CN116462377A - Recycling utilization method of high-heat-value wastewater of hazardous waste plant - Google Patents
Recycling utilization method of high-heat-value wastewater of hazardous waste plant Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 56
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 118
- 239000007788 liquid Substances 0.000 claims abstract description 115
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 30
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 24
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 fluoride ions Chemical class 0.000 claims abstract description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000001110 calcium chloride Substances 0.000 claims abstract description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 12
- 229910001634 calcium fluoride Inorganic materials 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 7
- 238000010979 pH adjustment Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 230000006872 improvement Effects 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
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- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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Classifications
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- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/02—Softening water by precipitation of the hardness
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention discloses a recycling method for high-heat-value wastewater of a hazardous waste plant, belonging to the technical field of wastewater treatment of the hazardous waste plant; it comprises the following steps: pH adjustment is carried out on high-calorific-value wastewater of a hazardous waste plant to obtain first waste liquid; introducing high-temperature steam into the first waste liquid to obtain second waste liquid; ozone is introduced into the second waste liquid to obtain third waste liquid; adding sodium hydroxide and calcium chloride into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid; adding sodium carbonate into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid; the fifth waste liquid is evaporated and crystallized to obtain condensate serving as an incineration heat source and concentrated solution serving as a solidification thickener, and the invention can separate fluoride ions, calcium and magnesium hardness ions and waste water in high-heat-value waste water of hazardous waste plants, so that the problems of system corrosion, scaling and the like caused by directly feeding the high-heat-value waste water into an incinerator for incineration are avoided; realizes the multi-level utilization of the high-heat-value wastewater of the hazardous waste plant and improves the economic value of the high-heat-value wastewater.
Description
Technical Field
The invention relates to the technical field of sewage treatment of hazardous waste plants, in particular to a recycling method for high-heat-value wastewater of hazardous waste plants.
Background
With the development of industry, the discharge of hazardous waste in industrial production process is increasing; the annual hazardous waste production worldwide is estimated to be 3.3 hundred million tons. Due to the serious pollution and potential serious impact of hazardous waste, it has the following drawbacks: (1) the ecological environment is destroyed, and the dangerous waste which is discharged and stored at will pollutes water and soil under the long-term permeation and diffusion effects of the rainwater and the underground water, so that the environmental function grade of the area is reduced; (2) hazardous waste is toxic by ingestion, inhalation, skin absorption, eye contact, or causes dangerous events such as burning, explosion, etc., affecting human health; long-term hazards include long-term poisoning, carcinogenesis, teratogenicity, etc. caused by repeated contact; (3) and the sustainable development is restricted, and the pollution of the atmosphere, water source, soil and the like caused by the non-treatment or non-standard treatment of the dangerous wastes can also become the bottleneck restricting the economic activity. The industrial developed countries are very sensitive to the problem of hazardous waste, a large number of hazardous waste treatment plants are set up, and the treatment cost of hazardous waste is relatively high.
The high heat value wastewater received by the dangerous waste projects in the present stage mainly comes from organic waste liquid, mineral oil fusion and the like generated in the industries of basic chemical raw material manufacture, petrochemical industry, medicine manufacture industry, refined product manufacture and the like, has very complex components, not only presents high heat value, but also has fluoride ions, calcium magnesium hardness ions with extremely high content and presents strong acid characteristics; has the characteristics of strong corrosiveness and strong scaling property.
According to the characteristics of the wastewater, a treatment method of direct incineration or physicochemical and biochemical treatment is adopted in China, but the direct incineration mode often causes the damage of the position of an incinerator and serious scaling of a system due to the characteristics of strong corrosiveness and strong scaling of the wastewater, and is frequent to clean; the treatment mode of 'materialization and biochemistry' not only can cause waste of heat value in the wastewater, but also can cause low efficiency of removing refractory organic matters of a biochemical system due to existence of a large amount of toxic substances in the water, and toxic substances in the wastewater are toxic to microorganisms for a long time, so that the biochemical system is crashed after long-time operation.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a recycling method for high-heat-value wastewater in a hazardous waste plant, which not only can realize the utilization of the high heat value of the wastewater, but also can avoid the problems of equipment corrosion caused by fluoride ions and equipment scaling caused by calcium and magnesium ions.
The invention discloses a recycling method of high-heat-value wastewater in a hazardous waste plant, which comprises the following steps:
pH adjustment is carried out on high-calorific-value wastewater of a hazardous waste plant to obtain first waste liquid;
introducing high-temperature steam into the first waste liquid to obtain second waste liquid;
ozone is introduced into the second waste liquid to obtain third waste liquid;
adding sodium hydroxide and calcium chloride into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid;
adding sodium carbonate into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid;
evaporating and crystallizing the fifth waste liquid to obtain condensate and concentrated solution;
and lifting the condensate to an incinerator to serve as an incineration heat source, and lifting the concentrated solution to a curing workshop to serve as a curing thickener.
