CN101928088A - Method for treating reverse osmosis concentrated water of petrochemical enterprises - Google Patents
Method for treating reverse osmosis concentrated water of petrochemical enterprises Download PDFInfo
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- CN101928088A CN101928088A CN2009100877811A CN200910087781A CN101928088A CN 101928088 A CN101928088 A CN 101928088A CN 2009100877811 A CN2009100877811 A CN 2009100877811A CN 200910087781 A CN200910087781 A CN 200910087781A CN 101928088 A CN101928088 A CN 101928088A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000001728 nano-filtration Methods 0.000 claims abstract description 54
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 238000001471 micro-filtration Methods 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000013535 sea water Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012510 hollow fiber Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000247 postprecipitation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 2
- 238000005188 flotation Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for treating reverse osmosis concentrated water. Aiming at the water quality characteristic of the reverse osmosis concentrated water of petrochemical enterprises, treatment processes of nanofiltration, alkalinity adjustment, air flotation for magnesium removal, calcium removal, microfiltration, neutralization, reverse osmosis, multiple-effect evaporation and desiccation are adopted. Producing water obtained by treatment can return to a previous-level reverse osmosis system to be recycled; and residue obtained in the treatment process can be treated in a centralized mode. The method reduces the membrane pollution of the reverse osmosis, improves treatment efficiency, reduces overall operating cost and has obvious social benefit and economic benefit; and the recovery rate of water reaches about 95 percent.
Description
Technical field
The present invention relates to a kind of processing method of industrial waste water, especially relate to a kind of advanced treatment and reclamation method of reverse osmosis concentrated water of petrochemical enterprises.
Background technology
In recent years, along with the fast development of industries such as China's chemical industry, metallurgy, reverse osmosis is substitution ion exchange and electrodialysis desalination technology gradually, becomes the one preferred technique of waste water recycling process field.Reverse-osmosis treated can produce the dense water more than 30%, and salinity, the hardness of this strand reverse osmosis concentrated water are higher, directly discharges serious environment pollution, and causes the waste of water resources.
In order to make full use of water resources, reduce the influence of high salt, high hard waste water to environment, need effectively administer reverse osmosis concentrated water, thoroughly remove wherein salinity and hardness.Economical, remove salinity and hardness in the reverse osmosis concentrated water effectively, become the key issue of reverse osmosis technology in using.
Remove the hardness in the waste water, generally adopt physics and chemistry to remove hard method.At present, conventional water softening method has the softening and ion exchange method of lime, though these methods are widely used, all has some shortcomings.Lime softening method, limited to the removal of hardness ions, water outlet generally more than 20mg/L (with CaCO
3Meter), effluent quality is wayward; The ion exchange softening method needs frequent regeneration, consumes a large amount of regenerators, the regenerative wastewater contaminate environment of generation.
Nanofiltration is as a kind of pressure-driven membrane process between reverse osmosis and ultrafiltration, have that working pressure is low, concentrated water discharge is few, effluent quality is excellent, simple to operate, advantage such as level of automation is high, floor space is little, overcome the shortcoming of lime softening method and ion exchange softening method, so the nanofiltration membrane tenderizer has very strong competitive power in removing hard technology.The working cost and the ion exchange method of nanofiltration are suitable, if add the wastewater treatment expense that ion-exchange produces, the working cost of nano filtering process is lower than ion exchange method, and it is economically viable therefore adopting nanofiltration tenderizer substitutional ion exchange tenderizer.
In the prior art, foreign patent US035278 has developed " (NF) → reverse osmosis (SWRO) → multistage flash evaporation (MSF) is softened in nanofiltration " sea water desaltination novel process.Seawater has been removed the hardness more than 80% after the NF pre-treatment, TDS has descended about 40%, and removed all organic pollutants, thereby improved the rate of recovery of SWRO, the concentrated seawater of SWRO process is handled via MSF again, obtain fresh water, the rate of recovery of whole process can be brought up to about 90%.It is obvious that this technology is used for the sea water desaltination treatment effect, and nanofiltration can effectively reduce the processing water yield of reverse osmosis seawater desalting as the pre-treatment of reverse osmosis, improves the cycles of concentration of reverse osmosis system.
