CN105036393A - Treating method and apparatus for high-hardness high-salinity waste water - Google Patents
Treating method and apparatus for high-hardness high-salinity waste water Download PDFInfo
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Abstract
The invention provides a treating method and apparatus for high-hardness high-salinity waste water. The treating method comprises the following steps: subjecting the high-hardness high-salinity waste water to nanofiltration and softening so as to obtain a first separated solution and a first concentrated solution; subjecting the first separated solution to forward osmosis and concentration so as to obtain a second concentrated solution and a second separated solution; and returning the second separated solution to production and separately crystallizing the first concentrated solution and the second concentrated solution so as to obtain solid salt. The treating apparatus comprises a nanofiltration and softening device, a forward osmosis and concentration device, a reuse water tank, a first crystallizer and a second crystallizer, wherein the nanofiltration and softening device comprises a first water inlet, a first concentrated solution outlet and a first separated solution outlet, the forward osmosis and concentration device comprises a second water inlet, a second concentrated solution outlet and a second separated solution outlet, and the reuse water tank is provided with a third water inlet. The treating method provided by the invention poses no pollution to the environment, is green and environment-friendly, has strong waste water treating capability and can realize zero discharge of waste water.
Description
Technical field
The present invention relates to field of industrial waste water treatment, in particular to a kind for the treatment of process and equipment of high rigidity high salinity waste water.
Background technology
The waste water produced in the Industrial processes such as electric power, metallurgy, chemical industry, sea water desaltination, printing and dyeing, papermaking is usually containing higher hardness and higher salinity, higher hardness mainly refers to that the total concn of calcium in sewage, magnesium ion is high, if the unprocessed direct discharge of such waste water, the salinization of water body and soil can be caused, harm physical environment.
At present, softening method for this high rigidity waste water mainly comprises chemical method and ion exchange method, chemical method goes in the practical application of calcium-magnesium removing the most general at various high slat-containing wastewater, its dominant mechanism is in waste water, add certain chemical agent, makes calcium ions and magnesium ions form difficulty soluble salt and the removing that precipitates or flocculate.In high slat-containing wastewater, the higher and water yield of hardness is comparatively large, and the chemical volume adopting chemical method to need to drop into is also corresponding comparatively large, costly; Chemical method often produces a large amount of mud and causes secondary pollution to environment simultaneously.Ion exchange method goes to be widely used in hardness production softening water at waste water.Ion exchange method effectively can remove calcium magnesium scale ion, but resin or carrier in use all exist regeneration issues.Generally all regenerative agent is needed, somewhat expensive and there is secondary pollution to environment, the needs that inapplicable high rigidity waste water is softening in regenerative process.
And embrane method and Re Fa are mainly comprised for the concentration method of high salinity waste water, because high slat-containing wastewater has higher osmotic pressure, the rate of recovery of reverse osmosis membrane to high slat-containing wastewater is lower, cannot be concentrated into the needs that higher multiple meets crystallizer.Adopt hot method to concentrate high slat-containing wastewater and need a large amount of steam, ton cost of water treatment is high, and requires higher to vaporizer material, and equipment investment cost is large.If adopt Mechanical Vapor Compression to reduce steam consumption, the cost of investment of same meeting increasing device and running cost.
Visible, mainly chemical method and hot method of enrichment are combined for the treatment process of high rigidity high salinity waste water in prior art, but this array mode not only consumes a large amount of chemical agents and steam, adds running cost virtually, but also pollutes the environment.
In view of this, special proposition the present invention.