As a further improvement of the invention, the pH of the high-calorific-value wastewater of the hazardous waste plant is adjusted to obtain a first waste liquid; comprising the following steps:
and adding sodium hydroxide into the high-calorific-value wastewater of the hazardous waste plant, and adjusting the pH to 2-3 to obtain the first waste liquid.
As a further improvement of the invention, the high-temperature steam is introduced into the first waste liquid to obtain a second waste liquid; comprising the following steps:
introducing high-temperature steam into the first waste liquid to perform high-temperature thermal reaction, so that oily matters wrapped on the surface of water drops in the first waste liquid are broken, and a second waste liquid is obtained; wherein the heating time is 50-60 min, and the water temperature is controlled to be 70-80 ℃.
As a further improvement of the invention, ozone is introduced into the second waste liquid to obtain a third waste liquid; comprising the following steps:
ozone is introduced into the second waste liquid to perform oxidation reaction, so that oily matters wrapped in water drops in the second waste liquid are released, and a third waste liquid is obtained; wherein the concentration of ozone is controlled to be 100-120 mg/L, and the reaction time is 2h.
As a further improvement of the invention, sodium hydroxide and calcium chloride are added into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid; comprising the following steps:
firstly adding sodium hydroxide into the third waste liquid, and controlling the pH value to be 9-10; then adding calcium chloride, enabling the calcium chloride to react with fluoride ions in the third waste liquid to generate calcium fluoride precipitates, and respectively obtaining calcium fluoride residues and fourth waste liquid through precipitation and filtration; wherein the molar content of the added calcium chloride is 1.2 times of the molar content of the fluoride ions in the third waste liquid, the reaction time is 45min, and the content of the fluoride ions in the fourth waste liquid is less than or equal to 20mg/L.
As a further improvement of the invention, sodium carbonate is added into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid; comprising the following steps:
adding sodium carbonate into the fourth waste liquid to react with calcium and magnesium ions in the fourth waste liquid to generate calcium carbonate and magnesium hydroxide precipitates, and respectively obtaining calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid through precipitation and filtration; wherein, the molar content of sodium carbonate added into the fourth waste liquid is 2 times of the molar content of calcium and magnesium ions in the fourth waste liquid, and the reaction time is 45min.
As a further improvement of the invention, the heat value of the high heat value wastewater of the hazardous waste plant is more than or equal to 4000cal/g, the fluorine ion is more than or equal to 1000mg/L, and the calcium and magnesium ion is more than or equal to 1500mg/L.
As a further improvement of the present invention, the high temperature steam is incineration boiler steam.
As a further improvement of the invention, the ozone is produced using an ozone generator.
As a further improvement of the invention, the evaporative crystallization adopts a process of three-effect evaporation and single-effect evaporation.
Compared with the prior art, the invention has the beneficial effects that:
the invention can separate the fluoride ions, calcium and magnesium hardness ions in the high heat value wastewater of the hazardous waste plant from the wastewater, thereby avoiding the problems of system corrosion, scaling and the like caused by directly feeding the high heat value wastewater into an incinerator for incineration; meanwhile, the easy-to-burn components in the high-heat-value wastewater are purified, so that the burning efficiency of a subsequent burning furnace is improved; the concentrated solution generated by the system can be used as a thickening agent required by a stabilizing and curing process of a curing workshop; realizes the multi-level utilization of the high-heat-value wastewater of the hazardous waste plant and improves the economic value of the high-heat-value wastewater.
