CN108793498A - A kind of sulfate radical removal precipitating reagent circulation utilization method - Google Patents
A kind of sulfate radical removal precipitating reagent circulation utilization method Download PDFInfo
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- CN108793498A CN108793498A CN201810689891.4A CN201810689891A CN108793498A CN 108793498 A CN108793498 A CN 108793498A CN 201810689891 A CN201810689891 A CN 201810689891A CN 108793498 A CN108793498 A CN 108793498A
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- precipitating reagent
- calcium
- sulfate radical
- sulfate
- pond
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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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F2101/101—Sulfur compounds
Abstract
The present invention relates to a kind of sulfate radicals to remove precipitating reagent circulation utilization method, includes the following steps：(a) containing sulfate radicals waste water is passed through in sulphur removal pond (1), adding medicament A makes its reaction generate entringite precipitation, and muddy water mixed solution is added settle after flocculation aid A and is separated by solid-liquid separation, sediment A feeding precipitating reagent separate tanks (3)；(b) recovery catalyst B is added, reacts, adds flocculation aid B, is separated by solid-liquid separation, isolated sediment B, which is sent into sulphur removal pond (1), is used as sulfate precipitation agent reuse；Supernatant B enters induction crystallizing pond (4)；(c) medicament C is added, converts sulfate radical to gypsum deposition, part gypsum flows back into induction crystallizing pond (4) as induction crystal seed reuse, and supernatant C is supplemented into as the calcium source of sulfate radical removal in sulphur removal pond (1).Compared with prior art, the present invention realizes the Sources decreasing of sulfate radical precipitating sludge while reducing reagent cost.
Description
Technical field
The present invention relates to environmental protection and water resources rational use technical field more particularly to a kind of sulfate radical in waste water are heavy
Removal of forming sediment recycles new technology with precipitating reagent.
Background technology
In the production process of the industries such as petrochemical industry, printing and dyeing, electric power, pharmacy, the largely Industry Waste containing SO42- will produce
Water is referred to as containing sulfate radicals waste water.In recent years, the discharge capacity of containing sulfate radicals waste water is with the fast development of these industries and year by year
Increase.There is containing sulfate radicals waste water toxicity to destroy the ecological balance such as without processing direct emission meeting polluted-water environment.Waste water
In sulfate can be converted in a reduction state with toxicity and corrosive hydrogen sulfide, can be different degrees of in processing procedure
Ground influences the normal operation of sewage treatment equipment, facility, threatens the safety of operational management personnel.Under the High Concentration Situation, waste water
In sulfate radical permanent calcium scale can be also formed with calcium binding, cause the decline of equipment scaling and heat transfer efficiency.Therefore, it needs
The efficient minimizing technology of sulfate radical is developed to control its pollution.
Sulfate radical content in waste water can have very big difference because generating the difference of industry, not lead to processing method also not
Together.Currently, the method for processing containing sulfate radicals waste water mainly has membrane separation process, ion-exchange, Anaerobic biotreatment method both at home and abroad
Deng.But usually it is faced with that higher cost, operating difficulties, equipment material requirement be relatively stringent, desulfuration efficiency in actual application
With problems such as limitations.In the prior art, the entringite precipitation method are high with removal efficiency, cost is relatively low, equipment is simple
Many advantages, such as single easily operated, but exist and add the problems such as reagent cost is high, sediment yield is big, and the entringite face of alkalinity
Face dehydration and disposes the problem of outlet.
Therefore, the removal of exploitation sulfate radical in waste water entringite method precipitation and precipitating reagent recycle utilization, are reducing medicament
The Sources decreasing of sulfate radical precipitating sludge is realized while cost, being utilized with recycling sludge to containing sulfate radicals wastewater treatment has
Important practical value.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of removal of sulfate radical is heavy
Shallow lake agent circulation utilization method.
