CN111087094A - Method and device for treating coal gasification fluorine-containing wastewater - Google Patents
Method and device for treating coal gasification fluorine-containing wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 153
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 139
- 239000011737 fluorine Substances 0.000 title claims abstract description 139
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000003245 coal Substances 0.000 title claims abstract description 56
- 238000002309 gasification Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006115 defluorination reaction Methods 0.000 claims abstract description 129
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000011282 treatment Methods 0.000 claims abstract description 32
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 30
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000004891 communication Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 39
- 239000011575 calcium Substances 0.000 claims description 28
- 238000007599 discharging Methods 0.000 claims description 26
- 238000005086 pumping Methods 0.000 claims description 23
- 239000010865 sewage Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 16
- 238000010790 dilution Methods 0.000 claims description 16
- 239000012895 dilution Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- -1 fluoride ions Chemical class 0.000 description 22
- 208000028659 discharge Diseases 0.000 description 13
- 239000003085 diluting agent Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 3
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- 239000010842 industrial wastewater Substances 0.000 description 2
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- 206010016818 Fluorosis Diseases 0.000 description 1
- 208000035719 Maculopathy Diseases 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical group [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
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- 238000005345 coagulation Methods 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- 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
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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
- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention relates to a method and a device for treating coal gasification fluorine-containing wastewater. The device for treating the coal gasification fluorine-containing wastewater comprises a primary fluorine removal reaction tank, a fine fluorine removal reactor, a fine fluorine removal settling tank, a treating agent preparation tank, a calcium hydroxide preparation tank, a tubular filter, a clarifying tank, a coal gasification device washing water tank and related communication pipelines; the defects of long reaction time and high total cost of wastewater treatment in the prior art are overcome, and compared with a resin adsorption method, the method has the advantages that a precise filtration system is not required to be added, wastewater discharged by a coal gasification device can be directly subjected to defluorination treatment, and the flow is simple; the reaction time in the wastewater treatment process is short, and the treated wastewater can be flexibly adjusted and recycled according to the production requirements, so that the total amount of wastewater treatment is reduced, and the comprehensive cost of enterprise wastewater treatment is effectively reduced; the content of fluorinion in the treated wastewater is lower than 10ppm, which reaches the national first-class discharge standard.
Description
Technical Field
The invention relates to a method and a device for treating fluorine-containing wastewater, in particular to a method and a device for treating coal gasification fluorine-containing wastewater.
Background
At present, the fluorine-containing wastewater mainly comes from the industries of chemical industry, pesticide, exploitation of fluorine ore, production of downstream products, thermal power generation and the like. In recent years, rapid development of fluorine chemical industry and related industries leads the quantity of the fluorine-containing wastewater discharged per year to increase in ten thousand tons; in addition, the relatively backward wastewater treatment technology causes a large amount of fluorine-containing wastewater to be discharged to the water areas around the factory, and the long-term drinking of water with the content of fluoride ions of residents which does not reach the standard causes diseases such as maculopathy, renal dysfunction, fluorosis and the like, so that the physical and psychological health is seriously affected.
For the discharge of fluorine in wastewater, the highest concentration discharge standard is specified in the national standard GB 8978-. In order to reach the national standard, the fluorine-containing wastewater has some progress on the treatment method. The methods reported at present include adsorption, chemical precipitation, coagulation precipitation, electric flocculation, reverse osmosis, and biochemical methods.
TABLE 1 maximum permissible fluoride emission concentration in wastewater GB 8978-1996
The adsorption method is generally used for treating low-concentration (<30ppm) fluorine-containing wastewater, and has remarkable effect. However, the method ensures that the waste water has enough residence time in the adsorbent, so that the method is not suitable for the working condition of treating the waste water with larger total amount; the chemical precipitation method is suitable for the primary treatment of high-concentration (>100ppm) fluorine-containing wastewater, a large amount of solid waste can be generated as a byproduct after the treatment, secondary pollution can be caused due to improper treatment, and the total treatment cost of the wastewater is higher; the coagulating sedimentation method is only suitable for treating low-concentration fluorine-containing wastewater and is not used independently; the electric flocculation and reverse osmosis methods have high investment cost and complex operation; the biochemical method is suitable for organic industrial wastewater with low fluorine concentration and aims to reduce the toxicity of the wastewater, but the method has higher requirements on parameters such as pH, COD and the like of the wastewater.
