CN109987747A - A kind of photovoltaic wastewater inorganic agent and its processing equipment and processing method - Google Patents
A kind of photovoltaic wastewater inorganic agent and its processing equipment and processing method Download PDFInfo
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- CN109987747A CN109987747A CN201910316285.2A CN201910316285A CN109987747A CN 109987747 A CN109987747 A CN 109987747A CN 201910316285 A CN201910316285 A CN 201910316285A CN 109987747 A CN109987747 A CN 109987747A
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- photovoltaic
- photovoltaic wastewater
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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
- 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
- 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
- C02F1/66—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention discloses a kind of photovoltaic wastewater inorganic agent and its processing equipments and processing method, belong to fluorine containing waste water processing technology field.Photovoltaic wastewater inorganic agent of the invention, it is as the main component with fluorine removal particle, defluorinating agent, sodium hydroxide and hydrochloric acid, wastewater treatment is carried out by integrated photovoltaic wastewater processing equipment.Each component synergistic effect solves the problems, such as that calcium fluoride particles precipitating is difficult in traditional calcium salt precipitation method, and be discharged F- concentration to drop to 10mg/L or less.It significantly reduces water outlet F- concentration, improve precipitated product settling property, strengthen defluorination effect.It is high to precipitate obtained solid Calcium Fluoride Content, can recycle, reduce cost for wastewater treatment, reduces enterprise to prevention and treatment water environment pollution cost input, improves economic benefit.Compared with the traditional handicraft of photovoltaic industry, improve work efficiency, flexible operation and convenient for management, convenient for promote.
Description
Technical field
The present invention relates to for fluoride waste in photovoltaic industry inorganic agent and its application, and in particular to a kind of photovoltaic wastewater
Inorganic agent and its processing equipment and processing method, belong to fluorine containing waste water processing technology field.
Background technique
The fast development of photovoltaic industry largely alleviates air pollution, but ring is also given in the production of photovoltaic device simultaneously
Border brings new problem, cleaning and silicon wafer, silicon rod preparation process in, ground in cutting, grinding, slice and silicon wafer
The auxiliary agent waste liquid and cleaning waste water generated during mill, burn into polishing etc., therefore can generate largely containing F-, SS, higher COD and
The waste water such as TN.
F in fluoride waste before the processing of photovoltaic industry-Concentration is generally all in 200mg/L or more, average annual total release
Reach tons up to ten thousand, it is serious to cause environmental pollution.The fluoride waste of high concentration usually requires to carry out multistage fluorine removal processing ability
Reach the industrial wastewater discharge standard limited value of GB8978-1996 " integrated wastewater discharge standard ".At the photovoltaic wastewater of the prior art
Reason method mainly has a chemical precipitation method and crystallisation, and chemical precipitation method has many advantages, such as technical maturity, low in cost, but at existing
Water outlet F after reason-The disadvantages of concentration is higher, body refuse sedimentation is slow and sludge solid waste yield is big；Although crystallisation can recycle money
Source, but there is a problem of that crystal growth is slow.
The fluorine-containing sludge main component that photovoltaic enterprise generates is CaF2、CaCO3、Ca(OH)2、CaSO4、SiO2And sandstone
Equal impurity, it is most to be stored by the way of concentrating stacking.Fluorine-containing sludge calorific value is low, general it is not recommended that incineration disposal is used, if association
Then there is corrosivity risk with disposition, general incineration disposal unit is refused actively to receive；There is also risks for landfill stabilization, are filling
Fluoride leaching concentration in environment is more than 100mg/L, disposes qualification to having inorganic fluoride waste (HW32) at present
The construction condition of hazardous waste landfill and to enter field condition high, is in addition influenced by business licence, can dispose the unit of HW32
Few, landfill stabilization is not optimal disposal options.At present both at home and abroad fluorine-containing sludge processing method mainly have landfill method and
Comprehensive use.Due to being limited by its hazard property, fluorine-containing sludge is utilized on a small quantity by collaboration or disposition, majority are finally filled
Or it is in stockpiling state, it has nowhere to go.Fluoride waste generates a large amount of fluorine-containing sludge through processing, wherein calcirm-fluoride account for 40% with
On, there is alternative natural fluorite ore after purification very high market to exploit potentialities.It must be combined in industrialization promotion
The compatibility of the operability of technology, economic feasibility and environment, becomes the critical issue of calcium fluoride sludge recycling.