The purpose of the present invention can be achieved through the following technical solutions：A kind of sulfate radical removal precipitating reagent side of recycling
Method, which is characterized in that include the following steps：
(a) it will be passed through in sulphur removal pond (1) by pretreated containing sulfate radicals waste water, medicine is added by the first dosing tank (2)
Agent A makes its reaction generate entringite precipitation, and muddy water mixed solution is added to settle after flocculation aid A and is separated by solid-liquid separation, and supernatant A is discharged into
Subsequent cell carries out advanced treating or qualified discharge, and sediment A is sent into precipitating reagent separate tank (3) and carries out subsequent processing；
(b) recovery catalyst B is added into precipitating reagent separate tank (3) by the second dosing tank (5), brings it about reaction；Pass through
First helps solidifying dosing tank (6) to add flocculation aid B into precipitating reagent separate tank (3), makes its separation of solid and liquid, isolated sediment
B, which is sent into sulphur removal pond (1), is used as sulfate precipitation agent reuse；Supernatant B enters induction crystallizing pond (4) and is further processed；
(c) medicament C is added into induction crystallizing pond (4) by third dosing tank (7), converting sulfate radical to gypsum sinks
It forms sediment, part gypsum flows back into induction crystallizing pond (4) as crystal seed reuse is induced, and comprehensive utilization is transported outward after remaining gypsum dehydration；
Supernatant C is supplemented into as the calcium source of sulfate radical removal in sulphur removal pond (1).
The medicament A is the conventional dose that the entringite precipitation method use, and includes the compound of calcium salt and aluminium salt, adds
Amount is 0.01-20g/L.
The medicament A preferred calcium salts and aluminium salt in mass ratio 1:1~5 compound, wherein calcium salt include calcium chloride, nitre
Sour calcium, calcium chlorate, Calcium perchlorate, calcium bicarbonate or calcium dihydrogen phosphate, aluminium salt include aluminium chloride, aluminum sulfate or aluminum nitrate.
The flocculation aid A be polydimethyl diallyl ammonium chloride, polyacrylamide or the two compound, add
Amount is 0.01-1g/L.
The recovery catalyst B is the compound of hydrochloric acid, nitric acid or the two, dosage 0.01-10g/L.
The preferred hydrochloric acid of recovery catalyst B, nitric acid in mass ratio 1:1~5 compound.
The flocculation aid B be polydimethyl diallyl ammonium chloride, polyacrylamide or the two compound, add
Amount is 0.01-1g/L.
The medicament C is that calcium chloride, calcium oxide, calcium hydroxide, calcium carbonate, calcium bicarbonate are one such or several,
Its dosage is 0.01-10g/L.
Compared with prior art, the invention has the advantages that：
(1) it is removed for sulfate radical by recycling precipitating reagent in sulfate precipitation object, greatly reduces the precipitation in sulphur removal pond
Agent dosage, has both practicability and economy；
(2) entringite is converted by gypsum by crystallization conversion, the warp of sediment is promoted while sludge Sources decreasing
Ji value；
(3) the supernatant calcium sulfur ratio of entringite crystallization conversion process is apparently higher than raw water, can be used as aids precipitation agent reflux
It is removed for sulfate radical to sulphur removal pond, realizes being kept completely separate with recycling (i.e. truly for sewage and sludge
Zero-emission).
Description of the drawings
Fig. 1 is present invention process flow diagram；
In figure, 1- sulphur removal pond, the first dosing tanks of 2-, 3- precipitating reagent separate tanks, 4- induction crystallizing ponds, the second dosing tanks of 5-,
6- first helps solidifying dosing tank, 7- third dosing tanks.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
As shown in Figure 1, the removal of sulfate radical in waste water precipitation and precipitating reagent circulation utilization method, are as follows：
(1) containing sulfate radicals waste water is flowed into after pretreatment in the sulphur removal pond 1, and medicament A is added by the first dosing tank 2
Its reaction is set to generate entringite precipitation, muddy water mixed solution is added to settle after flocculation aid A and is separated by solid-liquid separation, and reaches sulfate radical
Purpose.Supernatant is discharged into subsequent cell and carries out advanced treating or qualified discharge, and sediment is sent into precipitating reagent separate tank 3.Institute
The medicament A stated is calcium chloride and aluminium chloride in mass ratio 1:2 compound；Input amount is 1g/L, and flocculation aid A is poly dimethyl two
Allyl ammonium chloride, dosage 1g/L；
(2) recovery catalyst B is added into precipitating reagent separate tank 3 by the second dosing tank 5, brings it about reaction；Pass through first
It helps solidifying dosing tank 6 to add flocculation aid into precipitating reagent separate tank 3, its separation of solid and liquid, isolated sediment is made to be sent into sulphur removal
Sulfate precipitation agent reuse is used as in pond 1；Supernatant enters induction crystallizing pond 4.The recovery catalyst B is hydrochloric acid, nitric acid by matter
Measure ratio 1:2 compound, dosage 1g/L.The flocculation aid B is polydimethyl diallyl ammonium chloride, dosage
For 1g/L.