For example, the research center of the fluorine engineering technology in Hubei province utilizes calcium hydroxide to carry out primary defluorination on wastewater produced by lithium hexafluorophosphate, so that the fluorine ions in the wastewater are reduced to about 20ppm-30ppm, and then a self-made mineralizer (the main component is an iron-aluminum composite reagent and rare earth elements are mixed according to a certain proportion) is adopted to further treat the wastewater, and the concentration of the fluorine ions in the treated wastewater can reach the first-level standard of sewage discharge (the fluorine content is less than or equal to 10 ppm). Combined addition of Ca (OH) by Zhonghe nuclear fuel element Limited company2And CaCl2The fluorine removal effect is good when the fluorine removal is carried out on the nuclear industrial wastewater, and the fluorine ions in the wastewater with high fluorine content can be reduced to be below 10 ppm. However, the two fluorine removal processes have the problems of high energy consumption, long reaction time and the like, and if the technology is directly applied to the fluorine treatment of the coal gasification wastewater, chloride ions are introduced into a coal gasification system to cause the corrosion of chlorine radicals of the device.
In foreign countries, the treatment of fluorine in wastewater is concentrated on adsorption processes. Among them, the well-known resin adsorption method of Dusheng Tulsion series manufactured by Dusheng Missi corporation holds a place in the international market. After the resin is used for defluorination, the minimum content of fluorine ions in the wastewater can reach below 1 ppm. However, the process method has high requirements for pretreatment of wastewater, especially SS (suspended solids) and total hardness in the wastewater, and the excessive SS and total hardness can cause the resin surface to be polluted quickly, the pore diameter to be blocked, the adsorption period of the resin to be shortened greatly and the adsorption effect to be poor. The process needs to be matched with a precise wastewater pretreatment system, and the cost of the pretreatment system accounts for a large proportion of the total construction cost.
Therefore, the invention provides a process technology which has the advantages of short reaction time, low energy consumption, high fluorine removal efficiency and lower total construction and operation cost of the device.
Disclosure of Invention
The invention aims to solve the defects of long reaction time and high total cost of wastewater treatment in the prior art, and provides a method and a device for treating coal gasification fluorine-containing wastewater, so that the content of fluorine ions in the treated wastewater is lower than 10ppm and the national first-level discharge standard is reached on the premise of reducing the reaction time and the total cost.
The technical scheme of the invention is as follows:
the coal gasification fluorine-containing wastewater treatment device is realized; comprises a primary defluorination reaction tank 2, a fine defluorination reactor 5, a fine defluorination settling tank 10, a treating agent preparation tank 9 (hereinafter referred to as YL preparation tank), a calcium hydroxide preparation tank 3, a tubular filter 14, a clarifying tank 8, a coal gasification device washing water tank 16 and related communication pipelines; the device is characterized in that a top outlet of a primary defluorination reaction tank 2 is communicated with a bottom inlet of a fine defluorination reactor 5 through a pipeline by a primary defluorination sewage pump 4, a top outlet of the fine defluorination reactor 5 is communicated with a bottom inlet of a fine defluorination settling tank 10 through a pipeline, a bottom outlet of the fine defluorination settling tank is connected with a middle inlet of the fine defluorination reactor 5 through a circulating pump 12 and a pipeline, one path of the top outlet of the fine defluorination settling tank is communicated with an inlet of a tubular filter 14 through a pipeline, and the other path of the top outlet of the fine defluorination settling tank is communicated with a sewage treatment plant; one path of the outlet of the tubular filter is connected with a washing water barrel 16 of the coal gasification device through a water production pipeline 15, the other path of the outlet is respectively communicated with the inlet of an YL preparation tank 9 and the inlet at the top of a calcium hydroxide preparation tank 3 through the water production pipeline, the outlet of the YL preparation tank 9 is respectively connected with the inlet at the top of the refined fluorine removal reactor 5 and the inlet at the top of the refined fluorine removal settling tank 10 through pipelines, and the outlet of the calcium hydroxide preparation tank 3 is connected with the inlet at the top of the primary fluorine removal reaction tank 2 after being converged through a pipeline and a fluorine-containing wastewater pipeline provided with a sewage pump 1 on the pipeline; the bottom outlet of the primary defluorination reaction tank 2, the bottom outlet of the fine defluorination reactor 5 and the concentrated solution outlet of the tubular filter 14 are respectively communicated with a primary defluorination crystal slurry pump 6, a fine defluorination crystal slurry pump 11 and a concentrated liquid slurry pump 17 through a crystal slurry pipeline 7 and a clarifying barrel.
