝K2O·Al2O3·6SiO2+SO3↑
Na2O·SO3+Al2O3·2SiO2+4SiO2＝Na2O·Al2O3·6SiO2+SO3↑
K2O·SO3+Al2O3·2SiO2+2SiO2＝2KAlSi2O6+SO3↑
Na2O·SO3+Al2O3·2SiO2+2SiO2＝2NaAlSi2O6+SO3↑
preferably, the amount of the curing agent added in step (2) is 2 to 8 times, such as 2 times, 3 times, 3.5 times, 4 times, 4.5 times, 5 times, 5.5 times, 6 times, 7 times or 8 times, etc., more preferably 3 to 6 times, such as 3 times, 3.3 times, 3.5 times, 4 times, 4.5 times, 4.7 times, 5 times, 5.3 times, 5.5 times or 6 times, etc., of the mass of the sulfate-containing miscellaneous salt, but is not limited to the recited values, and other values not recited in the above numerical range are also applicable.
As a preferable technical scheme of the invention, grinding is carried out after the mixing in the step (2) to obtain a grinding mixture.
Preferably, the mixed particle size of the grinding mixture is 10 to 200 mesh, such as 10 mesh, 20 mesh, 50 mesh, 70 mesh, 100 mesh, 130 mesh, 150 mesh or 200 mesh, and more preferably 20 to 100 mesh, such as 20 mesh, 30 mesh, 40 mesh, 50 mesh, 60 mesh, 70 mesh, 80 mesh, 90 mesh or 100 mesh, but is not limited to the enumerated values, and other unrecited values within the above numerical range are also applicable.
In a preferred embodiment of the present invention, the pyrolysis curing temperature in step (2) is 800 to 1500 ℃, such as 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, or 1500 ℃, and more preferably 950 to 1300 ℃, such as 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, or 1300 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable.
Preferably, the pyrolysis curing time in the step (2) is 0.5 to 5 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, etc., more preferably 1 to 2 hours, such as 1 hour, 1.2 hours, 1.4 hours, 1.5 hours, 1.7 hours, 1.9 hours or 2 hours, etc., but not limited to the enumerated values, and other non-enumerated values in the above numerical range are also applicable.
Preferably, the mineral complex compound of step (2) comprises any one or a mixture of at least two of feldspar, jadeite, leucite, nepheline, mica or illite, typical but non-limiting examples of which are: a mixture of feldspar and leucite, a mixture of feldspar and mica, a mixture of jadeite and illite, a mixture of feldspar, nepheline and mica, or a mixture of jadeite, leucite and mica, and the like.
As a preferable technical scheme of the invention, the tail gas generated in the step (1) and the step (2) is discharged after reaching the standard.
Preferably, the tail gas treatment method includes a treatment method by any one or at least two of alkali absorption, dust removal, desulfurization, denitration, and dioxin removal, and typical but non-limiting examples of the treatment method are: a treatment method of alkali absorption, desulfurization and denitration, a treatment method of dust removal, desulfurization and denitration, a treatment method of desulfurization, denitration and dioxin removal, a treatment method of alkali absorption, desulfurization, denitration and dioxin removal, or the like.
As a preferable technical solution of the present invention, the processing method includes the steps of:
(1) mixing the residual crystallized salt with 1-5 times of sulfuric acid with the mass fraction of more than or equal to 70%, and heating at 100-600 ℃ for 1-5 hours to obtain the mixed salt containing sulfate;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 2-8 times of a curing agent, grinding to obtain a ground mixture with the mixed particle size of 10-200 meshes, and then performing pyrolysis curing at 800-1500 ℃ for 0.5-5 h to obtain the mineral composite compound.
Another object of the present invention is to provide a use of the mineral complex compound obtained by the treatment method of the present invention, which can be used as general industrial solid waste for comprehensive utilization, including but not limited to roadbed material, building lightweight aggregate, building block material, ceramic material or glass material.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the treatment method, inorganic salts in the salt residue of the salt-containing organic wastewater are converted into sulfate through sulfuric acid, and particularly, chloride ions and nitrate ions are separated in a gas form, so that the corrosion of chloride ions to equipment and the formation of water-soluble ionic compounds in a high-temperature curing process are avoided;
(2) according to the treatment method, through pyrolysis and solidification, organic matters in the salt-containing organic wastewater crystallization residual salt are completely decomposed and the residual salt is safely solidified, so that the moisture absorption and dissolution of water-soluble salt are reduced, and the leaching risk of toxic and harmful substances such as impurity organic matters and heavy metals in the residual salt is reduced;
(3) the solidification rate of the water-soluble salt in the mineral compound obtained by the invention is more than or equal to 99 percent, the TOC in the water leaching solution (1:10) of the mineral compound is less than or equal to 0.5mg/L, and the heavy metal content in the leaching solution meets the pollution control index limit value of a common industrial solid waste landfill.