Drawings
FIG. 1 is a flow chart of the method for recycling high-heat-value wastewater of the hazardous waste plant.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention is described in further detail below with reference to the attached drawing figures:
as shown in FIG. 1, the invention provides a recycling method for high-heat-value wastewater of a hazardous waste plant, which comprises the following steps:
step 1, adding alkali agent into high-calorific-value wastewater of a hazardous waste plant to carry out pH adjustment to obtain first waste liquid; wherein the heat value of the high heat value wastewater of the hazardous waste plant is more than or equal to 4000cal/g, the fluorine ion is more than or equal to 1000mg/L and the calcium and magnesium ion is more than or equal to 1500mg/L, and the alkali agent is preferably sodium hydroxide agent, and the pH is adjusted to 2-3;
step 2, introducing high-temperature steam into the first waste liquid to obtain second waste liquid; wherein the heating time is 50-60 min, and the water temperature is controlled to be 70-80 ℃;
step 3, introducing ozone into the second waste liquid to obtain a third waste liquid; wherein the concentration of ozone is controlled to be 100-120 mg/L, and the reaction time is 2 hours;
step 4, adding sodium hydroxide and calcium chloride into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid; wherein, adding sodium hydroxide, and controlling the pH value to be 9-10; the molar content of the added calcium chloride is 1.2 times of the molar content of the fluoride ions in the third waste liquid, namely the molar ratio of the calcium chloride to the fluoride ions is 1.2:1, the reaction time is 45min, and the content of the fluoride ions in the fourth waste liquid is less than or equal to 20mg/L;
step 5, adding sodium carbonate into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid; wherein, the molar content of sodium carbonate added into the fourth waste liquid is 2 times of the molar content of calcium and magnesium ions in the fourth waste liquid, namely the molar ratio of sodium carbonate to calcium and magnesium ions is 2:1, and the reaction time is 45min;
step 6, evaporating and crystallizing the fifth waste liquid to obtain condensate and concentrated solution;
and 7, lifting the condensate to an incinerator to serve as an incineration heat source, and lifting the concentrated solution to a curing workshop to serve as a curing thickener.
Examples
The invention provides a recycling method of high-heat-value wastewater in a hazardous waste plant, which comprises the following steps:
s1, adding a 40% sodium hydroxide reagent into high-heat-value wastewater of a hazardous waste plant with heat value of 4500cal/g, fluoride ion of 1200mg/L and calcium-magnesium ion of 1600mg/L, stirring by a stirrer, and regulating the pH value of the wastewater to 2-3 to obtain a first waste liquid;
s2, introducing 160 ℃ high-temperature steam provided by an incineration boiler into the first waste liquid, heating for 50-60 min, controlling the water temperature to be 70-80 ℃ so as to perform high-temperature thermal reaction, removing a waste water surfactant and inhibiting an electric double layer, so that oily matters wrapped on the surface of water drops in the first waste liquid are broken, and obtaining a second waste liquid;
s3, introducing ozone prepared by an ozone generator into the second waste liquid, controlling the ozone concentration to be 100-120 mg/L, performing oxidation reaction for 2 hours, decomposing macromolecular oil beads into small molecular oil beads by utilizing the strong oxidation property of hydroxyl radicals, and finally releasing oily matters wrapped inside the water beads in the waste liquid to obtain third waste liquid;
s4, firstly adding sodium hydroxide into the third waste liquid, and controlling the pH value to be 9-10; then adding a calcium chloride reagent to react with fluoride ions in the third waste liquid to generate calcium fluoride precipitates, wherein the content of the calcium chloride reagent is 1.2 times that of the fluoride ions in the third waste liquid, the reaction time is 45min, and the calcium fluoride residues and fourth waste liquid are respectively obtained through precipitation and filtration, and the content of the fluoride ions in the fourth waste liquid is less than or equal to 20mg/L;
s5, adding a sodium carbonate reagent into the fourth waste liquid, wherein the content of sodium carbonate is 2 times of the content of calcium and magnesium ions in the fourth waste liquid, reacting for 45min, enabling the sodium carbonate to react with the calcium and magnesium ions in the fourth waste liquid to generate calcium carbonate and magnesium hydroxide precipitates, and respectively obtaining calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid through precipitation and filtration, wherein the total hardness content in the fifth waste liquid is less than or equal to 100mg/L;
s6, carrying out evaporation crystallization of 'three-effect evaporation+single-effect evaporation' on the fifth waste liquid, heating the solution to enable water molecules and a large amount of low-boiling-point easily-burnt components in the solution to be evaporated and purified, concentrating, sticking and thickening the other part of the components which are not evaporated, so as to obtain condensate and concentrated solution, wherein the calorific value of the condensate after reaction is 2900cal/g;
s7, the obtained condensate is an easily incineratable component, so that the condensate is lifted to an incinerator to serve as an incineration heat source, and the incineration heat efficiency is improved; the obtained concentrated solution has higher viscosity and good accelerating effect on stabilization and solidification; thus, the concentrate is lifted to the curing shop as a curing thickener.