Summary of the invention
The water quality characteristics of, high salt hard at the reverse osmosis concentrated water of petrochemical enterprises height, the invention provides a kind of concentrated drying method, improve the recovery utilization rate (the water rate of recovery of whole process reaches about 95%) of water resources, avoid the discharging of reverse osmosis concentrated water, and the salinity in the waste water is converted into solid-state, be convenient to ultimate disposal.
Treatment process of the present invention is achieved in that
A kind of treatment process of reverse osmosis concentrated water, the pH of described reverse osmosis concentrated water is 7.0～10.0, specific conductivity is that 3000～7000 μ S/cm, total hardness are that 1000～3000mg/L, COD are 20～200mg/L, and the treatment process of described reverse osmosis concentrated water may further comprise the steps successively:
(1) described reverse osmosis concentrated water being carried out nanofiltration handles; Described nanofiltration is handled and adopted the aperture is flat, tubular type or the rolling nanofiltration membrane of 0.001～0.003 μ m; The working pressure that described nanofiltration is handled is that 0.2～1.0MPa, service temperature are that 10～50 ℃, pH are 6～9, and the rate of recovery of control nanofiltration membrane is 60～75%, permeation flux is 10～40L/m
2H;
(2) add NaOH in the dense water of nanofiltration that described nanofiltration processing produces, regulating its pH is 10.0～11.5; Then, the dense water of described nanofiltration is carried out air supporting handle, it is hard to remove magnesium; Air pressure 0.2～0.4MPa, gas-water ratio that described air supporting is handled are 2～6: 1; Then, in the dense water of described nanofiltration, add Na
2CO
3, through post precipitation, carrying out solid-liquid separation, to remove calcium hard; Described Na
2CO
3Add-on be Na
2CO
3Generate CaCO with calcium ion reaction in the dense water of described nanofiltration
3Required Na
2CO
31.0～1.2 times of theoretical value;
(3) the hard and calcium dense water of nanofiltration after hard carries out the micro-filtration processing to demagging; Described micro-filtration is handled and adopted the aperture is flat, pocket type or the hollow fiber microfiltration membrane of 0.1～1.0 μ m; The working pressure that described micro-filtration is handled is that-0.02～0.20MPa, service temperature are that 10～50 ℃, pH are 9.0～11.5, and the permeation flux of microfiltration membrane is 40～100L/m
2H;
(4) add hydrochloric acid in the product water that described micro-filtration is handled, regulating its pH is 6～9; Carry out reverse-osmosis treated then; Described reverse-osmosis treated adopts rolled membrane module; The operating pressure of described reverse-osmosis treated is that 1.8～4.0MPa, operating temperature are that 10～50 ℃, pH are 6～9, and membrane flux is 15～45L/m
2H, cycles of concentration are 3～5;
(5) the dense water that described reverse-osmosis treated is produced carries out the multiple-effect evaporation processing; Described multiple-effect evaporation is handled and is adopted 2～4 to imitate cocurrent flow type or counterflow evaporator, and the temperature head between imitating and imitating is not less than 12 ℃; Then described multiple-effect evaporation is handled the dense salt debris that produces and carry out drying and other treatment;
The multiple-effect evaporation that the nanofiltration product water that step (1) produces, the reverse osmosis produced water that step (4) produces and step (5) produce produces water, directly or according to the water requirement handles the back reuse; The mummification slag that the micro-filtration slag that air supporting slag that step (2) produces and deliming slag, step (3) produce, step (5) produce is disposed as solid waste.
In the specific implementation, in step (1), described nanofiltration is handled and adopted the aperture is the rolling nanofiltration membrane of 0.002 μ m; The working pressure that described nanofiltration is handled is that 0.6～0.8MPa, service temperature are that 15～25 ℃, pH are 7.0～7.5; In step (2), the pH that regulates the dense water of described nanofiltration is 10.8～11.2; The air pressure that described air supporting is handled is that 0.3～0.4MPa, gas-water ratio are 3～5: 1; Described Na
2CO
3Add-on be Na
2CO
3Generate CaCO with calcium ion reaction in the dense water of described nanofiltration
3Required Na
2CO
31.0 times of theoretical value; In step (3), described micro-filtration is handled and adopted the aperture is the hollow fiber microfiltration membrane of 0.2 μ m; The working pressure that described micro-filtration is handled is-0.008～-0.015MPa, service temperature are that 15～25 ℃, pH are 10～11; In step (4), described reverse-osmosis treated adopts sea water desaltination series rolled membrane module; Add hydrochloric acid in the product water that described micro-filtration is handled, regulating its pH is 6.5～7.5; The operating pressure of described reverse-osmosis treated is that 2.0～2.5MPa, operating temperature are that 15～25 ℃, pH are 6.8～7.2; In step (5), described multiple-effect evaporation is handled and is adopted 3 to imitate cocurrent flow type or counterflow evaporator; Described drying and other treatment adopts nature to place mummification.
