CN103304072B - Recycling method of industrial waste water - Google Patents
Recycling method of industrial waste water Download PDFInfo
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- CN103304072B CN103304072B CN201310292430.0A CN201310292430A CN103304072B CN 103304072 B CN103304072 B CN 103304072B CN 201310292430 A CN201310292430 A CN 201310292430A CN 103304072 B CN103304072 B CN 103304072B
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- waste water
- water
- reverse osmosis
- calcium
- precipitation
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 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 39
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 36
- 230000008569 process Effects 0.000 claims abstract description 21
- 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 5
- 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 22
- 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 13
- 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
- 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
- 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
- 238000007743 anodising Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 8
- 239000000243 solution 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
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution 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
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 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
- 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
- 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
Landscapes
- 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 taking sulfate system as main aluminum anode oxidized waste water treatment process.
Background technology
In aluminium section bar production process, aluminium shape surface processing per ton needs water 10～30m
3, therefrom produce a large amount of waste water.At present, treatment process is generally with alkali, the acid in waste water to be neutralized, and presses slag after adding flocculation agent to form precipitation, then clear water is discharged, seldom to reclaiming again and put into production use after wastewater treatment; In actual production, generally use in addition carbide slag (main effective constituent is calcium carbonate, calcium hydroxide and calcium oxide etc.) as neutralization alkali, some existing recovery schemes use reverse osmosis membrane to reclaim use to waste water, but in scheme, lack the special processing to calcium sulfate in waste water, the a large amount of existence relatively of calcium sulfate brought great burden to reverse osmosis membrane, and in the situation that calcium sulfate exists, existing scheme is infeasible.If Chinese Patent Application No. is CN201120360002.3, 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 mixed bed device by pipeline, and the connection between described nanofiltration device, reverse osmosis unit and mixed bed device is by multiple 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 extends relatively.And for example Chinese Patent Application No. 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 is connected with the import of concentrated solution collecting tank respectively one outlet of micro-filtration concentration basin with electric coagulation machine scum silica frost, and the outlet of concentrated solution collecting tank is connected with pressure filter, and Filter Press liquid is connected with wastewater disposal basin import.Heavy metal and salt that this patent structure can effectively be removed in waste water make waste water COD≤25mg/L after treatment, can not cause because of input coagulating agent, flocculation agent the secondary pollution of reuse water.But, simple multi-medium filtering processing power is very limited, cannot be except the ion in anhydrating, reverse osmosis treatment system is mainly 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
Object of the present invention is exactly the deficiency in order to solve prior art and a kind of technique of providing is simple, and wastewater recycle rate is high, extends the scavenging period of reverse osmosis membrane, so that the reuse method of the trade effluent that reverse osmosis system is applied.
The present invention adopts following technical solution to realize above-mentioned purpose: a kind of reuse method of alumilite process waste water, it is characterized in that, it is first in alumilite process waste water, to use neutralization alkali, generate sulfate system throw out, then by adding precipitation agent, make the abundant reaction precipitation of calcium ion filtering separation in waste water, remove the calcium sulfate dissolving in the former water of waste water, follow-uply carry out waste water recycling with reverse osmosis system.
As further illustrating of such scheme, its concrete steps comprise:
A, carry out neutralization reaction toward adding calcium carbonate, calcium hydroxide or calcium oxide in alumilite process waste water as neutralization alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through settling tank precipitate and separate;
C, enter reverse osmosis system and make reuse water.
In described processing step b, precipitation agent soluble carbonate salt adopts sodium carbonate.
In described processing step b, water is first to pass into tube settler through flocculation sediment water after treatment to precipitate, press slag processing; Then, pass into negative pressure water-absorbing tank, by raw water pump pumping, be transported in reaction tank through line mixer; In reaction tank, add precipitation agent soluble carbonate salt again, remove the calcium sulfate dissolving in waste water, generate the more lime deposit of indissoluble, then pass through inclined-plate clarifying basin precipitation process, then send into and in secondary flocculation basin, carry out flocculation sediment processing; Finally, send in clean water basin and send into again reverse osmosis system after dilution.