(4) The mineral state compound after pyrolysis and solidification can be comprehensively utilized as common industrial solid waste, so that the pollution of the compound to the environment can be eliminated, and the resource utilization and circular economy of byproducts can be realized;
(5) the treatment method has the advantages of cheap and easily-obtained raw materials, simple process and lower cost, and is beneficial to industrial implementation.
Drawings
FIG. 1 is a flow chart of the method for treating residual salt from crystallization of salt-containing organic wastewater
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The following example is to mix and heat the salt-containing organic wastewater crystallization residual salt with sulfuric acid, so that the inorganic salt in the crystallization residual salt is converted into sulfate, then mix the sulfate-containing mixed salt with a curing agent, and perform pyrolysis and curing to obtain a mineral composite compound. The mineral state compound can be comprehensively utilized as general industrial solid waste.
Example 1
(1) Mixing salt-containing organic wastewater crystallization residual salt with 2 times of sulfuric acid with the mass fraction of 95%, heating to 500 ℃, and reacting for 3 hours to obtain sulfate-containing mixed salt;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 4 times of kaolin: mixing the silica sand with a mixed curing agent in a ratio of 1:2, grinding to 100 meshes, and roasting at 1200 ℃ for 2 hours to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after separation crystallization of waste salt from a certain Shandong Weifang farm chemical plant, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 8000mg/kg, calcium is 620mg/kg, magnesium is 73mg/kg, aluminum is 95mg/kg, iron is 40mg/kg, and chromium is 20 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.6 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral state composite compound can be used as a ceramic raw material.
Example 2
(1) Mixing the salt-containing organic wastewater crystallization residual salt with 1 time of sulfuric acid with the mass fraction of 98%, heating to 100 ℃, and reacting for 1h to obtain mixed salt containing sulfate;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 3 times of red mud: mixing the fly ash and the mixed curing agent in a ratio of 1:3, grinding the mixture to 20 meshes, and roasting the mixture for 1 hour at 700 ℃ to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after separation crystallization of waste salt from a certain Shandong Weifang farm chemical plant, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 8000mg/kg, calcium is 620mg/kg, magnesium is 73mg/kg, aluminum is 95mg/kg, iron is 40mg/kg, and chromium is 20 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 95.1 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral state composite compound can be used as a ceramic raw material.
Example 3
(1) Mixing salt-containing organic wastewater crystallization residual salt with 2.5 times of sulfuric acid with the mass fraction of 95%, heating to 400 ℃, and reacting for 3 hours to obtain sulfate-containing mixed salt;
(2) mixing the mixed salt containing sulfate obtained in the step (1) with 4 times of fly ash, grinding to 50 meshes, and then roasting at 1150 ℃ for 2h to obtain the water-insoluble mineral composite compound.
The residual salt for crystallization used in this example is residual salt evaporated from concentrated mother liquor after fractional crystallization of waste salt from a chemical plant in Hebei, wherein the inorganic salt in the residual salt mainly comprises potassium chloride and potassium sulfate, and the residual salt contains 6500mg/kg of TOC, 400mg/kg of calcium, 80mg/kg of magnesium, 60mg/kg of aluminum, 76mg/kg of iron and 26mg/kg of chromium. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.5 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral state compound can be used as glass raw material.
Example 4
(1) Mixing the salt-containing organic wastewater crystallization residual salt with 1.35 times of sulfuric acid with the mass fraction of 95%, heating to 380 ℃, and reacting for 3 hours to obtain sulfate-containing mixed salt;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 4 times of kaolin: mixing the silica sand with a mixed curing agent in a ratio of 1:4, grinding to 100 meshes, and then roasting at 1200 ℃ for 2h to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after separation crystallization of waste salt from a certain Shandong Weifang farm chemical plant, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 8000mg/kg, calcium is 620mg/kg, magnesium is 73mg/kg, aluminum is 95mg/kg, iron is 40mg/kg, and chromium is 20 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.1 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral state composite compound can be used as a ceramic raw material.
Example 5
(1) Mixing the salt-containing organic wastewater crystallization residual salt with 1.6 times of sulfuric acid with the mass fraction of 98%, heating to 450 ℃, and reacting for 3 hours to obtain sulfate-containing mixed salt;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 4.5 times of kaolin: mixing the silica sand with a mixed curing agent in a ratio of 1:4, grinding to 50 meshes, and then roasting at 1100 ℃ for 1.5h to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after fractional crystallization of waste salt from a chemical plant in Jiangsu, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 6000mg/kg, calcium is 400mg/kg, magnesium is 86mg/kg, aluminum is 42mg/kg, iron is 46mg/kg, and chromium is 12 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.4 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral state composite compound can be used as a ceramic raw material.