(3) medicament C is added into induction crystallizing pond 4 by third dosing tank 7, converts sulfate radical to gypsum deposition, portion
Divide gypsum to flow back into induction crystallizing pond 4 as crystal seed reuse is induced, transports outward and comprehensively utilize after remaining gypsum dehydration；Supernatant is made
It is supplemented into sulphur removal pond 1 for the calcium source of sulfate radical removal.The medicament C is calcium chloride, dosage 1g/L.
In the present embodiment, power plant effluent containing sulfate radicals 4704mg/L.Sulfate radical is removed by the entringite precipitation method and is made
Treatment for reuse is carried out to precipitating sludge with precipitating reagent utilization process technology, flow recycles five times, and sulfate radical removal rate is successively
It is 98.9%, 93.2%, 91.3%, 95.1%, 91.9% and 92.6%.The precipitating reagent rate of recovery is followed successively by 91%, 72.9%,
72.3%, 84.3% and 82.9%.Compared with when not carrying out reuse to precipitating reagent, in turn reduce 82.2%, 67.8%,
72.2%, 75.5% and 85% precipitating reagent dosage.After third time circulating and recovering, technique overall operation effect tends to be steady
Fixed, precipitating reagent recycling rate of waterused is continuously improved, and dosage gradually decreases, and ton cost of water treatment reduces by 29.6 yuan.
Embodiment 2
Referring to embodiment 1, rubbish is burnt the specific steps of the removal of sulfate radical in waste water precipitation and precipitating reagent circulation utilization method
Burn factory nanofiltration concentrate containing sulfate radicals 5071mg/L.Sulfate radical is removed by the entringite precipitation method and is recycled using precipitating reagent
Technology carries out treatment for reuse to precipitating sludge, and flow recycles five times, sulfate radical removal rate is followed successively by 98.3%, 91.6%,
89.2%, 95.1% and 90.1%, 93.9%.The precipitating reagent rate of recovery is followed successively by 90.2%, 73.7%, 70.1%, 79.2 and
81.7%.It is compared when not carrying out reuse to precipitating reagent, in turn reduces 81.9%, 69.9%, 71.5%, 72.4% and 83.3%
Precipitating reagent dosage.After third time precipitating reagent circulating and recovering, technique overall operation effect tends towards stability, and precipitating reagent repeats profit
It is continuously improved with rate, dosage gradually decreases, and ton cost of water treatment reduces by 31.6 yuan.
Embodiment 3
The specific steps of the removal of sulfate radical in waste water precipitation and precipitating reagent circulation utilization method are referring to embodiment 1, coal chemical industry
Waste water containing sulfate radicals 2184mg/L.Sulfate radical is removed by the entringite precipitation method and uses precipitating reagent utilization process technology pair
Precipitating sludge carries out treatment for reuse, and flow recycles five times, sulfate radical removal rate is followed successively by 98.3%, 91.6%, 89.2%,
86.3%, 91.9% and 93.6%.The precipitating reagent rate of recovery is followed successively by 90.2%, 83.7%, 80.1%, 86.7% and 90.5%.
Compared with when not carrying out reuse to precipitating reagent, in turn reduce 81.7%, 68.8%, 65.9%, 73.8% and 87.4% it is heavy
Shallow lake agent dosage.After the 4th circulating and recovering, technique overall operation effect tends towards stability, and precipitating reagent recycling rate of waterused is continuous
It improves, dosage gradually decreases, and ton cost of water treatment reduces by 15.2 yuan.
Embodiment 4
Referring to embodiment 1, rubbish is burnt the specific steps of the removal of sulfate radical in waste water precipitation and precipitating reagent circulation utilization method
Burn the reverse osmosis waste water containing sulfate radicals 954.45mg/L of factory.Sulfate radical is removed by the entringite precipitation method and recycles profit using precipitating reagent
Treatment for reuse carried out to precipitating sludge with technology, flow recycles five times, sulfate radical removal rate is followed successively by 93.9%,
86.7%, 85.1%, 87.2% and 90.5%, 93.7%.The precipitating reagent rate of recovery is followed successively by 83.2%, 81.7%, 84.2%,
86.6% and 91.7%.Compared with when not carrying out reuse to precipitating reagent, in turn reduce 74.2%, 66.8%, 71.7%,
72.3% and 80.1% precipitating reagent dosage.After third time circulating and recovering, technique overall operation effect tends towards stability, and sinks
Agent recycling rate of waterused in shallow lake is continuously improved, and dosage gradually decreases, and ton cost of water treatment reduces by 6.3 yuan.