In prior art, generally all adopt the mode by chemical method combines with hot method of enrichment to carry out process waste water, but this mode not only consumes a large amount of chemical agents and steam, adds running cost virtually, but also pollute the environment.In order to overcome the above problems, embodiments provide a kind for the treatment of process of high rigidity high salinity waste water, first adopt sodium filter tenderizer process high rigidity waste water, nanofiltration membrane separation to divalent ion (as calcium ion, magnesium ion and sulfate ion etc.) and polyvalent ion have good rejection, calcium can be removed, magnesium, silicon and sulfate radical plasma, greatly reduce the possibility that incrustation scale is formed, wherein, the operating pressure of nanofiltration sofening treatment is preferably at 0.2-4.0MPa, calcium in waste water can be removed more efficiently, magnesium plasma, greatly reduce the possibility that incrustation scale is formed.Meanwhile, nanofiltration has environmental protection, can not to the advantage of environment.
In the present invention, employ positive osmose process process high salinity waste water through the product water of nanofiltration sofening treatment is creationary again, the permeable pressure head that positive osmosis concentration technique produces with semi-permeable membranes both sides, for motivating force, makes that water molecules is spontaneous is diffused into high osmotic pressure side from Hyposmolality side.Relative to reverse osmosis concentration technique, positive osmosis concentration has higher concentration rate.Relative to evaporative crystallization technique, positive osmosis concentration has lower energy consumption.Simultaneously, positive osmosis concentration device does not need high-pressure pump just can run, and therefore has higher antifouling property, less scaling, not yet find the report using positive osmosis concentration technical finesse waste water in prior art, the method for process high rigidity high salinity waste water of the present invention still belongs to the first.
Further, before nanofiltration sofening treatment is carried out to high rigidity high salinity waste water, preferably first pre-treatment is carried out to waste water, object is to remove in high rigidity high salinity waste water contained granule foreign or precipitation, and concrete pretreated method can adopt wherein one or more the combination of following several method: sand filtration, multi-medium filtering, flocculation, clarification etc.These methods all belong to the method for separating impurity common in prior art, by organically combining with other wastewater processing technologies of the present invention, achieve the efficient process of high rigidity high salinity waste water, the operational path of this concrete wastewater treatment is that contriver puts into practice out by great many of experiments, there is no record in prior art.
Further, in order to improve water treatment effect, preferably reverse osmosis being combined with positive osmosis concentration treatment process, therefore also comprising the steps: between described step (A) and described step (B)
First the first parting liquid is carried out reverse osmosis concentration and obtain the 3rd parting liquid and the 3rd concentrated solution; Then in described step (B), the 3rd concentrated solution is proceeded positive osmosis concentration and obtains the second concentrated solution and the second parting liquid, the 3rd parting liquid then return for the production of; Then in described step (C), the second parting liquid carries out a reverse osmosis concentration process again again.
By with the addition of reverse osmosis concentration treatment process, the product water now after positive osmosis concentration process returns production after first will returning and carrying out reverse-osmosis treated again, fully to carry the clean quiet degree of high yield water, meets the demand to the high user of water quality requirement.Wherein, the saltiness that nanofiltration can be produced water by reverse osmosis pre-concentration treatment process is promoted to 50000-80000mg/L by 5000-10000mg/L.And the product water of reverse osmosis directly uses as industrial reuse water, the concentrated solution of reverse osmosis continues to enter forward osmosis membrane concentration.The concentration of the concentrated solution after positive osmosis concentration process is 4-5 times of reverse osmosis concentrated liquid, now positive osmosis concentration liquid saltiness can reach 200000-250000mg/L, just permeating and producing water and be back to reverse osmosis pre-concentration and refine, positive osmosis concentration liquid then directly can carry out crystallization treatment, need not additionally find other treatment processs, not only saved manpower and materials, also reduced cost for wastewater treatment, this advantage nowadays any one method of wastewater treatment can not be compared.So positive infiltration and counter-infiltration process to be combined, namely ensure that the water quality of producing water can direct reuse, turn improve the concentration of concentrated solution, kill two birds with one stone, very environmental protection.
In order to meet the demand of different user, described positive osmosis concentration design can be single-stage or multiple-stage treatment, and described reverse osmosis concentration design also can be single-stage or multiple-stage treatment, regulates concentrated progression by the specific requirement of water quality.