Example 6
(1) Mixing salt-containing organic wastewater crystallization residual salt with 3 times of sulfuric acid with the mass fraction of 98.3%, heating to 600 ℃, and reacting for 2 hours to obtain mixed salt containing sulfate;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 2 times of kaolin: mixing the fly ash and the mixed curing agent in a ratio of 1:5, grinding the mixture to 200 meshes, and then roasting the mixture for 0.5h at 800 ℃ to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after separation crystallization of waste salt from a certain Shandong Weifang farm chemical plant, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 8000mg/kg, calcium is 620mg/kg, magnesium is 73mg/kg, aluminum is 95mg/kg, iron is 40mg/kg, and chromium is 20 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.1 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral composite compound can be used for preparing building blocks.
Example 7
(1) Mixing salt-containing organic wastewater crystallization residual salt with 5 times of sulfuric acid with the mass fraction of 98.3%, heating to 200 ℃, and reacting for 5 hours to obtain mixed salt containing sulfate;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with 8 times of kaolin: mixing the fly ash and the mixed curing agent in a ratio of 1:5, grinding the mixture to 10 meshes, and roasting the mixture at 1500 ℃ for 5 hours to obtain the water-insoluble mineral composite compound.
The residual salt from crystallization in this example is residual salt evaporated from concentrated mother liquor after fractional crystallization of waste salt from a chemical plant in Jiangsu, wherein the inorganic salt in the residual salt is mainly sodium chloride and sodium sulfate, and the TOC content in the residual salt is 6000mg/kg, calcium is 400mg/kg, magnesium is 86mg/kg, aluminum is 42mg/kg, iron is 46mg/kg, and chromium is 12 mg/kg. The mineral compound obtained by harmless treatment of the residual salt realizes that the solidification rate of water-soluble salt in the residual salt is more than or equal to 99.5 percent. The water extract (1:10) of the mineral compound has TOC less than or equal to 0.5mg/L, calcium less than or equal to 0.01mg/L, magnesium less than or equal to 0.01mg/L, aluminum less than or equal to 0.05mg/L, iron less than or equal to 0.05mg/L and chromium less than or equal to 0.05 mg/L. The mineral composite compound can be used for preparing building lightweight aggregate.
Comparative example 1
This comparative example was carried out under exactly the same conditions as example 1, except that no sulfuric acid was added.
The residual salt from the crystallization in this comparative example is residual salt evaporated from concentrated mother liquor after the waste salt from a certain pesticide factory in Shandong Weifang is subjected to quality-divided crystallization, wherein the inorganic salt in the residual salt mainly comprises sodium chloride and sodium sulfate, and the residual salt contains 8000mg/kg of TOC, 620mg/kg of calcium, 73mg/kg of magnesium, 95mg/kg of aluminum, 40mg/kg of iron and 20mg/kg of chromium. The solidification rate of the water-soluble salt in the mineral composite compound obtained by the process is 59.4%. The mineral compound water extract (1:10) contains TOC 450mg/L, calcium 52mg/L, magnesium 47mg/L, aluminum 43mg/L, iron 15mg/L and chromium 4 mg/L.
Comparative example 2
This comparative example was identical to example 3 except that no curing agent was added.
The residual salt used in the embodiment is residual salt obtained by concentrating and evaporating mother liquor after carrying out mass separation crystallization on waste salt of a certain chemical plant in Hebei, wherein inorganic salt in the residual salt mainly comprises potassium chloride and potassium sulfate, and TOC content in the residual salt is 6500mg/kg, calcium is 400mg/kg, magnesium is 80mg/kg, aluminum is 60mg/kg, iron is 76mg/kg, and chromium is 26 mg/kg. The mineral complex compound can not be obtained by the process, and the water-soluble salt in the crystallization residual salt can not be solidified.
As can be seen from examples 1 to 7, the solidification rate of the water-soluble salt in the mineral compound obtained by the treatment method is more than or equal to 99%, the TOC in the mineral compound water leaching solution (1:10) is less than or equal to 0.5mg/L, and the heavy metal content in the leaching solution meets the pollution control index limit value of a common industrial solid waste landfill. Comparative example 1 no sulfuric acid was added, resulting in a lower curing rate of water-soluble salts in the mineral-state composite compound obtained by the process, and an exceeding of each content in the aqueous immersion (1:10) of the mineral-state composite compound. Comparative example 2 no curing agent was added, so that the mineral complex compound could not be obtained at all by this process.
