CN104229856A - Method and device for desalting by utilizing waste liquor and preparing light barium sulphate simultaneously - Google Patents
Method and device for desalting by utilizing waste liquor and preparing light barium sulphate simultaneously Download PDFInfo
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- CN104229856A CN104229856A CN201410452970.5A CN201410452970A CN104229856A CN 104229856 A CN104229856 A CN 104229856A CN 201410452970 A CN201410452970 A CN 201410452970A CN 104229856 A CN104229856 A CN 104229856A
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Abstract
The invention discloses a method and device for desalting by utilizing waste liquor and preparing light barium sulphate simultaneously. The method for desalting by utilizing the waste liquor and preparing the light barium sulphate simultaneously adopts a magnesium sulphate solution as a drawing liquid and comprises the following steps: permeating by virtue of a forward osmosis unit and drawing water molecules in the waste liquor; adding a barium hydroxide solution into the obtained diluted magnesium sulphate solution and carrying out reaction, so that mixed and precipitated suspended solids containing magnesium hydroxide and barium sulphate are obtained; and carrying out precipitation separation on the suspended solids to obtain mixed precipitate and clean water, recycling the clean water, adding sulphuric acid into the mixed precipitate, carrying out an acidification reaction for dissolving and removing magnesium hydroxide, and thus obtaining the light barium sulphate, wherein the magnesium sulphate solution obtained by dissolving magnesium hydroxide by virtue of sulphuric acid is returned as the drawing liquid. The method and device for desalting by utilizing the waste liquor and preparing the light barium sulphate simultaneously have the advantages that equipment is simple, operation is easy, production cost and time cost for preparation of the barium sulphate are greatly reduced, the produced waste liquor still can be returned and used as the drawing liquid to feed, and zero discharge of the waste liquor is truly realized, so that the method and device for desalting by utilizing the waste liquor and preparing the light barium sulphate simultaneously have a good market prospect.
Description
Technical field
The present invention relates to wastewater treatment and chemical technology field, particularly a kind of method and device thereof utilizing waste water desalination to hold concurrently to prepare lightweight barium sulfate.
Background technology
At chemical technology field, barium sulfate is as industrial chemicals, of many uses, can be used in coating, paint, ink, poster paint, makeup, as raw material or the weighting agent of store battery, in rubber item, both make weighting agent, play strengthening action again, weighting agent and weighting agent is made in polychlorostyrene ethane resin, the surface coated agent of impression paper and art paper, the sizing agent of textile industry, is used as finings in glasswork, the effect etc. of froth breaking and increase gloss can be played, there is higher marketable value.
Usually, prepare barium sulfate many employings chemical method, barium sulfate cost is prepared higher with chemical method, complex process, as: Chinese patent CN201210163579.4 discloses a kind of method that manganous sulfate of purifying prepares barium sulfate simultaneously, the method is successively by sulfide removal of impurities, manganous sulfate and barium sulphide react, heat is washed, oxidation, barium sulfate product process, barium sulfate is prepared while the steps such as manganese sulfate product purification achieve purification manganous sulfate, this technique needs to add a large amount of chemical reagent and causes cost higher in treating processes, need strict to reaction conditions and to there is technological process more complicated, the problems such as inconvenient operation,
Chinese invention patent CN201010615443.3 discloses a kind of method that barium sulfate and co-produced iron protochloride prepared by bariumchloride waste residue, the method obtains bariumchloride and barium sulfide solution by dissolving bariumchloride waste residue, add hydrochloric acid make barium sulphide be converted into bariumchloride and with alkali lye removing hydrogen sulfide after, with ferrous sulfate sedimentation bariumchloride, thus obtained barium sulfate, there is complex process in the method, it is high and very easily cause secondary pollution problems if any careless manipulation to need to drop into a large amount of chemical reagent costs.Through for many years research but preparation method does not still have breakthrough progress.
