CN103304072A - Recycling method of industrial waste water - Google Patents
Recycling method of industrial waste water Download PDFInfo
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- CN103304072A CN103304072A CN2013102924300A CN201310292430A CN103304072A CN 103304072 A CN103304072 A CN 103304072A CN 2013102924300 A CN2013102924300 A CN 2013102924300A CN 201310292430 A CN201310292430 A CN 201310292430A CN 103304072 A CN103304072 A CN 103304072A
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- water
- waste water
- reverse osmosis
- calcium
- precipitation
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 239000010842 industrial wastewater Substances 0.000 title abstract 2
- 239000002351 wastewater Substances 0.000 claims abstract description 48
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000013049 sediment Substances 0.000 claims abstract description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 238000005189 flocculation Methods 0.000 claims description 14
- 230000016615 flocculation Effects 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 11
- 150000005323 carbonate salts Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 6
- 238000009287 sand filtration Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 3
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000004571 lime Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 238000007743 anodising Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- GCPRNIZDNTXQIX-NBPLQZBRSA-N 1-chloro-2-(2-chloroethylsulfanyl)ethane;dichloro-[(e)-3-chloroprop-2-enyl]arsane Chemical compound ClCCSCCCl.Cl\C=C\C[As](Cl)Cl GCPRNIZDNTXQIX-NBPLQZBRSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
Images
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- Separation Using Semi-Permeable Membranes (AREA)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a recycling method of industrial waste water. The recycling method is characterized in that alkali for neutralizing is used in aluminum anodizing waste water, precipitate of a sulfate system is generated, calcium ions in the waste water are fully reacted and sedimented by adding precipitator, the sediment is filtered and separated, calcium sulfate dissolved in waste water raw water is removed, and waste water recycling is conducted through a reverse osmosis system in the follow-up procedures. By means of the recycling method, the problem that a whole water production system fails due to the fact that a reverse osmosis film is blocked by a large amount of calcium sulfate is solved, a whole treatment process is continuous and reliable, management is simple, and operation is convenient.
Description
Technical field
The present invention relates to waste water treatment and reclamation and utilize technical field, relate to more specifically a kind of take sulfate system as main aluminum anode oxidized waste water treatment process.
Background technology
Aluminium shape surface per ton is processed in the aluminium section bar production process needs water 10～30m
3, therefrom produce a large amount of waste water.At present, treatment process generally is with alkali the acid in the waste water to be neutralized, and adds the rear pressure of flocculation agent formation precipitation slag, then with the clear water discharging, seldom puts into production use to reclaiming again after the wastewater treatment; Generally use in addition carbide slag (main effective constituent is calcium carbonate, calcium hydroxide and calcium oxide etc.) as neutralization alkali in the actual production, some existing recovery schemes use reverse osmosis membrane that waste water is reclaimed use, but lack the special processing to calcium sulfate in the waste water in the scheme, relatively a large amount of existence of calcium sulfate brings great burden to reverse osmosis membrane, in the situation that calcium sulfate exists existing scheme infeasible.Number be CN201120360002.3 such as Chinese patent application, denomination of invention is the advanced treatment system of alumilite process waste water, comprise: nanofiltration device, reverse osmosis unit and mixed bed device, described nanofiltration device is communicated with reverse osmosis unit by pipeline, described reverse osmosis unit is communicated with the mixed bed device by pipeline, and the connection between described nanofiltration device, reverse osmosis unit and the mixed bed device is by a plurality of valves and instrument control.By the way, the advanced treatment system of alumilite process waste water can reduce the cleaning frequency, and the reverse osmosis membrane life-span prolongs relatively.And for example Chinese patent application number is CN200920039070.2, a kind of aluminum oxidation wastewater treatment and middle water recycling device is characterized in that: it comprises that wastewater disposal basin, PH adjust pond, electric coagulation machine, electric coagulation machine outlet sump, micro-filtration concentration basin, microfiltration systems, reuse pool, reverse osmosis system, pure water storage tank, concentrated solution collecting tank and pressure filter; Wastewater disposal basin, PH adjustment pond, electric coagulation machine, electric coagulation machine outlet sump, micro-filtration concentration basin, microfiltration systems, reuse pool, reverse osmosis system, pure water storage tank are connected in series successively; Outlet links to each other with the import of concentrated solution collecting tank respectively one outlet of micro-filtration concentration basin with the electric coagulation machine scum silica frost, and the outlet of concentrated solution collecting tank links to each other with pressure filter, and Filter Press liquid links to each other with the wastewater disposal basin import.This patent structure can effectively be removed the waste water COD≤25mg/L after heavy metal in the waste water and salt make processing, can not cause because dropping into coagulating agent, flocculation agent the secondary pollution of reuse water.But, simple multi-medium filtering processing power is very limited, can't be except the ion in anhydrating, reverse osmosis treatment system mainly is the selection perviousness that relies on reverse osmosis membrane, can be except the most ions in anhydrating, but a large amount of existence of calcium sulfate can cause the obstruction of reverse osmosis membrane, cause whole water manufacturing system to lose efficacy.