Embodiment 5
A kind of sulfate radical removal precipitating reagent circulation utilization method, includes the following steps：
(a) it will be passed through in sulphur removal pond (1) by pretreated containing sulfate radicals waste water, medicine is added by the first dosing tank (2)
Agent A makes its reaction generate entringite precipitation, and muddy water mixed solution is added to settle after flocculation aid A and is separated by solid-liquid separation, and supernatant A is discharged into
Subsequent cell carries out advanced treating or qualified discharge, and sediment A is sent into precipitating reagent separate tank (3) and carries out subsequent processing；It is described
Medicament A be calcium nitrate and aluminum nitrate in mass ratio 1:1 compound, dosage 0.01g/L.The flocculation aid A is
The compound of polydimethyl diallyl ammonium chloride, polyacrylamide or the two, dosage 0.01g/L.
(b) recovery catalyst B is added into precipitating reagent separate tank (3) by the second dosing tank (5), brings it about reaction；Pass through
First helps solidifying dosing tank (6) to add flocculation aid B into precipitating reagent separate tank (3), makes its separation of solid and liquid, isolated sediment
B, which is sent into sulphur removal pond (1), is used as sulfate precipitation agent reuse；Supernatant B enters induction crystallizing pond (4) and is further processed；
The recovery catalyst B is hydrochloric acid, nitric acid in mass ratio 1:1 compound, dosage 0.01g/L.The flocculation aid B is
Polydimethyl diallyl ammonium chloride, dosage 0.01g/L.
(c) medicament C is added into induction crystallizing pond (4) by third dosing tank (7), converting sulfate radical to gypsum sinks
It forms sediment, part gypsum flows back into induction crystallizing pond (4) as crystal seed reuse is induced, and comprehensive utilization is transported outward after remaining gypsum dehydration；
Supernatant C is supplemented into as the calcium source of sulfate radical removal in sulphur removal pond (1).The medicament C is calcium oxide, dosage
For 0.01g/L.
Embodiment 6
A kind of sulfate radical removal precipitating reagent circulation utilization method, includes the following steps：
(a) it will be passed through in sulphur removal pond (1) by pretreated containing sulfate radicals waste water, medicine is added by the first dosing tank (2)
Agent A makes its reaction generate entringite precipitation, and muddy water mixed solution is added to settle after flocculation aid A and is separated by solid-liquid separation, and supernatant A is discharged into
Subsequent cell carries out advanced treating or qualified discharge, and sediment A is sent into precipitating reagent separate tank (3) and carries out subsequent processing；It is described
Medicament A be calcium nitrate and aluminum nitrate in mass ratio 1:5 compound, dosage 20g/L.The flocculation aid A is poly-
Acrylamide, dosage 1g/L.
(b) recovery catalyst B is added into precipitating reagent separate tank (3) by the second dosing tank (5), brings it about reaction；Pass through
First helps solidifying dosing tank (6) to add flocculation aid B into precipitating reagent separate tank (3), makes its separation of solid and liquid, isolated sediment
B, which is sent into sulphur removal pond (1), is used as sulfate precipitation agent reuse；Supernatant B enters induction crystallizing pond (4) and is further processed；
The recovery catalyst B is hydrochloric acid, nitric acid in mass ratio 1:5 compound, dosage 10g/L.The flocculation aid B is poly-
Acrylamide, dosage 1g/L.
(c) medicament C is added into induction crystallizing pond (4) by third dosing tank (7), converting sulfate radical to gypsum sinks
It forms sediment, part gypsum flows back into induction crystallizing pond (4) as crystal seed reuse is induced, and comprehensive utilization is transported outward after remaining gypsum dehydration；
Supernatant C is supplemented into as the calcium source of sulfate radical removal in sulphur removal pond (1).The medicament C is calcium bicarbonate, is added
Amount is 10g/L.