In described processing step c, the water of the precipitation process of process step b, is first successively by after sand filtration, charcoal filter, Bag filter, then enters 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 taking 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 processing; By adding precipitation agent sodium carbonate, make the abundant reaction precipitation of calcium ion filtering separation in 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 applied as the main waste water recycling process carrying out taking reverse osmosis system, obtain through test, wastewater recycle rate of the present invention can reach 80%.
Brief description of the 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 first in alumilite process waste water, to use neutralization alkali, generate sulfate system throw out, then by adding precipitation agent, make the abundant reaction precipitation of calcium ion filtering separation in waste water, remove the calcium sulfate dissolving 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, carry out neutralization reaction toward adding calcium carbonate, calcium hydroxide or calcium oxide in alumilite process waste water as neutralization alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through settling tank precipitate and separate;
C, enter reverse osmosis system and make reuse water.
In described processing step b, precipitation agent soluble carbonate salt adopts sodium carbonate.
In described processing step b, water is first to pass into tube settler through flocculation sediment water after treatment to precipitate, press slag processing; Then, pass into negative pressure water-absorbing tank, by raw water pump pumping, be transported in reaction tank through line mixer; In reaction tank, add precipitation agent soluble carbonate salt again, remove the calcium sulfate dissolving in waste water, generate the more lime deposit of indissoluble, then pass through inclined-plate clarifying basin precipitation process, then send into and in secondary flocculation basin, carry out flocculation sediment processing; Finally, send in clean water basin and send into again reverse osmosis system after dilution.
In described processing step c, the water of the precipitation process of process step b, is first successively by after sand filtration, charcoal filter, Bag filter, then enters reverse osmosis system.
Existing reverse osmosis water manufacturing system can not directly apply to the defined waste water of the present invention, mainly can stop up reverse osmosis membrane pipe due to a large amount of calcium sulfate precipitations wherein, concrete reason is that under normal temperature and pressure, calcium sulfate solubleness is higher, and under the normal pressure of calcium sulfate and calcium carbonate, solubleness is as following table:
| ? | 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
3between the two, solubleness differs hundred times, because the precipitation of calcium sulfate causes film blockage, reverse osmosis membrane to clean frequent, whole water manufacturing system and cannot use, so need to most of calcium ion precipitation be removed before waste water enters reverse osmosis system with precipitation agent.
The present invention selects sodium carbonate 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 DEG C of calcium sulfate and calcium carbonate can be calculated, 20 DEG C time, to substantially remove the calcium sulfate dissolving in waste water, the theoretical usage quantity of sodium carbonate is 1.23g/L, in order to make its sufficient reacting and precipitation completely, must make sodium carbonate excessive, the actual amount of calcium carbonate should be more than theoretical consumption.
From the data of solubleness, completely concentrated 1m in theory
3middle water, can produce fouling more than 2kg, and clear water after sedimentation and filtration, the amount that produces precipitation fouling after concentrated is reduced to 6.5g, the advantage place of technical solution of the present invention that Here it is.
Above-described is only the preferred embodiment of the present invention, should be understood that, the present invention is mainly for the reuse of aluminum oxidation waste water, 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 carbide slag (main component is calcium carbonate, calcium hydroxide or calcium oxide) and the situation of sulfur acid waste water, use material that other calcium carbonate, calcium hydroxide or calcium oxide are main component as neutralization alkali, 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 sodium carbonate as precipitation agent, uses other and the kin soluble carbonate salt of sodium carbonate as precipitation agent, should be deformation program of the present invention; The present invention selects sand filtration, carbon filter and bag type filtering, enters the treatment process before reverse osmosis system as the middle water of removing after calcium sulfate, as only used 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, without departing from the concept of the premise of the invention, can also make some distortion and improvement, these all belong to protection scope of the present invention.