Finally, in this step of concentrated solution crystallization, the concentrated solution obtained after positive osmosis concentration directly can carry out crystallization treatment because concentration own is higher, mainly obtains inorganic monovalent salt and the water of condensation such as sodium-chlor magma.Sodium-chlor magma, through centrifugation, drying and packing, obtains final sodium-chlor product, can direct marketing, and economic benefits, water of condensation then recycles.The concentrated solution crystallization that nanofiltration sofening treatment obtains mainly obtains bivalent inorganic salt, comprises magnesium sulfate, sodium sulfate and calcium sulfate, and through centrifugation, drying and packing, obtain sulfate product, water of condensation then recycles.
In addition, first concentrated solution crystallization treatment obtains the first mother liquor, first mother liquor and the second concentrated solution merge and carry out crystallization treatment and obtain the second mother liquor, be equivalent to the crystallization treatment again to mother liquor, described second mother liquor carries out nanofiltration sofening treatment again again, the saltiness of water inlet can be increased like this, be conducive to solution to bring up to concentration needed for crystallization.
The embodiment of the present invention additionally provides the supporting sewage treatment equipment of a kind of and above-mentioned treatment process, comprises nanofiltration softening installation, positive osmosis concentration device, reuse water tank and the first crystallizer, the second crystallizer; Described nanofiltration softening installation comprises the first water-in, the first concentrated solution outlet and the first discharge channel that enter for high rigidity high salinity waste water, described positive osmosis concentration device comprises the second water-in, the second concentrated solution outlet and the second discharge channel, described reuse water tank is provided with the 3rd water-in;
Described first discharge channel connects described second water-in, and described second discharge channel connects the 3rd water-in, and described first concentrated solution outlet connects described first crystallizer, and described second concentrated solution outlet connects described second crystallizer.
Further, also comprise for pretreated pretreatment unit, described pretreatment unit comprises the waste water inlet and wastewater outlet that enter for high rigidity high salinity waste water, and described wastewater outlet is connected with the first water-in of described nanofiltration softening installation.
Further, also comprise reverse osmosis concentrated compression apparatus, described reverse osmosis concentrated compression apparatus comprises the 3rd discharge channel, the 3rd concentrated solution outlet and the 4th water-in; Then described first discharge channel and described second discharge channel are connected described 4th water-in simultaneously, described 3rd discharge channel connects the 3rd water-in, described 3rd concentrated solution outlet connects the second water-in, described first concentrated solution outlet connects the first crystallizer, and described second concentrated solution outlet connects described second crystallizer.
The industrial wastewater treatment device of the embodiment of the present invention, floor space is little, low cost, match with method of wastewater treatment of the present invention, process waste water ability is strong, can realize wastewater zero discharge in whole technological process, all products are all recyclable or directly sold by further separation, economic benefit is good, is suitable for extensively promoting the use of, meets the requirement of different user to water quality.
Prior art is compared, and beneficial effect of the present invention is:
(1) a kind for the treatment of process of high rigidity high salinity waste water is embodiments provided, by nanofiltration, reverse osmosis and just permeating organically is combined, achieve the softening of high rigidity high salinity waste water and concentrate, not only easy to operate, treatment process is simple, and environmental protection, by the real-time adjusting process of the difference of different crowd to water quality requirement, very flexible, non-wastewater discharge in whole treating processes, can also the huge chemical by-product of output added value, form sales volume, create economic benefit;
(2) proposing of the invention utilizes positive osmosis concentration treatment process to process high rigidity high salinity waste water, the concentrated solution obtained has higher concentration, can realize direct crystallization process, need not extra other treatment process, reduce manpower and materials cost, simplify treatment process;
(3) embodiment of the present invention additionally provides the sewage treatment equipment that a kind of and above-mentioned high rigidity high-salinity waste water treatment method matches, compact construction, floor space is little, equipment manufacturing cost is low, and process waste water ability is strong, can realize wastewater zero discharge in whole technological process, the all products obtained all can reuse or directly sold by further separation, economic benefit is good, is suitable for extensively promoting the use of, can not causes secondary pollution to environment.