The invention relates to a method for treating coal gasification fluorine-containing wastewater, which comprises the following steps:
(1) directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution at an inlet of the wastewater entering the tank, reacting for 5-10 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding a treating agent solution (YL treating agent for short) at the top end of the fine defluorination reactor, and stirring for reacting for 5-10 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the fluorine content of the effluent obtained by overflowing can reach the national standard requirement; adding YL treating agent solution intermittently at the top of the fine defluorination settling tank, and pumping bottom floccule to a fine defluorination reactor;
(5) and (3) directly discharging one part of effluent in the fine defluorination settling tank to a sewage treatment company in the plant area, filtering the other part of effluent by using a tubular filter, taking the produced water as the dilution of calcium hydroxide and YL or the washing water of the device, and discharging the concentrated solution into a clarifying barrel.
The adding amount of the saturated calcium hydroxide solution in the step (1) is 0.05-1.0% of the wastewater treatment amount.
The addition amount of the YL treating agent solution in the step (3) is 0.1-1.0% of the wastewater treatment amount; the composition of the YL treatment agent solution was: 10.0% of polyacrylamide, 20% of sodium polyacrylate and 70% of polyaluminium chloride;
the effluent in the fine defluorination settling tank in the step (4) is characterized in that: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 200ppm to 400 ppm.
The pore diameter of the tubular filter in the step (5) is 0.1um-20 um;
the water production is characterized in that: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 80ppm to 120 ppm.
The concrete description is as follows:
calcium hydroxide is added into the primary defluorination reaction tank and Ca is mainly utilized2+And F-Calcium fluoride precipitates are easily generated by reaction, and the concentration of F-ions in the wastewater is preliminarily reduced.
Adding an YL treating agent into the fine defluorination reactor, and defluorinating F-particles by 3 modes of adsorption, ion exchange and complexation by utilizing flocs generated by the YL treating agent in water.
The tubular filter is used for removing most insoluble solid impurities in the wastewater of the fine-removal fluorine settling tank.
The method has the following advantages:
(1) compared with a resin adsorption method, the method has the advantages that a precise filtering system is not required to be added, the wastewater discharged by the coal gasification device can be directly subjected to defluorination treatment, the process is simple, and finally the content of fluorine ions in the wastewater reaches the primary discharge standard in the national standard GB 8978-.
(2) The reaction time is short in the wastewater treatment process, the treated wastewater can be flexibly adjusted and recycled according to production needs, and the total amount of wastewater treatment is reduced, so that the comprehensive cost of enterprise wastewater treatment is effectively reduced.
Drawings
FIG. 1 is a schematic flow diagram of a method and an apparatus for treating coal gasification fluorine-containing wastewater according to the present invention.
Wherein: 1-sewage pump, 2-primary defluorination reaction tank, 3-calcium hydroxide preparation tank, 4-primary defluorination sewage pump, 5-fine defluorination reactor, 6-primary defluorination crystal slurry pump, 7-crystal slurry pipeline, 8-clarifying tank, 9-YL preparation tank, 10-fine defluorination settling tank, 11-fine defluorination crystal slurry pump, 12-circulating pump, 13-sewage treatment plant, 14-tubular filter, 15-water production pipeline, 16-coal gasification device water washing tank and 17-concentrated liquid crystal slurry pump.
Detailed Description
The present invention will be described in detail with reference to specific examples.
As shown in the attached drawings, the invention discloses a method and a device for treating coal gasification fluorine-containing wastewater, the fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
It comprises the following steps:
(1) directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution at an inlet of the wastewater entering the tank, reacting for 5-10 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
the addition amount of the saturated calcium hydroxide solution is 0.05-1.0% of the total amount of the wastewater.
(2) Pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
the wastewater subjected to preliminary fluorine removal is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 9-12, fluorine ion content: 30ppm-40ppm, total hardness (as Ca)2+Meter): 100ppm to 140 ppm.