Therefore, it turns harm into good using the Treatment process of photovoltaic wastewater, develops a kind of photovoltaic wastewater inorganic agent and processing unit,
F in photovoltaic wastewater is able to solve while recycling calcium fluoride sludge-, SS and COD pollutant concentration is high, treatment effeciency is low etc. asks
Topic has important practical significance to ecological environmental protection and photovoltaic industry sustainable development is promoted.
Summary of the invention
In view of the deficienciess of the prior art, the object of the present invention is to provide a kind of photovoltaic wastewater inorganic agents and its processing to set
Standby and processing method to recycle calcirm-fluoride mud (Calcium Fluoride Content >=80%) as target, while solving fluorine ion in photovoltaic wastewater
The problems such as concentration is high, SS and COD pollutant is higher, energy consumption is high, treatment effeciency is low.
Above-mentioned technical purpose of the invention technical scheme is that, a kind of photovoltaic wastewater inorganic agent,
It is made of following raw materials, the number is parts by weight:
The defluorinating agent is calcium chloride and calcium hydroxide, and the fluorine removal particle is calcium fluoride particles, and the hydrochloric acid is dense
Degree is 35~37%.
Preferably, a kind of photovoltaic wastewater inorganic agent, is made of following raw materials, and the number is parts by weight:
A kind of photovoltaic wastewater processing equipment carrying out photovoltaic wastewater processing using above-mentioned photovoltaic wastewater inorganic agent, including it is interior
Cylinder, outer cylinder, baffle and agitating paddle, the inner barrel and outer barrel are cylinder, and outer cylinder is placed on the outside of inner cylinder, outer cylinder it is upper it is following
Respectively lower than inner cylinder is upper following, and the following of the following and inner cylinder of outer cylinder connects into cone；Inner cylinder lower part is equipped with and outer cylinder
The opening that lower part communicates, the top of inner cylinder are equipped with waste water inlet and medicament inlet, and inner cylinder bottom is equipped with precipitating outlet, outer cylinder outside
Top is set there are two water outlet；Baffle is equipped between inner barrel and outer barrel, baffle is sludge strainer, is equipped with agitating paddle inside inner cylinder.
In treatment process, waste water and inorganic agent enter inner cylinder from waste water inlet and medicament inlet respectively, in the work of agitating paddle
It is reacted under, the water after reaction flows through the opening that inner cylinder lower part is communicated with outer cylinder lower part and enters outer cylinder.Into the water of outer cylinder
Stream under the action of the baffle, is separated by solid-liquid separation, and the water outlet outflow that supernatant is arranged from outer cylinder outer upper, sludge enters dress
Bottom set portion, from precipitating outlet discharge, circular treatment completes photovoltaic wastewater treatment process.
It is a kind of using above-mentioned photovoltaic wastewater inorganic agent and the photovoltaic wastewater processing method of photovoltaic wastewater processing equipment, including with
Lower step:
A) photovoltaic wastewater after the progress pH adjusting in collecting-tank is sent into photovoltaic wastewater processing equipment from waste water inlet
In inner cylinder, the fluorine removal particle calcium fluoride particles of proportional quantity are added from medicament inlet to inner cylinder；
B) sodium hydrate aqueous solution, defluorinating agent calcium chloride and hydrogen-oxygen of proportional quantity is added into photovoltaic wastewater from medicament inlet
Change the stirring collaboration processing of calcium aqueous solution, stir to after being completely dissolved, with sodium hydrate aqueous solution or salt acid for adjusting pH to 8.5~
9.0, continue to stir；After separation of solid and liquid, supernatant and fluorine-containing precipitating respectively enter next step processing links；
C) after being separated by solid-liquid separation, fluorine-containing precipitating is taken, after dense fluorine waste water adjusting pH to 3.0~3.5 is added, hydrogen is reused after stirring
Aqueous solution of sodium oxide carries out pH and is adjusted to 8.5~9.0；
D) it is separated by solid-liquid separation again through the baffle in outer cylinder after precipitating, detects be fluorinated in supernatant fluorine content and solid respectively
Calcium content；
E) it by b) and d) fluorine content supernatant up to standard is discharged by water outlet in step, carries out disinfection place into filter tank
Reason detects rear discharge up to standard；Precipitating mud is segregated into sludge-tank by precipitating outlet and carries out filters pressing, finally obtains sludge bulking；It presses
After normal flow running, inorganic agent, circular treatment are added into equipment by batch processed amount.