The applicant states that the present invention is illustrated by the above examples of the treatment method of the present invention, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (27)

1. The method for treating the residual salt from the crystallization of the salt-containing organic wastewater is characterized by comprising the following steps of:
(1) mixing and heating salt-containing organic wastewater crystallization residual salt and sulfuric acid to convert inorganic salt in the crystallization residual salt into sulfate, so as to obtain mixed salt containing sulfate;
(2) mixing the sulfate-containing mixed salt obtained in the step (1) with a curing agent, and carrying out pyrolysis curing to obtain a mineral composite compound;
the mineral state compound comprises one or a mixture of at least two of feldspar, jadeite, leucite, nepheline, mica and illite;
and (3) the curing agent in the step (2) is a mineral containing silicon and/or aluminum.
2. The method for treating the salt residues from the crystallization of salt-containing organic wastewater in claim 1, wherein the inorganic salt in the salt residues from step (1) comprises any one or a mixture of at least two of halide, sulfate, sulfite, metal sulfide, nitrate or nitrite.
3. The method for treating salt-containing organic wastewater crystal residual salt according to claim 2, wherein the inorganic salt in the crystal residual salt in the step (1) comprises any one or a mixture of at least two of sodium chloride, sodium sulfate, sodium sulfite, sodium sulfide, sodium nitrate, sodium nitrite, potassium chloride, potassium sulfate, potassium sulfite, potassium sulfide, potassium nitrate and potassium nitrite.
4. The method for treating the residual crystallized salt of the salt-containing organic wastewater according to claim 1, wherein the TOC content of the residual crystallized salt in step (1) is 50-100000 mg/kg.
5. The method for treating the salt residue from the salt-containing organic wastewater crystallization in claim 1, wherein the heavy metal content of the salt residue from the step (1) is 0.5-10000 mg/kg.
6. The method for treating the salt residues from the crystallization of salt-containing organic wastewater as claimed in claim 5, wherein the heavy metal comprises any one or a mixture of at least two of copper, lead, zinc, tin, nickel, cobalt, antimony, mercury, cadmium, bismuth, chromium, vanadium, thallium or manganese.
7. Root of herbaceous plantThe method for treating the salt residue generated by crystallizing the salt-containing organic wastewater as claimed in claim 1, wherein the pure H in the sulfuric acid in the step (1)2SO4The mass fraction of the component (A) is more than or equal to 70 percent.
8. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the amount of the sulfuric acid added in the step (1) is 1-5 times of the mass of the salt residue.
9. The method for treating the salt residues from the crystallization of the salt-containing organic wastewater according to claim 8, wherein the amount of the sulfuric acid added in the step (1) is 2-3 times of the mass of the salt residues.
10. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the heating time in step (1) is 1-5 h.
11. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 10, wherein the heating time in step (1) is 1-3 h.
12. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the heating temperature in step (1) is 100-600 ℃.
13. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 12, wherein the heating temperature in step (1) is 200-500 ℃.
14. The method for treating the salt residue from the crystallization of salt-containing organic wastewater according to claim 1, wherein the mineral containing silicon and/or aluminum comprises one or a mixture of at least two of kaolin, silica sand, alumina, bauxite, red mud or fly ash.
15. The method for treating the salt residue from the crystallization of salt-containing organic wastewater as claimed in claim 14, wherein the mineral containing silicon and/or aluminum is one or a mixture of at least two of kaolin, red mud or fly ash.
16. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the amount of the curing agent added in the step (2) is 2-8 times of the mass of the salt residue.
17. The method for treating the salt residues in the crystallization of the salt-containing organic wastewater according to claim 16, wherein the amount of the curing agent added in the step (2) is 3-6 times of the mass of the salt residues.
18. The method for treating the salt residues from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the step (2) is followed by grinding to obtain a grinding mixture.
19. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater as claimed in claim 18, wherein the mixed particle size of the grinding mixture is 10-200 mesh.
20. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater as claimed in claim 19, wherein the mixed particle size of the grinding mixture is 20-100 mesh.
21. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the pyrolysis and solidification temperature in step (2) is 800-1500 ℃.
22. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater as claimed in claim 21, wherein the temperature of the pyrolysis and solidification in step (2) is 950-1300 ℃.
23. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the pyrolysis and solidification time in step (2) is 0.5-5 h.
24. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 23, wherein the pyrolysis and solidification time in step (2) is 1-2 h.
25. The method for treating the salt residue from the crystallization of the salt-containing organic wastewater according to claim 1, wherein the tail gas generated in step (1) and step (2) is discharged after reaching the standard.
26. The method for treating the salt of the salt-containing organic wastewater crystal residual according to claim 25, wherein the tail gas treatment method comprises any one or at least two of alkali absorption, dust removal, desulfurization, denitrification and dioxin removal.
27. Use of the mineral complex compound obtained by the treatment method according to any one of claims 1 to 26, wherein the mineral complex compound is used as general industrial solid waste for comprehensive utilization, including but not limited to building lightweight aggregate, building block raw material, ceramic raw material or glass raw material.
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