Utilize nanofiltration membrane to divalence, polyvalent ion (Ca
2+, Mg
2+, SO
4 2-) and the organic height of molecular weight between 200～1000 held back and to univalent ion (K
+, Na
+, Cl
-) the low characteristic of holding back, can realize dense water softening, softening mainly is to remove incrustation ion (Ca in the reverse osmosis concentrated water
2+And Mg
2+), can not remove all inorganic salt in the dense water.Adopt method of the present invention, bivalent ions clearance is more than 83% in the reverse osmosis concentrated water, and the COD clearance is 35～95%, and the TDS clearance is 35～95%
The present invention is through alkali adjusting and hardness removing, and the magnesium in the dense water is removed to below the 10mg/L firmly, calcium is firmly almost all removed.Behind the alkali adjusting and hardness removing, the dense water turbidity of waste water raises, and may contain a certain amount of suspended solids, must remove turbidity and SS in the water.Handle through micro-filtration, the hard and SS of the calcium in the dense water almost all is removed, and the product water turbidity is lower than 0.05NTU, and remaining magnesium is had certain removal effect firmly.
Through the dense water after alkali adjusting and hardness removing and the micro-filtration processing, the pH value is very high, is about about 10～11, for calcium, the magnesium scale that prevents from not remove in the dense water, must carry out neutralizing treatment, reduces dense water pH value.Dense water after the neutralization, monovalent salt concentration are very high, and the hardness in the dense water is almost all got rid of, and this just greatly reduces the possibility of fouling, adopt reverse osmosis system that dense water is further concentrated, and remove the unit price salt in the dense water.What reverse osmosis was selected for use is sea water desaltination series rolled membrane module, feed water by reverse osmosis SDI≤3.Ratio of desalinization reaches more than 95%, and the reverse osmosis concentration multiple is 3～5 times.
After the reverse osmosis system concentration, the salt concn in the dense water by adopting multiple-effect evaporation, with the further spissated while of dense water, realizes the reuse of vaporize water near supersaturation.The effect number of multiple-effect evaporation depends primarily on the temperature head that is evaporated between material maximum heating temperature and effect and the effect.Usually for electrolyte solution, adopt two to imitate or triple effect evaporation.
Adopt method of the present invention, after reverse osmosis concentrated water is handled through nanofiltration, nanofiltration is produced water and is returned the prime reverse osmosis system, after the dense water that nanofiltration produces is removed hardness, enter reverse osmosis system and concentrate, the dense water that reverse osmosis concentration produces enters multi-effect evaporation system, and the steam condensate of reverse osmosis produced water and multiple-effect evaporation can be back to production technique, high salt debris behind the multiple-effect evaporation obtains the salt slag by natural mummification, centrally disposes.Method of the present invention has realized " zero release " of reverse osmosis concentrated water basically, has remarkable social benefit and economic benefit.
The present invention adopts nanofiltration pre-treatment reverse osmosis concentrated water first, greatly reduce the water yield of alkali adjusting and hardness removing step, with NaOH is the alkali adjusting and hardness removing medicament, and the employing air floating method is removed the magnesium in the dense water, clearance height to calcium, magnesium, reduced the processing load of follow-up reverse osmosis concentrated compression system, the films such as fouling that reduced reverse osmosis membrane pollute, and have guaranteed long-term safety, the steady running of reverse osmosis membrane assembly.