Summary of the invention
Purpose of the present invention is exactly that a kind of technique that provides for the deficiency that solves prior art is simple, and wastewater recycle rate is high, prolongs the scavenging period of reverse osmosis membrane, so that the reuse method of the trade effluent that reverse osmosis system is used.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of alumilite process reuse of wastewater method, it is characterized in that, it is to use first neutralization alkali in alumilite process waste water, generate the sulfate system throw out, then by adding precipitation agent, make the abundant reaction precipitation of calcium ion and filtering separation in the waste water, remove the calcium sulfate that dissolves in the former water of waste water, follow-uply carry out waste water recycling with reverse osmosis system.
As further specifying of such scheme, its concrete steps comprise:
A, add calcium carbonate, calcium hydroxide or calcium oxide in the alumilite process waste water and carry out neutralization reaction as neutralization with alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through the settling tank precipitate and separate;
C, enter reverse osmosis system and make reuse water.
In described processing step b, the precipitation agent soluble carbonate salt adopts yellow soda ash.
In described processing step b, water is to pass into tube settler through the water after the flocculation sediment processing first to precipitate, press slag to process; Then, pass into the negative pressure water-absorbing tank, by the raw water pump pumping, be transported in the reaction tank through line mixer; In reaction tank, add the precipitation agent soluble carbonate salt again, remove the calcium sulfate that dissolves in the waste water, generate the more lime deposit of indissoluble, then pass through the inclined-plate clarifying basin precipitation process, send into again and carry out the flocculation sediment processing in the secondary flocculation basin; At last, send into again reverse osmosis system after sending in the clean water basin dilution.
In described processing step c, pass through the water of the precipitation process of step b, be first successively by behind sand filtration, charcoal filter, the Bag filter, enter again reverse osmosis system.
The beneficial effect that the present invention adopts above-mentioned technical solution to reach is:
The present invention adopts mainly for the former water of waste water take sulfate system as main, and uses calcium carbonate, calcium hydroxide or calcium oxide as neutralization alkali, and generation sulfate system throw out is dissolved with the waste water of more vitriol after the processing; By adding precipitation agent yellow soda ash, make the abundant reaction precipitation of calcium ion and filtering separation in the waste water, remove a large amount of calcium sulfate that dissolve in the former water of waste water; Have benefited from the removal of calcium sulfate, follow-uply used as the main waste water recycling process that carries out take reverse osmosis system, obtain through test, wastewater recycle rate of the present invention can reach 80%.
Description of drawings
Fig. 1 is process flow diagram of the present invention;
Fig. 2 is principle of operation figure of the present invention.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described in further detail.
As shown in Figure 1, the reuse method of a kind of trade effluent of the present invention, it is to use first neutralization alkali in alumilite process waste water, generate the sulfate system throw out, then by adding precipitation agent, make the abundant reaction precipitation of calcium ion and filtering separation in the waste water, remove the calcium sulfate that dissolves in the former water of waste water, follow-uply carry out waste water recycling with reverse osmosis system.