Summary of the invention
The first object of the present invention is the treatment process providing a kind of high rigidity high salinity waste water, it is simple that described method has treatment process, easy to operate, can not to the abundant environmental protection of environment, waste treatment capacity is strong, can realize the advantages such as wastewater zero discharge.
The second object of the present invention is the treatment facility providing a kind of high rigidity high salinity waste water, and described sewage treatment equipment well can coordinate the advantage of the zero release achieving waste water with treatment process.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
Embodiments provide a kind for the treatment of process of high rigidity high salinity waste water, comprise the steps:
(A) first nanofiltration sofening treatment is carried out to high rigidity high salinity waste water and obtain the first parting liquid and the first concentrated solution;
(B) the second concentrated solution and the second parting liquid is obtained after the first parting liquid being carried out positive osmosis concentration;
(C) the second parting liquid return for the production of, the first concentrated solution and the second concentrated solution separately crystallization treatment obtain solid salt.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below.
Fig. 1 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention one;
Fig. 2 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention two;
Fig. 3 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention three;
Reference numeral:
101-pretreatment unit; 102-settling pond;
103-more medium filter; 104-nanofiltration softening installation;
The reverse osmosis concentrated compression apparatus of 105-; The positive osmosis concentration device of 106-
107-reuse water tank; 108-first crystallizer;
109-second crystallizer.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Accompanying drawing 1 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention one, specifically comprises nanofiltration softening installation 104, positive osmosis concentration device 106, reuse water tank 107 and the first crystallizer 108, second crystallizer 109; Described nanofiltration softening installation 104 comprises the first water-in, the first concentrated solution outlet and the first discharge channel that enter for high rigidity high salinity waste water, described positive osmosis concentration device 106 comprises the second water-in, the second concentrated solution outlet and the second discharge channel, described reuse water tank 107 is provided with the 3rd water-in;
Wherein, described first discharge channel connects described second water-in, and described second discharge channel connects the 3rd water-in, and described first concentrated solution outlet connects described first crystallizer, and described second concentrated solution outlet connects described second crystallizer.
The specific works flow process of the high rigidity high salinity waste water treatment facility of the present embodiment is: as can be seen from Fig. 1, waste water specifically moves towards also, waste water first processes through nanofiltration softening installation 104, nanofiltration is softened concentrated solution and is directly entered the first crystallizer 108 and carry out crystallization treatment, first crystallizer there is condensation-water drain export with vitriol magma, vitriol magma, through centrifugation, drying and packing, finally obtains sulfate product; Water of condensation then recycles.The softening water that produces of nanofiltration enters positive osmosis concentration device 106, reuse water tank 107 direct reuse is walked from positive osmosis concentration device 106 product water out, and concentrated solution enters the second crystallizer 109 crystallization treatment, second crystallizer contains condensation-water drain and the outlet of sodium-chlor magma, sodium-chlor magma, through centrifugation, drying and packing, obtains final sodium-chlor product; Water of condensation recycles, thus completes whole wastewater treatment process, and whole technique is discharged without waste water, can not cause secondary pollution to environment.