Data statistics display after deliberation, in field of waste water treatment, forward osmosis technology receives much concern because of advantages such as its technique is simple, less energy-consumption, low fouling membrane, high rejection.In actual waste water process application process, forward osmosis technology generally adopts NaCl solution as drawing liquid, the liquid that draws after dilution is mainly used in further concentration and recovery pure water, the liquid that draws after concentrated returns as drawing liquid water inlet, draw liquid kind single, to drawing the research that liquid recycles further less.
In sum, in conjunction with chemical technology field and forward osmosis technology application present situation in the treatment of waste water, contriver is through experimental study for many years, develop and a kind ofly utilize double new process and the device thereof preparing barium sulfate of waste water desalination, in this technological process, select Adlerika as drawing liquid, for preparation lightweight barium sulfate provides SO after this draws liquid dilution
4 2+ion, and subsequently through the Ba adding barium hydroxide solution and provide
2+ionic bond forms precipitation, is further purified the waste liquid obtained and still can returns as drawing liquid water inlet.The method technique and device is simple, easy to operate, cost is lower, also achieve the preparation of barium sulfate while not only achieving wastewater treatment like a cork, obtained lightweight barium sulfate purity is high, has good market application foreground.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of method and device thereof that utilize waste water desalination to hold concurrently to prepare lightweight barium sulfate.This processing method and device is simple, cost is low, operating process easily controls, the preparation of barium sulfate is achieved while realizing waste water desalination, the barium sulfate purity prepared is higher, and the waste liquid of generation still can return as drawing liquid water inlet, has good market application foreground.
For reaching this object, the present invention by the following technical solutions:
Utilize waste water desalination to hold concurrently and prepare a method for lightweight barium sulfate, it is characterized in that, described technique adopts Adlerika as drawing liquid, is permeated the water molecules drawn in waste water by forward osmosis unit; Obtain adding barium hydroxide solution reaction in the Adlerika after diluting, obtain containing magnesium hydroxide and barium sulfate mixed precipitation suspended substance, described suspended substance obtains mixed precipitation and clear water through precipitate and separate, described clear water carries out reuse, described mixed precipitation adds sulfuric acid acidation reaction dissolving removal magnesium hydroxide and obtains the pure barium sulfate of lightweight, and the Adlerika that sulfuric acid dissolution magnesium hydroxide obtains returns as drawing liquid.
The described Adlerika concentration as drawing liquid is greater than raw material waste water total dissolved solid concentration.
The described Adlerika concentration as drawing liquid is 16 ~ 250g/L, is preferably 60 g/L.
First waste water enter pretreatment unit carries out pre-treatment and removes suspended substance and colloid, then enters forward osmosis unit; Magnesium sulfate in forward osmosis unit draws the liquid water drawn in waste water and is formed and draw liquid water outlet and flow into precipitation unit and barium hydroxide solution and react and generate magnesium hydroxide and barium sulfate mixture suspension, described mixture suspension obtains mixed sediment and clear water through precipitate and separate, described clear water carries out reuse, described mixed sediment dissolves removal magnesium hydroxide by sulfuric acid acidation reaction and obtains the pure barium sulfate of lightweight, and the Adlerika that sulfuric acid dissolution magnesium hydroxide obtains returns as drawing liquid water inlet after ultra-filtration filters.
Preferably, described sulfuric acid adopts mass concentration to be the sulfuric acid of 20 ~ 40%.
Present invention also offers and a kind ofly realize utilizing as mentioned above waste water desalination to hold concurrently the device of preparation lightweight barium sulfate method, described device comprises forward osmosis unit, reaction precipitation unit, the first precipitate and separate unit, resolution of precipitate unit and the second precipitate and separate unit, the water outlet of described forward osmosis unit is communicated with reaction precipitation unit water-in, and the liquid outlet of reaction precipitation unit is connected by the water-in of slush pump with the first precipitate and separate unit; The clear water output on the first precipitate and separate unit top is connected with reuse water pipe, and base sludge outlet is connected with resolution of precipitate unit water-in; Described resolution of precipitate unit liquid outlet is connected with the second precipitate and separate unit water-in.