As shown in Figure 2, its concrete steps comprise:
A, add calcium carbonate, calcium hydroxide or calcium oxide in the alumilite process waste water and carry out neutralization reaction as neutralization with alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through the settling tank precipitate and separate;
C, enter reverse osmosis system and make reuse water.
In described processing step b, the precipitation agent soluble carbonate salt adopts yellow soda ash.
In described processing step b, water is to pass into tube settler through the water after the flocculation sediment processing first to precipitate, press slag to process; Then, pass into the negative pressure water-absorbing tank, by the raw water pump pumping, be transported in the reaction tank through line mixer; In reaction tank, add the precipitation agent soluble carbonate salt again, remove the calcium sulfate that dissolves in the waste water, generate the more lime deposit of indissoluble, then pass through the inclined-plate clarifying basin precipitation process, send into again and carry out the flocculation sediment processing in the secondary flocculation basin; At last, send into again reverse osmosis system after sending in the clean water basin dilution.
In described processing step c, pass through the water of the precipitation process of step b, be first successively by behind sand filtration, charcoal filter, the Bag filter, enter again reverse osmosis system.
Existing reverse osmosis water manufacturing system can not directly apply to the defined waste water of the present invention, mainly be since wherein a large amount of calcium sulfate precipitations can stop up the reverse osmosis membrane pipe, concrete reason is that calcium sulfate solubleness is higher under the normal temperature and pressure, solubleness such as following table under the normal pressure of calcium sulfate and calcium carbonate:
| ? | 0℃ | 10℃ | 20℃ | 30℃ | 40℃ |
| CaSO 4·2H 2O/g | 0.18 | 0.19 | 0.2 | 0.21 | 0.21 |
| CaCO 3/mg | 8.1 | 7.0 | 6.5 | 5.2 | 4.4 |
As can be seen from the above table, CaSO
42H
2O and CaCO
3Solubleness differs hundred times between the two, because the precipitation of calcium sulfate causes film blockage, reverse osmosis membrane to clean frequent, whole water manufacturing system and can't use, so need to before waste water advances reverse osmosis system most of calcium ion precipitation be removed with precipitation agent.
The present invention selects yellow soda ash as precipitation agent, and the chemical equation of itself and calcium sulfate is as follows:
CaSO
4+Na
2CO
3→CaCO
3↓+Na
2SO
4
Dissolubility data according to 20 ℃ of calcium sulfate and calcium carbonate can be calculated, to substantially remove the calcium sulfate that dissolves in the waste water in the time of 20 ℃, the theoretical usage quantity of yellow soda ash is 1.23g/L, in order to make its sufficient reacting and precipitation fully, must make yellow soda ash excessive, the actual amount of calcium carbonate should be more than theoretical consumption.
By the data of solubleness as can be known, fully concentrated 1m in theory
3Middle water can produce the above fouling of 2kg, and through the clear water behind the sedimentation and filtration, the amount that produces the precipitation fouling after concentrating is reduced to 6.5g, the advantage place of technical solution of the present invention that Here it is.
Above-described only is preferred implementation of the present invention, should be understood that, the present invention is mainly for the aluminum oxidation reuse of wastewater, the waste water that other sulphate contents are higher, use calcium carbonate, calcium hydroxide or calcium oxide as neutralization bases, and follow-up use reverse osmosis system water processed, should be change design direction of the present invention; The present invention is mainly for using in the carbide slag (main component is calcium carbonate, calcium hydroxide or calcium oxide) and the situation of sulfur acid waste water, use other calcium carbonate, calcium hydroxide or calcium oxide to use alkali as the material of main component as neutralizing, be used for and sulfur acid waste water, and follow-up use reverse osmosis system water processed, should be deformation program of the present invention; The present invention selects yellow soda ash as precipitation agent, uses other and the kin soluble carbonate salt of yellow soda ash as precipitation agent, should be deformation program of the present invention; The present invention selects the filter of sand filtration, carbon and bag type filtering, and the treatment process as removing before middle water behind the calcium sulfate enters reverse osmosis system as only using other filtrations and processing mode or not processing direct use reverse osmosis system water processed, should be deformation program of the present invention; For the person of ordinary skill of the art, under the prerequisite that does not break away from the invention design, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (5)
1. the reuse method of a trade effluent, it is characterized in that, it is to use first neutralization alkali in alumilite process waste water, generate the sulfate system throw out, then by adding precipitation agent, make the abundant reaction precipitation of calcium ion and filtering separation in the waste water, remove the calcium sulfate that dissolves in the former water of waste water, follow-uply carry out waste water recycling with reverse osmosis system.