Accompanying drawing 2 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention two, is further preferred embodiment, meets the user high to water quality requirement.Specifically comprise more medium filter 103, nanofiltration softening installation 104, reverse osmosis concentrated compression apparatus 105, positive osmosis concentration device 106, reuse water tank 107 and the first crystallizer 108, second crystallizer 109; More medium filter is provided with the waste water inlet and wastewater outlet that enter for high rigidity high salinity waste water, described nanofiltration softening installation 104 comprises the first water-in, the first concentrated solution outlet and the first discharge channel, described reverse osmosis concentrated compression apparatus 105 comprises the 3rd discharge channel, 3rd concentrated solution outlet and the 4th water-in, described positive osmosis concentration device 106 comprises the second water-in, the second concentrated solution outlet and the second discharge channel, described reuse water tank 107 is provided with the 3rd water-in;
Wherein, described first discharge channel and described second discharge channel are connected described 4th water-in simultaneously, described 3rd discharge channel connects the 3rd water-in, described 3rd concentrated solution outlet connects the second water-in, described first concentrated solution outlet connects the import of the first crystallizer, and described second concentrated solution outlet connects the import of described second crystallizer, and the mother liquor outlet of the first crystallizer connects the import of the second crystallizer, the outlet of the second crystallizer connects the first water-in
The specific works flow process of the high rigidity high salinity waste water treatment facility of the present embodiment is: as can be seen from Fig. 2, waste water specifically moves towards also, waste water first filters out after residue through more medium filter, enter nanofiltration softening installation 104 to process, nanofiltration is softened concentrated solution and is directly entered the first crystallizer 108 and carry out crystallization treatment, first crystallizer there is condensation-water drain export with vitriol magma, vitriol magma is through centrifugation, drying and packing, obtain final sulfate product, the first crystallizer mother liquor out goes the second crystallizer to carry out crystallization treatment; Water of condensation recycles.The softening water that produces of nanofiltration enters reverse osmosis concentrated compression apparatus 105, enter positive osmosis concentration device 106 from reverse osmosis concentrated compression apparatus 105 concentrated solution out and concentrate further, reuse water tank 107 direct reuse is walked from reverse osmosis concentrated compression apparatus 105 product water out, and concentrated solution out enters the second crystallizer 109 crystallization treatment from positive osmosis concentration device 106, second crystallizer contains condensation-water drain and the outlet of sodium-chlor magma, sodium-chlor magma, through centrifugation, drying and packing, obtains final sodium-chlor product; Water of condensation then recycles, second crystallizer mother liquor out goes nanofiltration softening installation to carry out nanofiltration sofening treatment, from positive osmosis concentration device 106, product water out returns after reverse osmosis treatment device processes and returns production again, so complete whole wastewater treatment process, whole technique is discharged without waste water, can not cause secondary pollution to environment.
Accompanying drawing 3 is the treatment facility structure iron of the high rigidity high salinity waste water of the embodiment of the present invention three.The concrete structure of the present embodiment is substantially the same manner as Example 2, just in pretreatment unit 101, add settling pond 102 more, now pretreatment unit 101 comprises settling pond 102 and more medium filter 103, the wastewater outlet of settling pond 102 connects more medium filter 103, and the wastewater outlet of more medium filter 103 connects the first water-in of nanofiltration softening installation 104.
During concrete enforcement, the specific works flow process of the high rigidity high salinity waste water treatment facility of the present embodiment is identical with embodiment 2, just regulate wastewater pH to 10-11 by adding calcium hydroxide in settling pond, magnesium ion is precipitated with the form of magnesium hydroxide, the magma main component of the first crystallizer can be made to be sodium sulfate and calcium sulfate, to obtain vitriol through centrifugation, drying and packing.
Certainly, in the present embodiment, reverse osmosis concentrated compression apparatus 105 all can be set to multilevel hierarchy with positive osmosis concentration device 106.
The present invention can realize point system of monovalent salt, divalent salts and a polyvalent salt by nanofiltration, simplify the flow process of crystallization processes, and creationaryly employ permeable pressure head that positive osmosis concentration technique produces with semi-permeable membranes both sides for motivating force, make that water molecules is spontaneous is diffused into high osmotic pressure side from Hyposmolality side.Relative to reverse osmosis concentration technique, positive osmosis concentration has higher concentration rate.Relative to evaporative crystallization technique, positive osmosis concentration has lower energy consumption.Meanwhile, positive osmosis concentration system does not need high-pressure pump just can run, and therefore has higher antifouling property, less scaling, can realize the zero release of high rigidity high salinity waste water, whole technological process and device thereof do not produce waste water, can not cause secondary pollution to environment.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. a treatment process for high rigidity high salinity waste water, is characterized in that, comprises the steps:
(A) first nanofiltration sofening treatment is carried out to high rigidity high salinity waste water and obtain the first parting liquid and the first concentrated solution;
(B) the second concentrated solution and the second parting liquid is obtained after the first parting liquid being carried out positive osmosis concentration;
(C) the second parting liquid return for the production of, the first concentrated solution and the second concentrated solution separately crystallization treatment obtain solid salt.