Compare with seawater, waste water quality of the present invention is more complicated, except that having higher electricity leads, also contain higher hardness and COD, " (NF) → reverse osmosis (SWRO) → multistage flash evaporation (MSF) is softened in nanofiltration " desalination process is compared, the present invention is directed to the reverse osmosis concentrated water of petrochemical enterprises water quality characteristics, after the process nanofiltration is softening, remove hardness through demagging, deliming, improve cycles of concentration to 3～5 times of reverse osmosis concentrated water, reduced the fouling of reverse osmosis membrane, reduced the load of follow-up multiple-effect evaporation, and the water rate of recovery of whole process is reached about 95%.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
Embodiment 1～3
Certain reverse osmosis concentrated water of petrochemical enterprises, its electricity is led, TDS and always higher firmly, and contains a small amount of organism.The water quality and the analytical procedure of this dense water see Table 1.
Table 1
| Sequence number | Project | The dense water water quality of RO |
| 1 | pH | 7.34 |
| 2 | Electricity is led (μ S/cm) | 5323 |
| 3 | Colourity | 69 |
| 4 | Turbidity (NTU) | 0.19 |
| 5 | TDS(mg/L) | 2820 |
| 6 | Total alkalinity (CaCO 3)(mg/L) | 591.2 |
| 7 | Total hardness (CaCO 3)(mg/L) | 1121.6 |
| 8 | Solvable silicon (mg/L) | 8.91 |
| 9 | Total silicon (mg/L) | 9.56 |
| 10 | Ferrous (mg/L) | ＜0.03 |
| 11 | Total iron (mg/L) | ＜0.03 |
| 12 | Total phosphorus (mg/L) | 11.19 |
| 13 | COD cr(mg/L) | 68 |
| 14 | TOC(mg/L) | 32.68 |
| 15 | TN(mg/L) | 32.14 |
| 16 | K +(mg/L) | 23.0 |
| 17 | Na +(mg/L) | 650.7 |
| 18 | Ca 2+(mg/L) | 306.8 |
| 19 | Mg 2+(mg/L) | 80.3 |
| 20 | NH 4 +-N(mg/L) | ＜0.2 |
| 21 | F -(mg/L) | 1.6 |
| 22 | Cl -(mg/L) | 704.6 |
| 23 | NO 3 -(mg/L) | 147.6 |
| 24 | PO 4 3-(mg/L) | 17.3 |
| 25 | SO 4 2-(mg/L) | 698.4 |
| 26 | Petroleum-type (mg/L) | 0.21 |
| 27 | Mn 2+(mg/L) | 0.054 |
1, add an amount of organic inhibitor agent (Hypersperse MDC220) at reverse osmosis concentrated water, behind the adjusting pH, the employing aperture is that the rolling nanofiltration membrane of 0.002 μ m is carried out the nanofiltration processing;
2, in the dense water of nanofiltration, add NaOH and regulate pH; Then, the dense water of nanofiltration is carried out air supporting handle, it is hard to remove magnesium, adds Na in the dense water of nanofiltration
2CO
3, it is hard to remove calcium through precipitate and separate;
3, adopting the aperture is that the hollow fiber microfiltration membrane of the 0.2 μ m waste water after to alkali adjusting and hardness removing carries out micro-filtration and handles;
4, in micro-filtration product water, add hydrochloric acid, regulate its pH; Adopt sea water desaltination series rolled membrane module (Tao Shi SW30 sea water desaltination series rolled membrane module) to carry out reverse-osmosis treated then;
5, adopt 3 to imitate the cocurrent flow type vaporizer, the dense water that reverse-osmosis treated is produced carries out the multiple-effect evaporation processing, carries out nature then and places mummification.
The nanofiltration that said process produces is produced water, reverse osmosis produced water and multiple-effect evaporation and is produced water, the reverse osmosis system before getting back to, reuse after treatment; Air supporting slag that said process produces and deliming slag, micro-filtration slag, mummification slag centrally dispose as solid waste.
The operational condition of embodiment 1～3 each processing unit sees Table 2, and treatment effect sees 3.