(3) Continuously adding YL treating agent solution at the top end of the fine defluorination reactor, and stirring for reacting for 5-10 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
the addition amount of the YL treating agent solution is 0.1-1.0% of the total amount of the wastewater; the composition of the YL treatment agent solution was: 10.0% of polyacrylamide, 20% of sodium polyacrylate and 70% of polyaluminium chloride;
(4) and (4) settling the wastewater in the fine defluorination settling tank for half an hour again, and overflowing the obtained effluent. Adding YL treating agent solution intermittently at the top of the fine defluorination settling tank, and pumping bottom floccule to a fine defluorination reactor;
the effluent characteristic of the fine defluorination settling tank is as follows: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 200ppm to 400 ppm.
(5) And (3) directly discharging one part of effluent in the fine defluorination settling tank to a sewage treatment company in the plant area, filtering the other part of effluent by using a tubular filter, taking the produced water as the dilution of calcium hydroxide and YL or the washing water of the device, and discharging the concentrated solution into a clarifying barrel.
The pore diameter of the tubular filter is 0.1um-20 um;
the water production is characterized in that: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 80ppm to 120 ppm.
The invention discloses a method and a device for treating coal gasification fluorine-containing wastewater, which are shown in the attached drawing, and comprise a primary fluorine removal reaction tank 2, a fine fluorine removal reactor 5, a fine fluorine removal settling tank 10, an YL preparation tank 9, a calcium hydroxide preparation tank 3, a tubular filter 14, a clarifying tank 8, a coal gasification device water washing tank 16 and related communication pipelines; the device is characterized in that the top outlet of a primary defluorination reaction tank 2 is communicated with the bottom inlet of a fine defluorination reactor 5 through a pipeline and a primary defluorination sewage pump 4, the bottom inlet of a fine defluorination settling tank 10 is communicated with the top outlet of the fine defluorination reactor 5 through a pipeline, the bottom outlet of the fine defluorination settling tank is connected with the middle inlet of the fine defluorination reactor 5 through a circulating pump 12 and a pipeline, one path of the top outlet of the fine defluorination settling tank is communicated with the inlet of a tubular filter 14 through a pipeline, and the other path of the top outlet of the fine defluorination settling tank is communicated with a sewage treatment plant. The outlet of the tubular filter is connected with the top inlets of the YL preparation tank 9 and the calcium hydroxide preparation tank 3 through a water production pipeline 15, the outlet of the YL preparation tank 9 is connected with the top inlets of the fine defluorination reactor 5 and the fine defluorination settling tank 10 through pipelines, the outlet of the calcium hydroxide preparation tank 3 is converged with a fluorine-containing wastewater pipeline provided with a sewage pump 1 on the pipeline through a pipeline and then connected with the top inlet of the primary defluorination reaction tank, the outlet of the bottom of the primary defluorination reaction tank 2, the outlet of the bottom of the fine defluorination reactor 5 and the concentrated solution of the tubular filter 14 are respectively connected with the primary defluorination crystal pulp pump 6 through a crystal pulp pipeline 7, and the fine defluorination crystal pulp pump 11 and the concentrated liquid crystal pulp pump 17 are communicated with the clarifying barrel.
Example 1
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 0.05 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 5 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of YL treating agent solution to wastewater is 0.1%, and stirring for reaction for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) and (4) settling the wastewater in the fine defluorination settling tank for half an hour again, and overflowing the obtained effluent.
(5) Effluent in the fine defluorination settling tank is directly discharged to a sewage treatment company in a plant area, the other part of effluent is filtered by a 10-micron tubular filter, produced water is used as dilution of calcium hydroxide and YL or washing water of the device, and concentrated solution is discharged to a clarifying barrel.
The diluent of the calcium hydroxide in the step (1) and the diluent of the YL treatment agent in the step (3) come from primary water in a whole plant system.
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH is 9, and the content of fluorine ions is as follows: 38ppm, Total hardness (in Ca)2+Meter): 100ppm to 110 ppm;
the temperature of the effluent in the fine defluorination settling tank is 40-45 ℃, the pH value is 7.5, the content of fluorinion is 6.66-7.2 ppm, and the total hardness is Ca2+Calculated) is 340ppm to 380 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 7.5, and the content of fluorine ions is as follows: 6.5ppm-7.2ppm, total hardness (in Ca)2+Calculated) is 110ppm to 120 ppm.
