CN113788564A - Method for treating and comprehensively utilizing mixed wastewater - Google Patents
Method for treating and comprehensively utilizing mixed wastewater Download PDFInfo
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- CN113788564A CN113788564A CN202111139985.2A CN202111139985A CN113788564A CN 113788564 A CN113788564 A CN 113788564A CN 202111139985 A CN202111139985 A CN 202111139985A CN 113788564 A CN113788564 A CN 113788564A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 59
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001103 potassium chloride Substances 0.000 claims abstract description 25
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000010802 sludge Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011591 potassium Substances 0.000 claims abstract description 16
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 15
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 14
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 14
- 239000004571 lime Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 239000003814 drug Substances 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 235000015097 nutrients Nutrition 0.000 claims abstract description 5
- 230000000813 microbial effect Effects 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims abstract description 4
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 48
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 42
- 238000004062 sedimentation Methods 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 25
- 238000005086 pumping Methods 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 12
- 238000009388 chemical precipitation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 9
- 239000011575 calcium Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- -1 Lithium hexafluorophosphate Chemical compound 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 5
- 229910001634 calcium fluoride Inorganic materials 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910004074 SiF6 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
Abstract
The invention relates to a method for treating mixed wastewater and comprehensively utilizing the mixed wastewater, which is characterized in that three kinds of wastewater in lithium salt industry, phosphorization industry and biological medicine industry are mixed, silicon dioxide, potassium chloride and other substances are added to produce potassium fluosilicate chemical products, the rest wastewater is subjected to twice chemical precipitation through lime emulsion and calcium chloride solution, deep decalcification is performed at the later stage, sludge generated by the third precipitation is squeezed and then is subjected to two-stage drying to obtain finished double-ash powder, and the wastewater subjected to the third precipitation can be used as nutrient solution of a microbial oil recovery aid. The invention makes full use of various substances in the waste water, and realizes the purposes of treating waste by waste, protecting the environment and saving energy.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of industrial wastewater, and particularly relates to a method for treating and comprehensively utilizing mixed wastewater.
Background
A large amount of mixed acid is produced in the lithium salt industry as a byproduct, a large amount of fluorine-containing wastewater is produced in the phosphorus chemical industry as a byproduct, and the large amount of waste mixed acid as a byproduct can cause great pollution to the environment if being directly discharged without being treated.
Lithium hexafluorophosphate (LiPF)6) Is a main raw material for producing lithium batteries, and can gradually generate a byproduct in various links of producing lithium hexafluorophosphate: the main components of the mixed acid are hydrogen fluoride and hydrogen chloride, and a small amount of sulfuric acid and carbonic acid are also contained. At present, lime treatment is mostly adopted in the industry, after calcium-containing sludge and high-salinity wastewater are obtained, the calcium-containing sludge can be buried in an industrial solid waste landfill, and the high-salinity wastewater can still pollute the environment if directly discharged.
Sodium fluorosilicate (Na)2SiF6) The sodium fluosilicate is an inorganic substance, belongs to a complex salt, is the most used fluosilicate variety in the building and building material industry, and a large amount of fluosilicate exists in an aqueous solution in the form of ions in the process of producing sodium fluosilicate, thereby causing a large amount of waste. At present, lime is commonly used in industry for neutralization and then subsequent treatment is carried out, so that silicate ions in the solution are not fully utilized, and the subsequent treatment also increases the economic cost.
The biological medicine industry often produces high-concentration potassium chloride wastewater, the salt content is too high, the wastewater cannot be directly discharged, the potassium chloride is often recovered by an evaporation crystallization method and then the wastewater is discharged, and the treatment cost is too high.
The development of the waste production industry is troubled by industrial by-product calcium-containing solid waste for many years. Many enterprises are forced to deposit and store in the factory, which causes great potential safety and environmental protection hazards. In the era of global advocating energy conservation, consumption reduction and low-carbon economy development, the exploration of new production technology and process becomes a consensus of the people in the industry. Although the calcium-containing mixed sludge can be buried in industrial solid waste landfill sites, if the calcium-containing mixed sludge is directly buried, the calcium fluoride is harmful to soil, although the calcium fluoride is slightly soluble in water, fluoride ions are reformed due to rain wash in the nature to influence the surface water quality, and secondary pollution is caused, so that the waste of resources is avoided, the secondary pollution of the environment is more easily caused, and the calcium-containing mixed sludge is not suitable for being buried. The sludge incineration method can only treat some organic residue sludge, but has large investment and high cost, and is not suitable for being adopted.
At present, the sewage is treated respectively in the industry, and various substances in the wastewater can be combined and fully utilized, so that the aims of treating the waste by the waste, protecting the environment and saving energy are fulfilled.