The invention has the advantages that:
the invention can separate the fluoride ions, calcium and magnesium hardness ions in the high heat value wastewater of the hazardous waste plant from the wastewater, thereby avoiding the problems of system corrosion, scaling and the like caused by directly feeding the high heat value wastewater into an incinerator for incineration; meanwhile, the easy-to-burn components in the high-heat-value wastewater are purified, so that the burning efficiency of a subsequent burning furnace is improved; the concentrated solution generated by the system can be used as a thickening agent required by a stabilizing and curing process of a curing workshop; realizes the multi-level utilization of the high-heat-value wastewater of the hazardous waste plant and improves the economic value of the high-heat-value wastewater.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A recycling method for high-heat-value wastewater of a hazardous waste plant is characterized by comprising the following steps:
pH adjustment is carried out on high-calorific-value wastewater of a hazardous waste plant to obtain first waste liquid;
introducing high-temperature steam into the first waste liquid to obtain second waste liquid;
ozone is introduced into the second waste liquid to obtain third waste liquid;
adding sodium hydroxide and calcium chloride into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid;
adding sodium carbonate into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid;
evaporating and crystallizing the fifth waste liquid to obtain condensate and concentrated solution;
and lifting the condensate to an incinerator to serve as an incineration heat source, and lifting the concentrated solution to a curing workshop to serve as a curing thickener.
2. The method for recycling high-heat-value wastewater of a hazardous waste plant according to claim 1, wherein the method is characterized in that the pH of the high-heat-value wastewater of the hazardous waste plant is adjusted to obtain a first waste liquid; comprising the following steps:
and adding sodium hydroxide into the high-calorific-value wastewater of the hazardous waste plant, and adjusting the pH to 2-3 to obtain the first waste liquid.
3. The method for recycling high-heat-value wastewater of a hazardous waste plant according to claim 1, wherein the method is characterized in that high-temperature steam is introduced into the first waste liquid to obtain a second waste liquid; comprising the following steps:
introducing high-temperature steam into the first waste liquid to perform high-temperature thermal reaction, so that oily matters wrapped on the surface of water drops in the first waste liquid are broken, and a second waste liquid is obtained; wherein the heating time is 50-60 min, and the water temperature is controlled to be 70-80 ℃.
4. The method for recycling high-calorific-value wastewater of a hazardous waste plant according to claim 1, wherein ozone is introduced into the second waste liquid to obtain a third waste liquid; comprising the following steps:
ozone is introduced into the second waste liquid to perform oxidation reaction, so that oily matters wrapped in water drops in the second waste liquid are released, and a third waste liquid is obtained; wherein the concentration of ozone is controlled to be 100-120 mg/L, and the reaction time is 2h.
5. The method for recycling high-calorific-value wastewater of hazardous waste plants according to claim 1, wherein sodium hydroxide and calcium chloride are added into the third waste liquid to obtain calcium fluoride slag and fourth waste liquid; comprising the following steps:
firstly adding sodium hydroxide into the third waste liquid, and controlling the pH value to be 9-10; then adding calcium chloride, enabling the calcium chloride to react with fluoride ions in the third waste liquid to generate calcium fluoride precipitates, and respectively obtaining calcium fluoride residues and fourth waste liquid through precipitation and filtration; wherein the molar content of the added calcium chloride is 1.2 times of the molar content of the fluoride ions in the third waste liquid, the reaction time is 45min, and the content of the fluoride ions in the fourth waste liquid is less than or equal to 20mg/L.
6. The recycling method of high-heat-value wastewater in hazardous waste plants according to claim 1, wherein sodium carbonate is added into the fourth waste liquid to obtain calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid; comprising the following steps:
adding sodium carbonate into the fourth waste liquid to react with calcium and magnesium ions in the fourth waste liquid to generate calcium carbonate and magnesium hydroxide precipitates, and respectively obtaining calcium carbonate slag, magnesium hydroxide slag and fifth waste liquid through precipitation and filtration; wherein, the molar content of sodium carbonate added into the fourth waste liquid is 2 times of the molar content of calcium and magnesium ions in the fourth waste liquid, and the reaction time is 45min.
7. The recycling method for high-heat-value wastewater of a hazardous waste plant according to any one of claims 1 to 6, wherein the heat value of the high-heat-value wastewater of the hazardous waste plant is more than or equal to 4000cal/g, the fluorine ion is more than or equal to 1000mg/L, and the calcium and magnesium ion are more than or equal to 1500mg/L.
8. The recycling method for high-heat-value wastewater of a hazardous waste plant according to any one of claims 1 to 6, wherein the high-temperature steam is incineration boiler steam.
9. The method for recycling high-calorific-value wastewater of a hazardous waste plant according to any one of claims 1 to 6, wherein the ozone is prepared by an ozone generator.
10. The recycling method for high-heat-value wastewater of a hazardous waste plant according to any one of claims 1-6, wherein the evaporation crystallization adopts a three-effect evaporation and single-effect evaporation process.
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