Preferably, pH is adjusted in collecting-tank described in the step a), adjusts pH to 8.5~9.0.
Preferably, sodium hydrate aqueous solution input amount is the 20% of overall reaction volume in the step b), and hydrochloric acid is total anti-
Answer the 10% of volume.
Preferably, calcium chloride and calcium hydroxide mass ratio are 1:10 in defluorinating agent in the step b).
Preferably, in the step b) and treatment process c) in photovoltaic wastewater processing equipment mixing speed be 100~
400r/min, mixing time are 10~60min.
Preferably, it in the step c), after the stirring in photovoltaic wastewater processing equipment stops, standing sewage and stops 5
~60min.
Preferably, in the step e), fluorine content detection is reduced to 10mg/L, and the following are water outlets up to standard.
In conclusion the invention has the following advantages:
(1) it solves the problems, such as that calcium fluoride particles precipitating is difficult in traditional calcium salt precipitation method, and is discharged F-Concentration can also drop
To 10mg/L or less；Significantly reduce water outlet F-Concentration improves precipitated product settling property, strengthens defluorination effect；Precipitating gained
Solid fluorinated calcium content is high, can recycle, and reduces cost for wastewater treatment, reduces enterprise to prevention and treatment water environment pollution cost
Investment, improves economic benefit.
(2) simultaneously by photovoltaic industry waste water dilute fluorine waste water and concentrated base waste water collaboration processing, dense fluorine waste water and soda acid give up
Content is higher after water collaboration processing and the calcirm-fluoride drying being finally settled out, and can replace fluorite ore as industrial application.
(3) present invention is handled using integrated processor, easy to use, compared with the traditional handicraft of photovoltaic industry, is mentioned
High working efficiency, flexible operation and convenient for management, convenient for promoting.
Detailed description of the invention
Fig. 1 is photovoltaic wastewater processing equipment structural schematic diagram of the invention.
Fig. 2 is photovoltaic wastewater processing method process flow chart of the present invention.
In figure: 1, inner cylinder, 2, outer cylinder, 3, baffle, 4, agitating paddle, 5, waste water inlet, 6, medicament inlet, 7, water outlet, 8,
Precipitating outlet.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention, specifically
Embodiment does not limit the present invention.
Embodiment 1
A kind of photovoltaic wastewater inorganic agent, is made of following raw materials, and the number is parts by weight:
The concentration of hydrochloric acid is 35~37%.
A kind of photovoltaic wastewater processing equipment carrying out photovoltaic wastewater processing using above-mentioned photovoltaic wastewater inorganic agent, including inner cylinder
1, outer cylinder 2, baffle 3 and agitating paddle 4, the inner cylinder 1 and outer cylinder 2 are cylinder, and outer cylinder 2 is placed on 1 outside of inner cylinder, outer cylinder 2
Upper following to divide equally upper not following lower than inner cylinder 1, and the following of the following and inner cylinder 1 of outer cylinder 2 connects into cone；Under inner cylinder 1
Portion is equipped with the opening communicated with 2 lower part of outer cylinder, and the top of inner cylinder 1 is equipped with waste water inlet 5 and medicament inlet 6, and 1 bottom of inner cylinder is equipped with
Precipitating outlet 8,2 outer upper of outer cylinder is set there are two water outlet 7；Baffle 3 is equipped between inner cylinder 1 and outer cylinder 2, baffle is sludge filtering
Net is separated by solid-liquid separation, and agitating paddle 4 is equipped with inside inner cylinder 1.
In treatment process, waste water and inorganic agent enter inside inner cylinder 1 from waste water inlet 5 and medicament inlet 6 respectively, are stirring
It is reacted under the action of paddle 4, the water after reaction flows through the opening that 1 lower part of inner cylinder is communicated with 2 lower part of outer cylinder and enters outer cylinder 2.Into
Enter the water flow of outer cylinder 2 under the action of baffle 3, be separated by solid-liquid separation, the water outlet 7 that supernatant is arranged from outer cylinder outer upper flows
Out, sludge enters bottom of device, and from 8 discharge of precipitating outlet, circular treatment completes photovoltaic wastewater processing.