Disclosure of Invention
The invention aims to solve the problems and provides a method for treating mixed wastewater and comprehensively utilizing the mixed wastewater, so as to achieve the purposes of treating wastes with processes of wastes against one another, protecting the environment and saving energy.
The invention is realized by adopting the following technical scheme: a method for treating mixed wastewater and comprehensively utilizing the mixed wastewater is characterized by comprising the following steps:
step S1, mixing and pumping the wastewater 1 and the wastewater 2 into a reaction kettle, measuring the concentrations of fluosilicic acid and hydrofluoric acid in the mixed wastewater, and adding silicon dioxide according to the proportion;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, and pumping the saturated potassium chloride liquid into the reaction kettle in the step S1 according to a certain proportion;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, and washing and drying the filtered solid to obtain a finished product of potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation;
step S5, deep decalcification is carried out on the liquid obtained after the secondary precipitation in the step S4;
step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room, and carrying out flash drying and sieving to obtain finished double ash powder;
the wastewater 1 is from the lithium salt industry and contains high-concentration hydrogen fluoride, the wastewater 2 is from the phosphorus chemical industry and contains high-concentration fluosilicic acid, and the wastewater 3 is from the biological medicine industry and contains high-concentration potassium chloride.
Further, the adding amount of the silicon dioxide in the step S1 is 47-49% of the mass of the hydrofluoric acid according to the mass fraction.
Further, in the step S1, the reaction temperature of the hydrofluoric acid and the silicon dioxide is 60-80 ℃, and the reaction time is 3-5 hours.
Further, according to the reaction amount, an equivalent amount of potassium chloride is added in the step S2 to react with the fluosilicic acid, and the reaction equivalent amount of the potassium chloride and the fluosilicic acid is 2: 1.
further, in the step S2, the reaction temperature of the potassium chloride and the fluosilicic acid is 60-80 ℃, and the reaction time is 1.5-3 hours.
Further, the lime emulsion is added in the step S4 until the pH value of the sedimentation tank is 5-7, and then the calcium chloride solution is added for secondary sedimentation until no sediment is generated.
Further, the decalcifying agent in step S5 is sodium sulfate.
Further, the liquid after deep decalcification in step S5 can be used as a nutrient solution for a microbial oil recovery aid.
Further, the drying time of the sunlight room in the step S6 is 20-24 hours, and the flash evaporation drying temperature is 330-350 ℃.
The invention has the beneficial effects that:
1. the invention creatively mixes the three waste waters of lithium salt industry, phosphorization industry and biological medicine industry and adds silicon dioxide, potassium chloride and other substances to produce potassium fluosilicate chemical products, the sludge obtained by processing the residual sewage can be used as double ash powder in building industry after being dried, and the high-salinity water solution can be used as nutrient solution to culture microorganisms, thereby really realizing the purposes of treating waste by waste, protecting environment and saving energy.
2. The method simultaneously mixes the waste water 1 in the lithium salt industry and the waste water 2 in the phosphorus chemical industry, reacts with hydrofluoric acid to generate fluosilicic acid under the condition of high temperature by adding silicon dioxide, and generates chemical product potassium fluosilicate with the waste water 3 in the biological medicine industry.
3. The waste water after producing the potassium fluosilicate is subjected to twice chemical precipitation by the lime emulsion and the calcium chloride solution, and the decalcifying agent is added in the later period, so that the waste water after the three-time precipitation contains high-concentration salt, and can be used as a nutrient solution of a microbial oil recovery auxiliary agent.
4. The calcium-containing sludge produced by squeezing the sludge produced by the three-time precipitation is dried in two stages, most of water in the calcium-containing sludge is removed by drying in a sunlight room, and then the finished product double-ash powder is obtained by flash evaporation drying. The main components of the calcium-containing sludge are calcium fluoride, calcium sulfate, calcium hydroxide and calcium carbonate, and the four materials are exactly the materials commonly used in cement building materials.