2. the reuse method of a kind of trade effluent according to claim 1 is characterized in that, its concrete steps comprise:
A, add calcium carbonate, calcium hydroxide or calcium oxide in the alumilite process waste water and carry out neutralization reaction as neutralization with alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through the settling tank precipitate and separate;
C, enter reverse osmosis system and make reuse water.
3. the reuse method of a kind of trade effluent according to claim 2 is characterized in that, in described processing step b, the precipitation agent soluble carbonate salt adopts yellow soda ash.
4. the reuse method of a kind of trade effluent according to claim 2 is characterized in that, in described processing step b, water is to pass into tube settler through the water after the flocculation sediment processing first to precipitate, press slag to process; Then, pass into the negative pressure water-absorbing tank, by the raw water pump pumping, be transported in the reaction tank through line mixer; In reaction tank, add the precipitation agent soluble carbonate salt again, remove the calcium sulfate that dissolves in the waste water, generate the more lime deposit of indissoluble, then pass through the inclined-plate clarifying basin precipitation process, send into again and carry out the flocculation sediment processing in the secondary flocculation basin; At last, send into again reverse osmosis system after sending in the clean water basin dilution.
5. the reuse method of a kind of trade effluent according to claim 2 is characterized in that, in described processing step c, passes through the water of the precipitation process of step b, is first successively by behind sand filtration, charcoal filter, the Bag filter, enters reverse osmosis system again.
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|---|---|---|---|
| CN201310292430.0A CN103304072B (en) | 2013-07-11 | 2013-07-11 | Recycling method of industrial waste water |
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|---|---|---|---|
| CN201310292430.0A CN103304072B (en) | 2013-07-11 | 2013-07-11 | Recycling method of industrial waste water |
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Cited By (4)
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|---|---|---|---|---|
| CN105621741A (en) * | 2016-01-30 | 2016-06-01 | 内蒙古久科康瑞环保科技有限公司 | Novel integral softening and treating device for industrial wastewater with high salt content |
| CN107758913A (en) * | 2016-08-19 | 2018-03-06 | 宝山钢铁股份有限公司 | A kind of method and apparatus for removing total organic carbon in cold rolling acid waste water |
| CN109607880A (en) * | 2019-01-28 | 2019-04-12 | 杭州秀澈环保科技有限公司 | Applicable to the maintenance method of the separation membrane for the treatment of sulfate-containing wastewater |
| CN112429882A (en) * | 2020-12-03 | 2021-03-02 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
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Cited By (5)
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|---|---|---|---|---|
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| CN107758913A (en) * | 2016-08-19 | 2018-03-06 | 宝山钢铁股份有限公司 | A kind of method and apparatus for removing total organic carbon in cold rolling acid waste water |
| CN109607880A (en) * | 2019-01-28 | 2019-04-12 | 杭州秀澈环保科技有限公司 | Applicable to the maintenance method of the separation membrane for the treatment of sulfate-containing wastewater |
| CN112429882A (en) * | 2020-12-03 | 2021-03-02 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
| CN112429882B (en) * | 2020-12-03 | 2023-01-20 | 南宁市泽威尔饲料有限责任公司 | Method and device for treating ferrous fumarate wastewater |
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| Publication number | Publication date |
|---|---|
| CN103304072B (en) | 2014-10-15 |
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