2. the treatment process of high rigidity high salinity waste water according to claim 1, is characterized in that, also comprises the steps: high rigidity high salinity waste water to be carried out pre-treatment to remove solid particle polluter wherein before described step (A).
3. the treatment process of high rigidity high salinity waste water according to claim 2, is characterized in that, described pretreatment mode comprises the combination of one or more methods in sand filtration, multi-medium filtering, flocculation and clarifying treatment method.
4. the treatment process of high rigidity high salinity waste water according to claim 1, is characterized in that, also comprises the steps: between described step (A) and described step (B)
First the first parting liquid is carried out reverse osmosis concentration and obtain the 3rd parting liquid and the 3rd concentrated solution;
Then in described step (B), the 3rd concentrated solution is proceeded positive osmosis concentration and obtains the second concentrated solution and the second parting liquid, the 3rd parting liquid then return for the production of;
Then in described step (C), the second parting liquid carries out a reverse osmosis concentration process again again;
Preferably, in described step (C), the first concentrated solution crystallization treatment obtains the first mother liquor, and the first mother liquor and the second concentrated solution merge and carry out crystallization treatment and obtain the second mother liquor, and described second mother liquor carries out nanofiltration sofening treatment again again.
5. the treatment process of the high rigidity high salinity waste water according to any one of claim 1-4, is characterized in that, in described step (A), the operating pressure of nanofiltration sofening treatment is 0.2-4.0MPa.
6. the treatment process of high rigidity high salinity waste water according to claim 4, is characterized in that, described positive osmosis concentration is designed to single-stage or multiple-stage treatment.
7. the treatment process of high rigidity high salinity waste water according to claim 4, is characterized in that, described reverse osmosis concentration is designed to single-stage or multiple-stage treatment.
8. described in the disposal methods of any one of claim 1-7, the treatment facility of high rigidity high salinity waste water, is characterized in that, comprises nanofiltration softening installation, positive osmosis concentration device, reuse water tank and the first crystallizer, the second crystallizer; Described nanofiltration softening installation comprises the first water-in, the first concentrated solution outlet and the first discharge channel that enter for high rigidity high salinity waste water, described positive osmosis concentration device comprises the second water-in, the second concentrated solution outlet and the second discharge channel, described reuse water tank is provided with the 3rd water-in;
Described first discharge channel connects described second water-in, and described second discharge channel connects the 3rd water-in, and described first concentrated solution outlet connects described first crystallizer, and described second concentrated solution outlet connects described second crystallizer.
9. the treatment facility of high rigidity high salinity waste water according to claim 8, it is characterized in that, also comprise pretreatment unit, described pretreatment unit comprises the waste water inlet and wastewater outlet that enter for high rigidity high salinity waste water, and described wastewater outlet is connected with the first water-in of described nanofiltration softening installation.
10. the treatment facility of high rigidity high salinity waste water according to claim 9, is characterized in that, also comprises reverse osmosis concentrated compression apparatus, and described reverse osmosis concentrated compression apparatus comprises the 3rd discharge channel, the 3rd concentrated solution outlet and the 4th water-in;
Then described first discharge channel and described second discharge channel are connected described 4th water-in simultaneously, described 3rd discharge channel connects the 3rd water-in, described 3rd concentrated solution outlet connects the second water-in, described first concentrated solution outlet connects the first crystallizer, and described second concentrated solution outlet connects described second crystallizer.
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