Detailed Description
The technical solutions in the examples will be clearly and completely described below. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
The wastewater 1 is from the lithium salt industry and contains high-concentration hydrogen fluoride, the wastewater 2 is from the phosphorus chemical industry and contains high-concentration fluosilicic acid, and the wastewater 3 is from the biological medicine industry and contains high-concentration potassium chloride;
step S1, mixing 50kg of wastewater 1 and 50kg of wastewater 2, pumping into a reaction kettle, measuring the concentration of fluosilicic acid and hydrofluoric acid in the mixed wastewater, adding silicon dioxide according to 47% of the mass of hydrofluoric acid, wherein the reaction temperature is 60 ℃, and the reaction time is 3 hours;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, reacting potassium chloride with fluosilicic acid in equivalent amount in the liquid, pumping the liquid into the reaction kettle in the step S1, wherein the reaction temperature is 60 ℃, and the reaction time is 1.5 h;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, washing and drying the filtered solid to obtain a finished product of potassium fluosilicate, and determining the purity of the potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank until the pH value in the sedimentation tank is 5, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation until no sediment is generated;
step S5, taking out a part of the liquid after the secondary precipitation in the step S4, measuring the concentration of calcium ions in the solution, and adding equivalent sodium sulfate to carry out deep decalcification;
and step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room for 20 hours, passing through a flash evaporation dryer with the flash evaporation temperature of 330 ℃, and finally sieving to obtain the finished double-ash powder.
Example 2
The wastewater was the same as in example 1;
step S1, mixing 50kg of wastewater 1 and 50kg of wastewater 2, pumping into a reaction kettle, measuring the concentration of fluosilicic acid and hydrofluoric acid in the mixed wastewater, adding silicon dioxide according to 49% of the mass of the hydrofluoric acid, wherein the reaction temperature is 80 ℃, and the reaction time is 5 hours;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, reacting potassium chloride with fluosilicic acid in equivalent amount in the liquid, pumping the liquid into the reaction kettle in the step S1, wherein the reaction temperature is 80 ℃, and the reaction time is 3 hours;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, washing and drying the filtered solid to obtain a finished product of potassium fluosilicate, and determining the purity of the potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank until the pH value in the sedimentation tank is 7, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation until no sediment is generated;
step S5, taking out a part of the liquid after the secondary precipitation in the step S4, measuring the concentration of calcium ions in the solution, and adding equivalent sodium sulfate to carry out deep decalcification;
and step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room for 24 hours, passing through a flash evaporation dryer with the flash evaporation temperature of 350 ℃, and finally sieving to obtain the finished double-ash powder.
Example 3
The wastewater was the same as in example 1;
step S1, mixing 50kg of wastewater 1 and 50kg of wastewater 2, pumping into a reaction kettle, measuring the concentration of fluosilicic acid and hydrofluoric acid in the mixed wastewater, adding silicon dioxide according to 48% of the mass of the hydrofluoric acid, wherein the reaction temperature is 70 ℃, and the reaction time is 4 hours;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, reacting potassium chloride with fluosilicic acid in equivalent amount in the liquid, pumping the liquid into the reaction kettle in the step S1, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, washing and drying the filtered solid to obtain a finished product of potassium fluosilicate, and determining the purity of the potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank until the pH value in the sedimentation tank is 6, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation until no sediment is generated;
step S5, taking out a part of the liquid after the secondary precipitation in the step S4, measuring the concentration of calcium ions in the solution, and adding equivalent sodium sulfate to carry out deep decalcification;
and step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room for 22 hours, passing through a flash evaporation dryer with the flash evaporation temperature of 340 ℃, and finally sieving to obtain the finished double-ash powder.
Example 4
The wastewater was the same as in example 1;
step S1, mixing 50kg of wastewater 1 and 50kg of wastewater 2, pumping into a reaction kettle, measuring the concentrations of fluosilicic acid and hydrofluoric acid in the mixed wastewater, and adding silicon dioxide according to the reaction equivalent of the hydrofluoric acid, wherein the reaction temperature is 70 ℃, and the reaction time is 4 hours;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, reacting potassium chloride with fluosilicic acid in equivalent amount in the liquid, pumping the liquid into the reaction kettle in the step S1, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, washing and drying the filtered solid to obtain a finished product of potassium fluosilicate, and determining the purity of the potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank until the pH value in the sedimentation tank is 6, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation until no sediment is generated;
step S5, taking out a part of the liquid after the secondary precipitation in the step S4, measuring the concentration of calcium ions in the solution, and adding equivalent sodium sulfate to carry out deep decalcification;
and step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room for 22 hours, passing through a flash evaporation dryer with the flash evaporation temperature of 340 ℃, and finally sieving to obtain the finished double-ash powder.
Example 5
The wastewater was the same as in example 1;
step S1, mixing 50kg of wastewater 1 and 50kg of wastewater 2, pumping into a reaction kettle, measuring the concentration of fluosilicic acid and hydrofluoric acid in the mixed wastewater, adding silicon dioxide according to 48% of the mass of the hydrofluoric acid, wherein the reaction temperature is 70 ℃, and the reaction time is 4 hours;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, reacting potassium chloride with fluosilicic acid in equivalent amount in the liquid, pumping the liquid into the reaction kettle in the step S1, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, washing and drying the filtered solid to obtain a finished product of potassium fluosilicate, and determining the purity of the potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank until the sedimentation in the sedimentation tank is complete, and filtering after primary sedimentation;
step S5, taking out a part of the liquid precipitated in step S4, measuring the concentration of calcium ions in the solution, and adding equivalent sodium sulfate to deeply decalcify;
and step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room for 22 hours, passing through a flash evaporation dryer with the flash evaporation temperature of 340 ℃, and finally sieving to obtain the finished double-ash powder.