Example 2
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 0.05 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 6 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of the YL treating agent solution to the wastewater is 1.0%, and stirring for reacting for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) and (4) settling the wastewater in the fine defluorination settling tank for half an hour again, and overflowing the obtained effluent.
(5) Effluent in the fine defluorination settling tank is directly discharged to a sewage treatment company in a plant area, the other part of effluent is filtered by a 10-micron tubular filter, produced water is used as dilution of calcium hydroxide and YL or washing water of the device, and concentrated solution is discharged to a clarifying barrel.
The diluent of the calcium hydroxide in the step (1) and the diluent of the YL treatment agent in the step (3) come from primary water in a whole plant system.
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH is 9, and the content of fluorine ions is as follows: 38ppm, Total hardness (in Ca)2+Meter): 100ppm to 110 ppm;
the temperature of the effluent in the fine defluorination settling tank is 40-45 ℃, the pH value is 6.5, the content of fluorinion is 0.6-0.9 ppm, and the total hardness is (by Ca)2+Calculated) is 360ppm to 390 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 6.5, and the content of fluorine ions is as follows: 0.6ppm to 0.9ppm, total hardness (in Ca)2+Calculated) is 117ppm to 120 ppm.
Example 3
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 0.06% of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 10 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of YL treating agent solution to wastewater is 0.4%, and stirring for reaction for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the obtained effluent is overflowed;
(5) and (3) discharging part of the effluent of the fine defluorination settling tank to a sewage treatment company in the plant area, passing the other part of the effluent through a 10-micron tubular filter, using the produced water as a diluent of calcium hydroxide and YL or washing water of the device, and discharging the concentrated solution to a clarifying barrel.
The dilution of calcium hydroxide in step (1) and the dilution of YL treatment agent in step (3) are derived from the water produced in step (5).
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH value is 10, and the content of fluorine ions is as follows: 35ppm, Total hardness (in Ca)2+Meter): 113ppm to 116 ppm;
the temperature of the effluent in the fine defluorination settling tank is 40-45 ℃, the pH value is 7.0, the content of fluorinion is 6.0-6.5 ppm, and the total hardness is (by Ca)2+Calculated) is 350ppm to 362 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 7.0, and the content of fluorine ions is as follows: 6.0ppm to 6.5ppm, total hardness (in Ca)2+Calculated) is 112ppm to 118 ppm.
Example 4
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 1.0 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 6 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of YL treating agent solution to wastewater is 0.12%, and stirring for reaction for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the obtained effluent is overflowed;
(5) and (3) discharging part of the effluent of the fine defluorination settling tank to a sewage treatment company in the plant area, passing the other part of the effluent through a 10-micron tubular filter, using the produced water as a diluent of calcium hydroxide and YL or washing water of the device, and discharging the concentrated solution to a clarifying barrel.
The dilution of calcium hydroxide in step (1) and the dilution of YL treatment agent in step (3) are derived from the water produced in step (5).
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH value is 12, and the content of fluorine ions is as follows: 30ppm, Total hardness (in Ca)2+Meter): 130ppm to 140 ppm;
the temperature of the effluent in the fine defluorination settling tank is 40-45 ℃, the pH value is 11, the content of fluorinion is 8.5-9.0 ppm, and the total hardness is Ca2+Based on the total weight of the crude oil) is 375ppm to 390 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH value is 11, and the content of fluorine ions is as follows: 8.5ppm to 9.0ppm, total hardness (in terms of Ca)2+Calculated) is 115ppm to 119 ppm.
Example 5
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 1.0 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 6 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of the YL treating agent solution to the wastewater is 1.0%, and stirring for reacting for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the obtained effluent is overflowed;
(5) and (3) directly discharging one part of the effluent of the fine defluorination settling tank to a sewage treatment company in the plant area, passing the other part of the effluent through a 20-micron tubular filter, producing water serving as a diluent of calcium hydroxide and YL or washing water of the device, and discharging the concentrated solution to a clarifying barrel.
The dilution of calcium hydroxide in step (1) and the dilution of YL treatment agent in step (3) are derived from the water produced in step (5).
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH value is 12, and the content of fluorine ions is as follows: 30ppm, Total hardness (in Ca)2+Meter): 130ppm to 140 ppm;
the temperature of the effluent of the fine defluorination settling tank is 40-45 ℃, the pH value is 8.2, the content of fluorinion is 1.2-1.6 ppm, and the total hardness is (by Ca)2+Calculated) is 380ppm to 400 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 8.2, and the content of fluorine ions is as follows: 1.2ppm to 1.6ppm, total hardness (in Ca)2+Calculated) is 118ppm to 120 ppm.