A kind of photovoltaic wastewater processing method using above-mentioned photovoltaic wastewater inorganic agent, comprising the following steps:
A) photovoltaic wastewater after pH is adjusted to 8.5~9.0 will be carried out in collecting-tank be sent into photovoltaic wastewater from waste water inlet
In processing equipment inner cylinder, the fluorine removal particle calcium fluoride particles of proportional quantity are added from medicament inlet to inner cylinder；
B) sodium hydrate aqueous solution, defluorinating agent calcium chloride and hydrogen-oxygen of proportional quantity is added into photovoltaic wastewater from medicament inlet
Change the stirring collaboration processing of calcium aqueous solution, stir to after being completely dissolved, with sodium hydrate aqueous solution or salt acid for adjusting pH to 8.5~
9.0, continue to stir；After separation of solid and liquid, supernatant and fluorine-containing precipitating respectively enter next step processing links；Wherein chlorine in defluorinating agent
Change calcium and calcium hydroxide mass ratio is 1:10；Mixing speed is 100~400r/min, and mixing time is 10~60min；
C) after being separated by solid-liquid separation, fluorine-containing precipitating is taken, after dense fluorine waste water adjusting pH to 3.0~3.5 is added, hydrogen is reused after stirring
Aqueous solution of sodium oxide carries out pH and is adjusted to 8.5~9.0；Mixing speed is 100~400r/min, and mixing time is 10~60min,
After stirring stops, standing sewage and stop 5~60min；
D) it is separated by solid-liquid separation again through the baffle in outer cylinder after precipitating, detects be fluorinated in supernatant fluorine content and solid respectively
Calcium content；
E) it by b) and d) fluorine content supernatant up to standard is discharged by water outlet in step, carries out disinfection place into filter tank
Reason detects rear discharge up to standard, and the detection of supernatant fluorine content is reduced to 10mg/L, and the following are water outlets up to standard.Mud is precipitated by being settled out
Mouth is segregated into sludge-tank and carries out filters pressing, finally obtains sludge bulking.After being operated by normal flow, by batch processed amount into equipment
Inorganic agent is added, is recycled.
Embodiment 2
A kind of photovoltaic wastewater inorganic agent, is made of following raw materials, and the number is parts by weight:
The concentration of hydrochloric acid is 35~37%.
It handles application apparatus and processing method with embodiment 1.
Embodiment 3
A kind of photovoltaic wastewater inorganic agent, is made of following raw materials, and the number is parts by weight:
The concentration of hydrochloric acid is 35~37%.
It handles application apparatus and processing method with embodiment 1.
Comparative example 1
Calcium chloride is not only had to, other are the same as embodiment 1.
Comparative example 2
Calcium hydroxide is not only had to, other are the same as embodiment 2.
Comparative example 3
Calcirm-fluoride is not only had to, other are the same as embodiment 2.
To Examples 1 to 3 and comparative example 1~3, treated after calcium fluoride sludge carried out Calcium Fluoride Content detection, processing
Water outlet has carried out main water quality parameter detection, such as F-, COD, ammonia nitrogen and total phosphorus content, as a result and index comparison is such as the following table 1 and 2 institutes
Show.
1 calcium fluoride containing sludge detection data of table
| Batch | Coloration | Calcium Fluoride Content (detects) after drying |
| Embodiment 1 | White | 90.1% |
| Embodiment 2 | White | 92.3% |
| Embodiment 3 | White | 88.9% |
| Comparative example 1 | White | 82.1% |
| Comparative example 2 | White | 85.3% |
| Comparative example 3 | White | 70.2% |
The treatment effect of the inorganic agent of the invention of table 2 and its technique to photovoltaic wastewater
The stability that inorganic agent of the invention handles photovoltaic wastewater it can be seen from the above results is preferable, so that mainly
Pollutant F-, COD, ammonia nitrogen and total phosphorus content be remarkably decreased, while having significant effect to the processing of pH and conductivity.This
The inorganic agent of invention has effects that very significantly to handle for photovoltaic wastewater, and indices reach national regulation discharge mark
Standard, preparation method is simple, simplifies processing equipment, has high economic benefit.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of photovoltaic wastewater inorganic agent, it is characterised in that be made of the raw material of following portions by weight:
The defluorinating agent is calcium chloride and calcium hydroxide, and the fluorine removal particle is calcium fluoride particles, and the concentration of hydrochloric acid is
35~37%.