The production of examples 1 to 5 was carried out according to the process, and the results of the amounts of the respective substances and the concentrations of the main substances in the examples are shown in Table 1.
TABLE 1 EXAMPLES 1 to 5 examples 1 to 5 added amounts of the respective substances and concentrations of the main substances
As can be seen from the data in table 1, in examples 1 to 3, hydrofluoric acid is slightly excessive, and in example 4, silicon dioxide is added according to a reaction equivalent, but in example 4, not only the purity of potassium fluorosilicate is significantly reduced, but also the concentrations of the double ash powder and the sodium chloride after decalcification are significantly increased, which indicates that the slightly excessive hydrofluoric acid can produce potassium fluorosilicate with higher purity, so that the utilization rate of fluorine is increased, and the generation amount of sludge can be reduced, and because the utilization rate of fluorine is increased, the amount of calcium fluoride in the double ash powder can be correspondingly reduced, so that the proportions of calcium fluoride, calcium sulfate, calcium hydroxide and calcium carbonate in the double ash powder are more uniform, and the utilization rate of the double ash powder in the process of adapting the putty powder is also increased. In the example 5, only the lime emulsion is added in the neutralization process, so that the concentration of fluoride ions in the decalcified solution is obviously increased, the sewage can be discharged or used for other purposes only after further treatment, and the concentration of sodium chloride in the decalcified solution is also obviously increased.
Claims (9)
1. A method for treating mixed wastewater and comprehensively utilizing the mixed wastewater is characterized by comprising the following steps:
step S1, mixing and pumping the wastewater 1 and the wastewater 2 into a reaction kettle, measuring the concentrations of fluosilicic acid and hydrofluoric acid in the mixed wastewater, and adding silicon dioxide according to the proportion;
step S2, adding solid potassium chloride into the wastewater 3, stirring to form saturated potassium chloride liquid, and pumping the saturated potassium chloride liquid into the reaction kettle in the step S1 according to a certain proportion;
step S3, filtering the liquid after the reaction in the reaction kettle of the step S2, and washing and drying the filtered solid to obtain a finished product of potassium fluosilicate;
step S4, pumping the liquid filtered in the step S3 into a sedimentation tank, adding lime emulsion into the sedimentation tank, filtering after primary sedimentation, and adding a calcium chloride solution again for secondary sedimentation;
step S5, deep decalcification is carried out on the liquid obtained after the secondary precipitation in the step S4;
step S6, collecting filter cakes formed by filter pressing the sludge precipitated in the steps S4 and S5, drying the filter cakes in a sunlight room, and carrying out flash drying and sieving to obtain finished double ash powder;
the wastewater 1 is from the lithium salt industry and contains high-concentration hydrogen fluoride, the wastewater 2 is from the phosphorus chemical industry and contains high-concentration fluosilicic acid, and the wastewater 3 is from the biological medicine industry and contains high-concentration potassium chloride.
2. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: according to the mass fraction, the adding amount of the silicon dioxide in the step S1 is 47-49% of the mass of the hydrofluoric acid.
3. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: in the step S1, the reaction temperature of the hydrofluoric acid and the silicon dioxide is 60-80 ℃, and the reaction time is 3-5 hours.
4. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: adding equivalent potassium chloride and fluosilicic acid in the step S2 to react according to reaction equivalent, wherein the reaction equivalent of the potassium chloride and the fluosilicic acid is 2: 1.
5. the method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: in the step S2, the reaction temperature of the potassium chloride and the fluosilicic acid is 60-80 ℃, and the reaction time is 1.5-3 h.
6. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: and S4, adding the lime emulsion until the pH value of the sedimentation tank is 5-7, and adding a calcium chloride solution for secondary sedimentation until no sediment is generated.
7. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: the decalcifying agent in the step S5 is sodium sulfate.
8. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: the liquid after deep decalcification in the step S5 can be used as a nutrient solution of the microbial oil recovery aid.
9. The method for treating and comprehensively utilizing mixed wastewater according to claim 1, characterized in that: the drying time of the sunlight room in the step S6 is 20-24 hours, and the flash evaporation drying temperature is 330-350 ℃.
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