Example 6
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 1.0 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 6 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of the YL treating agent solution to the wastewater is 1.0%, and stirring for reacting for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the obtained effluent is overflowed;
(5) and (3) directly discharging one part of the effluent of the fine defluorination settling tank to a sewage treatment company in the plant area, passing the other part of the effluent through a 0.1um tubular filter, using the produced water as a dilution of calcium hydroxide and YL or washing water of the device, and discharging the concentrated solution into a clarifying barrel.
The dilution of calcium hydroxide in step (1) and the dilution of YL treatment agent in step (3) are derived from the water produced in step (5).
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH value is 12, and the content of fluorine ions is as follows: 30ppm, Total hardness (in Ca)2+Meter): 130ppm to 140 ppm;
the temperature of the effluent of the fine defluorination settling tank is 40-45 ℃, the pH value is 8.2, the content of fluorinion is 1.2-1.6 ppm, and the total hardness is (by Ca)2+Calculated) is 380ppm to 400 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 8.2, and the content of fluorine ions is as follows: 1.2ppm to 1.6ppm, total hardness (in Ca)2+Calculated) is 85ppm to 88 ppm.
Example 7
The fluorine-containing wastewater is mixed wastewater discharged by two shell-plate furnaces of a coal gasification device, and the wastewater is characterized in that: temperature: 40 ℃ to 50 ℃, pH: 6-7, fluorine ion content: 100-2+Meter): 120ppm-160ppm, total mixed discharge amount of 40m3/h；
(1) Directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution accounting for 1.0 percent of the mass of the wastewater at an inlet of the wastewater into the tank, reacting for 6 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding YL treating agent solution (composed of 10.0% polyacrylamide, 20% sodium polyacrylate and 70% polyaluminium chloride) at the top of the fine defluorination reactor, wherein the mass ratio of the YL treating agent solution to the wastewater is 1.0%, and stirring for reacting for 6 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the obtained effluent is overflowed;
(5) and (3) discharging part of the effluent of the fine defluorination settling tank to a sewage treatment company in the plant area, passing the other part of the effluent through a 10-micron tubular filter, using the produced water as a diluent of calcium hydroxide and YL or washing water of the device, and discharging the concentrated solution to a clarifying barrel.
The dilution of calcium hydroxide in step (1) and the dilution of YL treatment agent in step (3) are derived from the water produced in step (5).
Through detection: the temperature of the wastewater subjected to preliminary fluorine removal is 40-50 ℃, the pH value is 12, and the content of fluorine ions is as follows: 30ppm, Total hardness (in Ca)2+Meter): 130ppm to 140 ppm;
the temperature of the effluent of the fine defluorination settling tank is 40-45 ℃, the pH value is 8.2, the content of fluorinion is 1.2-1.6 ppm, and the total hardness is (by Ca)2+Calculated) is 380ppm to 400 ppm;
the temperature of the produced water after passing through the tubular filter is 40-45 ℃, the pH is 8.2, and the content of fluorine ions is as follows: 1.2ppm to 1.6ppm, total hardness (in Ca)2+Calculated) is 92ppm to 98 ppm.
Claims (6)
1. A method for treating coal gasification fluorine-containing wastewater is characterized by comprising the following steps:
(1) directly pumping fluorine-containing wastewater discharged by a coal gasification device into a primary defluorination reaction tank, adding a saturated calcium hydroxide solution at an inlet of the wastewater entering the tank, reacting for 5-10 minutes, and overflowing after the reaction to obtain primary defluorination wastewater;
(2) pumping the wastewater subjected to primary fluorine removal to the bottom of a fine fluorine removal reactor, and returning crystal slurry at the bottom of a reaction tank to a clarifying barrel matched with a coal gasification device;
(3) continuously adding a treating agent solution (YL treating agent for short) at the top end of the fine defluorination reactor, and stirring for reacting for 5-10 minutes; conveying reaction overflow liquid from the side part of the reactor to the bottom of a fine fluorine removal settling tank, and periodically discharging floccules at the bottom of the fine fluorine removal reactor into a clarifying barrel;
(4) the wastewater entering the fine defluorination settling tank is settled for half an hour again, and the fluorine content of the effluent obtained by overflowing can reach the national standard requirement; adding YL treating agent solution intermittently at the top of the fine defluorination settling tank, and pumping bottom floccule to a fine defluorination reactor;
(5) and (3) directly discharging one part of effluent in the fine defluorination settling tank to a sewage treatment company in the plant area, filtering the other part of effluent by using a tubular filter, taking the produced water as the dilution of calcium hydroxide and YL or the washing water of the device, and discharging the concentrated solution into a clarifying barrel.