2. a kind of photovoltaic wastewater inorganic agent as described in claim 1, it is characterised in that be made of the raw material of following portions by weight:
3. a kind of photovoltaic wastewater processing for carrying out photovoltaic wastewater processing using photovoltaic wastewater inorganic agent described in claim 1 is set
It is standby, including inner cylinder, outer cylinder, baffle and agitating paddle, it is characterised in that: the inner barrel and outer barrel is cylinder, and outer cylinder is placed on interior
Cylinder outside, outer cylinder it is upper it is following divide equally upper not following lower than inner cylinder, and the following of the following and inner cylinder of outer cylinder connects into cone
Body；Inner cylinder lower part is equipped with the opening communicated with outer cylinder lower part, and the top of inner cylinder is equipped with waste water inlet and medicament inlet, inner cylinder bottom
It is exported equipped with precipitating, outer cylinder outer upper is set there are two water outlet；Baffle is equipped between inner barrel and outer barrel, baffle is sludge filtering
Net is separated by solid-liquid separation, and agitating paddle is equipped with inside inner cylinder.
4. a kind of utilize photovoltaic wastewater inorganic agent described in claim 1 and photovoltaic wastewater processing equipment as claimed in claim 3
Photovoltaic wastewater processing method, it is characterised in that the following steps are included:
A) photovoltaic wastewater after the progress pH adjusting in collecting-tank is sent into the inner cylinder of photovoltaic wastewater processing equipment from waste water inlet
In, the fluorine removal particle calcium fluoride particles of proportional quantity are added from medicament inlet to inner cylinder；
B) sodium hydrate aqueous solution, defluorinating agent calcium chloride and calcium hydroxide of proportional quantity is added into photovoltaic wastewater from medicament inlet
Aqueous solution stirs collaboration processing, stirs to after being completely dissolved, with sodium hydrate aqueous solution or salt acid for adjusting pH to 8.5~9.0, after
Continuous stirring；After separation of solid and liquid, supernatant and fluorine-containing precipitating respectively enter next step processing links；
C) after being separated by solid-liquid separation, fluorine-containing precipitating is taken, after dense fluorine waste water adjusting pH to 3.0~3.5 is added, hydroxide is reused after stirring
Sodium water solution carries out pH and is adjusted to 8.5~9.0；
D) it is separated by solid-liquid separation again through the baffle in outer cylinder after precipitating, detects calcirm-fluoride in supernatant fluorine content and solid respectively and contain
Amount；
E) it by b) and d) fluorine content supernatant up to standard is discharged by water outlet in step, carries out disinfection processing, examines into filter tank
Survey rear discharge up to standard；Precipitating mud is segregated into sludge-tank by precipitating outlet and carries out filters pressing, finally obtains sludge bulking；By normal stream
After Cheng Yunzuo, inorganic agent, circular treatment are added into equipment by batch processed amount.
5. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: in collecting-tank described in step a)
PH is adjusted, and adjusts pH to 8.5~9.0.
6. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: sodium hydrate aqueous solution in step b)
Input amount is the 20% of overall reaction volume, and hydrochloric acid is the 10% of overall reaction volume.
7. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: calcium chloride in defluorinating agent in step b)
It is 1:10 with calcium hydroxide mass ratio.
8. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: in step b) and treatment process c)
Mixing speed is 100~400r/min in photovoltaic wastewater processing equipment, and mixing time is 10~60min.
9. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: in step c), at photovoltaic wastewater
After managing the stirring stopping in equipment, stands sewage and stop 5~60min.
10. a kind of photovoltaic wastewater processing method as claimed in claim 4, it is characterised in that: in step e), fluorine content detection drop
It is low that for 10mg/L, the following are water outlets up to standard.
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| CN111717969A (en) * | 2020-05-29 | 2020-09-29 | 苏州乔发环保科技股份有限公司 | A deposit and divide salt device for strong brine waste water |
| CN113912212A (en) * | 2021-10-18 | 2022-01-11 | 江苏南大华兴环保科技股份公司 | Recovery reaction device, recovery device and recovery process for sand-like cryolite in fluorine-containing wastewater |
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| CN113912212A (en) * | 2021-10-18 | 2022-01-11 | 江苏南大华兴环保科技股份公司 | Recovery reaction device, recovery device and recovery process for sand-like cryolite in fluorine-containing wastewater |
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Application publication date: 20190709 |