Table 2
Each cell processing effect among table 3 embodiment
Claims (2)
1. the treatment process of a reverse osmosis concentrated water, the pH of described reverse osmosis concentrated water is 7.0～10.0, specific conductivity is that 3000～7000 μ S/cm, total hardness are that 1000～3000mg/L, COD are 20～200mg/L, and the treatment process of described reverse osmosis concentrated water may further comprise the steps successively:
(1) described reverse osmosis concentrated water being carried out nanofiltration handles; Described nanofiltration is handled and adopted the aperture is flat, tubular type or the rolling nanofiltration membrane of 0.001～0.003 μ m; The working pressure that described nanofiltration is handled is that 0.2～1.0MPa, service temperature are that 10～50 ℃, pH are 6～9, and the rate of recovery of control nanofiltration membrane is 60～75%, permeation flux is 10～40L/m
2H;
(2) add NaOH in the dense water of nanofiltration that described nanofiltration processing produces, regulating its pH is 10.0～11.5; Then, the dense water of described nanofiltration is carried out air supporting handle, it is hard to remove magnesium; The air pressure that described air supporting is handled is that 0.2～0.4MPa, gas-water ratio are 2～6: 1; Then, in the dense water of described nanofiltration, add Na
2CO
3, through post precipitation, carrying out solid-liquid separation, to remove calcium hard; Described Na
2CO
3Add-on be Na
2CO
3Generate CaCO with calcium ion reaction in the dense water of described nanofiltration
3Required Na
2CO
31.0～1.2 times of theoretical value;
(3) the hard and calcium dense water of nanofiltration after hard carries out the micro-filtration processing to demagging; Described micro-filtration is handled and adopted the aperture is flat, pocket type or the hollow fiber microfiltration membrane of 0.1～1.0 μ m; The working pressure that described micro-filtration is handled is that-0.02～0.20MPa, service temperature are that 10～50 ℃, pH are 9.0～11.5, and the permeation flux of microfiltration membrane is 40～100L/m
2H;
(4) add hydrochloric acid in the product water that described micro-filtration is handled, regulating its pH is 6～9; Carry out reverse-osmosis treated then; Described reverse-osmosis treated adopts rolled membrane module; The operating pressure of described reverse-osmosis treated is that 1.8～4.0MPa, operating temperature are that 10～50 ℃, pH are 6～9, and membrane flux is 15～45L/m
2H, cycles of concentration are 3～5;
(5) the dense water that described reverse-osmosis treated is produced carries out the multiple-effect evaporation processing; Described multiple-effect evaporation is handled and is adopted 2～4 to imitate cocurrent flow type or counterflow evaporator, and the temperature head between imitating and imitating is not less than 12 ℃; Then described multiple-effect evaporation is handled the dense salt debris that produces and carry out drying and other treatment;
Wherein, the multiple-effect evaporation that the nanofiltration product water that step (1) produces, the reverse osmosis produced water that step (4) produces and step (5) produce produces water, directly or according to the water requirement handles the back reuse; The mummification slag that the micro-filtration slag that air supporting slag that step (2) produces and deliming slag, step (3) produce, step (5) produce is disposed as solid waste.
2. treatment process according to claim 1 is characterized in that:
In step (1), described nanofiltration is handled and adopted the aperture is the rolling nanofiltration membrane of 0.002 μ m; The working pressure that described nanofiltration is handled is that 0.6～0.8MPa, service temperature are that 15～25 ℃, pH are 7.0～7.5;
In step (2), the pH that regulates the dense water of described nanofiltration is 10.8～11.2; The air pressure that described air supporting is handled is that 0.3～0.4MPa, gas-water ratio are 3～5: 1; Described Na
2CO
3Add-on be Na
2CO
3Generate CaCO with calcium ion reaction in the dense water of described nanofiltration
3Required Na
2CO
31.0 times of theoretical value;
In step (3), described micro-filtration is handled and adopted the aperture is the hollow fiber microfiltration membrane of 0.2 μ m; The working pressure that described micro-filtration is handled is-0.008～-0.015MPa, service temperature are that 15～25 ℃, pH are 10～11;
In step (4), described reverse-osmosis treated adopts sea water desaltination series rolled membrane module; Add hydrochloric acid in the product water that described micro-filtration is handled, regulating its pH is 6.5～7.5; The operating pressure of described reverse-osmosis treated is that 2.0～2.5MPa, operating temperature are that 15～25 ℃, pH are 6.8～7.2;
In step (5), described multiple-effect evaporation is handled and is adopted 3 to imitate cocurrent flow type or counterflow evaporator; Described drying and other treatment adopts nature to place mummification.
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