Claims (8)
1. a kind of sulfate radical removes precipitating reagent circulation utilization method, which is characterized in that include the following steps：
(a) it will be passed through in sulphur removal pond (1) by pretreated containing sulfate radicals waste water, adding medicament A by the first dosing tank (2) makes
It, which is reacted, generates entringite precipitation, and muddy water mixed solution is added to settle after flocculation aid A and is separated by solid-liquid separation, and supernatant A is discharged into subsequently
Unit carries out advanced treating or qualified discharge, and sediment A is sent into precipitating reagent separate tank (3) and carries out subsequent processing；
(b) recovery catalyst B is added into precipitating reagent separate tank (3) by the second dosing tank (5), brings it about reaction；Pass through first
It helps solidifying dosing tank (6) to add flocculation aid B into precipitating reagent separate tank (3), its separation of solid and liquid, isolated sediment B is made to send
Enter and is used as sulfate precipitation agent reuse in sulphur removal pond (1)；Supernatant B enters induction crystallizing pond (4) and is further processed；
(c) medicament C is added into induction crystallizing pond (4) by third dosing tank (7), converts sulfate radical to gypsum deposition, portion
Divide gypsum to flow back into induction crystallizing pond (4) as crystal seed reuse is induced, transports outward and comprehensively utilize after remaining gypsum dehydration；Supernatant
C is supplemented into as the calcium source of sulfate radical removal in sulphur removal pond (1).
2. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that the medicine
Agent A is the conventional dose that the entringite precipitation method use, and includes the compound of calcium salt and aluminium salt, dosage 0.01-20g/L.
3. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that the medicine
Agent A preferred calcium salts and aluminium salt in mass ratio 1:1~5 compound, wherein calcium salt include calcium chloride, calcium nitrate, calcium chlorate, high chlorine
Sour calcium, calcium bicarbonate or calcium dihydrogen phosphate, aluminium salt include aluminium chloride, aluminum sulfate or aluminum nitrate.
4. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that described helps
Agent A is coagulated for polydimethyl diallyl ammonium chloride, the compound of polyacrylamide or the two, dosage 0.01-1g/L.
5. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that described returns
Receive the compound that agent B is hydrochloric acid, nitric acid or the two, dosage 0.01-10g/L.
6. a kind of sulfate radical according to claim 5 removes precipitating reagent circulation utilization method, which is characterized in that described returns
Receive the preferred hydrochloric acid of agent B, nitric acid in mass ratio 1:1~5 compound.
7. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that described helps
Agent B is coagulated for polydimethyl diallyl ammonium chloride, the compound of polyacrylamide or the two, dosage 0.01-1g/L.
8. a kind of sulfate radical according to claim 1 removes precipitating reagent circulation utilization method, which is characterized in that the medicine
Agent C is that calcium chloride, calcium oxide, calcium hydroxide, calcium carbonate, calcium bicarbonate are one such or several, dosage 0.01-
10g/L。
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| CN110590040A (en) * | 2019-09-30 | 2019-12-20 | 江苏源拓环境科技有限公司 | Wastewater treatment method and wastewater treatment system |
| CN110668540A (en) * | 2019-10-28 | 2020-01-10 | 上海电力大学 | High-salinity wastewater precipitation desalination recycling process |
| CN113461130A (en) * | 2021-07-14 | 2021-10-01 | 浙江大学 | Papermaking wastewater treatment method utilizing seed crystal mediated enhanced calcium precipitation |
| CN114275959A (en) * | 2021-12-29 | 2022-04-05 | 吉林省拓达环保设备工程有限公司 | Agent for removing high-concentration sulfate and nitrate in water and removing method and device |
| CN115784408A (en) * | 2022-08-31 | 2023-03-14 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization |
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| CN113461130A (en) * | 2021-07-14 | 2021-10-01 | 浙江大学 | Papermaking wastewater treatment method utilizing seed crystal mediated enhanced calcium precipitation |
| CN114275959A (en) * | 2021-12-29 | 2022-04-05 | 吉林省拓达环保设备工程有限公司 | Agent for removing high-concentration sulfate and nitrate in water and removing method and device |
| CN114275959B (en) * | 2021-12-29 | 2023-12-01 | 吉林省拓达环保设备工程有限公司 | Medicament for removing high-concentration sulfate and nitrate in water and removing method and device |
| CN115784408A (en) * | 2022-08-31 | 2023-03-14 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by using modified seed crystal for induced crystallization |
| CN115784408B (en) * | 2022-08-31 | 2023-09-12 | 哈尔滨工业大学 | Method for removing phosphorus, fluorine and heavy metals in wastewater by utilizing modified seed crystal induced crystallization |
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Application publication date: 20181113 |