Claims (1)
1. the reuse method of a trade effluent; it is characterized in that; it is first in alumilite process waste water, to use neutralization alkali; generate sulfate system throw out; then by adding precipitation agent; make the abundant reaction precipitation of calcium ion filtering separation in waste water, remove the calcium sulfate dissolving in the former water of waste water, follow-uply carry out waste water recycling with reverse osmosis system; Its concrete steps comprise:
A, carry out neutralization reaction toward adding calcium carbonate, calcium hydroxide or calcium oxide in alumilite process waste water as neutralization alkali;
B, add flocculation agent polyacrylamide solution and precipitation agent soluble carbonate salt successively, through settling tank precipitate and separate; First pass into tube settler through flocculation sediment water after treatment and precipitate, press slag processing; Then, pass into negative pressure water-absorbing tank, by raw water pump pumping, be transported in reaction tank through line mixer; In reaction tank, add precipitation agent soluble carbonate salt again, remove the calcium sulfate dissolving in waste water, generate the more lime deposit of indissoluble, then pass through inclined-plate clarifying basin precipitation process, send into again in secondary flocculation basin and carry out flocculation sediment processing, send in clean water basin and dilute;
C, enter reverse osmosis system and make reuse water.
2
.the reuse method of a kind of trade effluent according to claim 1, is characterized in that, in described processing step b, precipitation agent soluble carbonate salt adopts sodium carbonate.
3
.the reuse method of a kind of trade effluent according to claim 1, is characterized in that, in described processing step c, the water of the precipitation process of process step b, is first successively by after sand filtration, charcoal filter, Bag filter, then enters reverse osmosis system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310292430.0A CN103304072B (en) | 2013-07-11 | 2013-07-11 | Recycling method of industrial waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310292430.0A CN103304072B (en) | 2013-07-11 | 2013-07-11 | Recycling method of industrial waste water |
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| Publication Number | Publication Date |
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| CN103304072A CN103304072A (en) | 2013-09-18 |
| CN103304072B true CN103304072B (en) | 2014-10-15 |
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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 |
| 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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| JPS50124467A (en) * | 1974-02-27 | 1975-09-30 | ||
| CN100411988C (en) * | 2005-09-23 | 2008-08-20 | 清华大学 | Calcium removal and purification method for industrial potassium chloride |
| CN100429157C (en) * | 2005-10-31 | 2008-10-29 | 中国石油化工股份有限公司 | Method for treating ammonia nitrogen wastewater |
| WO2009121123A1 (en) * | 2008-04-01 | 2009-10-08 | Ultimate Nominees Pty Ltd | Non-toxic liquids for water treatment |
| CN101353210B (en) * | 2008-09-22 | 2011-05-04 | 华南理工大学 | Method for processing aluminum section bar chromizing waste water with calcium sulfite type desulphurization mortar |
| CN101717162A (en) * | 2009-12-02 | 2010-06-02 | 厦门世达膜科技有限公司 | Method for treating and recycling wastewater generated by processing surface of aluminum profile |
| CN201785261U (en) * | 2009-12-31 | 2011-04-06 | 上海轻工业研究所有限公司 | Treatment and recovery device for aluminum oxidation rinsing wastewater |
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Address after: 528231 Guangdong city of Foshan province caobian Dali Town Nanhai District Industrial Zone Third prosperous road No. 2 two Patentee after: FOSHAN CITY JILIDA ALUMINUM TECHNOLOGY CO.,LTD. Address before: 528231 Guangdong province Dali Nanhai District of Foshan City, Cao edge industrial zone three new Wai Road No. 19 Patentee before: Foshan City Kyrgyzstan Lida aluminum auxiliary material Ltd. Address after: 528231 Guangdong province Dali Nanhai District of Foshan City, Cao edge industrial zone three new Wai Road No. 19 Patentee after: Foshan City Kyrgyzstan Lida aluminum auxiliary material Ltd. Address before: 528231 Guangdong Province, Foshan City Nanhai Dali Taiping stone Buyi Patentee before: Foshan Nanhai District Dali Jilida Aluminum Auxiliary Material Factory |
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Effective date of registration: 20200618 Address after: 528200 Dali town industrial area, Nanhai District, Foshan, Guangdong Patentee after: FOSHAN NANHAI DALI DATONG JINWEI ALUMINUM INDUSTRY Co.,Ltd. Address before: 528231 Guangdong city of Foshan province caobian Dali Town Nanhai District Industrial Zone Third prosperous road No. 2 two Patentee before: FOSHAN CITY JILIDA ALUMINUM TECHNOLOGY Co.,Ltd. |
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