2. The method for treating coal gasification fluorine-containing wastewater according to claim 1, characterized in that: the adding amount of the saturated calcium hydroxide solution in the step (1) is 0.05-1.0% of the total amount of the wastewater.
3. The method for treating coal gasification fluorine-containing wastewater according to claim 1, characterized in that: the addition amount of the YL treating agent solution in the step (3) is 0.1-1.0% of the wastewater treatment amount; the composition of the YL treatment agent solution was: 10.0% of polyacrylamide, 20% of sodium polyacrylate and 70% of polyaluminium chloride.
4. The method for treating coal gasification wastewater containing fluorine according to claim 1, wherein the effluent of the fine defluorination settling tank in the step (4) is characterized in that: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 200ppm to 400 ppm.
5. The method for treating coal gasification wastewater containing fluorine according to claim 1, wherein the pore size of the tubular filter in the step (5) is 0.1um to 20 um; the water production is characterized in that: temperature 40-45 ℃, pH: 6.5-11, fluorine ion content: 0.6ppm to 9ppm, total hardness (in terms of Ca)2+Meter): 80ppm to 120 ppm.
6. The method and the device for treating the coal gasification fluorine-containing wastewater realize the method of claim 1: comprises a primary defluorination reaction tank (2), a fine defluorination reactor (5), a fine defluorination settling tank (10), a treating agent preparation tank (9) (hereinafter referred to as YL preparation tank), a calcium hydroxide preparation tank (3), a tubular filter (14), a clarifying tank (8), a coal gasification device washing water tank (16) and related communication pipelines; the device is characterized in that a top outlet of a primary defluorination reaction tank (2) is communicated with a bottom inlet of a fine defluorination reactor (5) through a pipeline by a primary defluorination sewage pump (4), a top outlet of the fine defluorination reactor (5) is communicated with a bottom inlet of a fine defluorination settling tank (10) through a pipeline, a bottom outlet of the fine defluorination settling tank is connected with a middle inlet of the fine defluorination reactor (5) through a circulating pump (12) and a pipeline, one path of the top outlet of the fine defluorination settling tank is communicated with an inlet of a tubular filter (14) through a pipeline, and the other path of the top outlet of the fine defluorination settling tank is communicated with a sewage treatment plant (13); one path of an outlet of the tubular filter is connected with a washing water barrel (16) of the coal gasification device through a water production pipeline (15), the other path of the outlet is respectively communicated with an inlet of an YL preparation tank (9) and an inlet at the top of a calcium hydroxide preparation tank (3) through the water production pipeline, an outlet of the YL preparation tank (9) is respectively connected with an inlet at the top of the fine defluorination reactor (5) and an inlet at the top of the fine defluorination settling tank (10) through pipelines, and an outlet of the calcium hydroxide preparation tank (3) is connected with an inlet at the top of the primary defluorination reaction tank (2) after being converged with a fluorine-containing waste water pipeline provided with a sewage pump (1) on the pipeline through a pipeline; the bottom outlet of the primary defluorination reaction tank (2), the bottom outlet of the fine defluorination reactor (5) and the concentrated solution outlet of the tubular filter (14) are respectively communicated with a primary defluorination crystal slurry pump (6), a fine defluorination crystal slurry pump (11) and a concentrated liquid slurry pump (17) through crystal slurry pipelines (7) and a clarifying barrel.
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| US20140161714A1 (en) * | 2012-12-08 | 2014-06-12 | Beijing Guohuan Tsinghua Environment Engineering Design & Research Institute Co., Ltd. | Process for recovery of fluoride from wastewater produced in crystalline silicon solar cell manufacturing |
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| CN202038939U (en) * | 2011-05-19 | 2011-11-16 | 山东昭和新材料科技股份有限公司 | Fluorine-contained wastewater treatment system |
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