Wherein, pretreatment unit is connected with before described forward osmosis unit; Preferably, described pretreatment unit comprises sand-bed filter and immersion ultrafiltration tank; Described forward osmosis unit comprises waste water room, semipermeable partition and draws room, and described waste water room and described drawing between room use semipermeable partition to separate; Described semipermeable partition is preferably polyamide composite film; Described drawing above room is connected with Adlerika filling, and the lower dilute sulphuric acid magnesium solution that can be connected with is filled with, and described dilute sulphuric acid magnesium solution is filled with and passed into described reaction precipitation unit again; Described reaction precipitation unit is connected with barium hydroxide solution tank, and installs agitator and stir; Described resolution of precipitate unit is connected with sulphuric acid soln tank, and installs agitator and stir; Described second precipitate and separate unit supernatant liquor outlet is connected with immersion ultrafiltration pond water-in, and described first and second precipitation unit preferably all adopt radical sedimentation basin.
Compared with prior art, the present invention has following beneficial effect:
(1) the invention discloses a kind of new process and the device of preparing lightweight barium sulfate;
(2) processing method provided by the invention and equipment is simple, cost is low, there is not secondary pollution, has a good application prospect;
(3) the barium sulfate purity prepared by processing method of the present invention is higher, and gained waste liquid still can be used for returning as drawing liquid water inlet, and the resource utilization really achieving waste water reclaims;
(4) present invention achieves forward osmosis technology is applied to chemical technology field, utilize desalination process for waste water to prepare barium sulfate, greatly reduce production cost and the time cost of barium sulfate, there is stronger practicality.
Accompanying drawing explanation
Fig. 1 a kind ofly described in the specific embodiment of the invention utilizes waste water desalination to hold concurrently the device of preparation lightweight barium sulfate;
In figure: 1-sand-bed filter; 2-immersion ultrafiltration tank; 3-forward osmosis unit; 4-reaction precipitation unit; 5-first precipitate and separate room; 6-semipermeable partition; 7-resolution of precipitate unit; 8-second precipitate and separate unit; 9-immersion ultrafiltration pond.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with drawings and Examples;
Utilize waste water desalination to hold concurrently and prepare a method for lightweight barium sulfate, described technique adopts Adlerika as drawing liquid, is permeated the water molecules drawn in waste water by forward osmosis unit 3; Obtain adding barium hydroxide solution reaction in the Adlerika after diluting, obtain the mixed precipitation suspended substance containing magnesium hydroxide and barium sulfate, described suspended substance obtains mixed precipitation and clear water through precipitate and separate, described clear water carries out reuse, described mixed precipitation adds sulfuric acid acidation reaction dissolving removal magnesium hydroxide and obtains the pure barium sulfate of lightweight, and the Adlerika that sulfuric acid dissolution magnesium hydroxide obtains returns as drawing liquid.
Wherein, the described Adlerika concentration as drawing liquid is greater than raw material waste water total dissolved solid concentration, and the described Adlerika concentration as drawing liquid is 16 ~ 250g/L, is preferably 60g/L; Described sulfuric acid adopts mass concentration to be the sulfuric acid of 20 ~ 40%.
First waste water enter pretreatment unit carries out pre-treatment and removes suspended substance and colloid, then enters forward osmosis unit 3; The liquid that draws in forward osmosis unit 3 chooses the MgSO that concentration is 16 ~ 250g/L
4solution, is preferably 60g/L, MgSO
4the solution water drawn in waste water is formed and draws liquid water outlet inflow reaction precipitation unit 4 and Ba (OH)
2solution reaction generates the mixed precipitation suspension containing magnesium hydroxide and barium sulfate.This mixed precipitation suspension obtains mixed precipitation and clear water through the further precipitate and separate of the first precipitate and separate unit 5, clear water is because the lower direct reuse of salinity is in production, and mixed precipitation enters resolution of precipitate unit 7 and dissolves removal Mg (OH) by the sulfuric acid acidation reaction that mass concentration is 20 ~ 40%
2obtain containing the pure BaSO of lightweight
4the MgSO of precipitation
4solution, described solution obtains the pure BaSO of lightweight through the second precipitate and separate unit 8 precipitate and separate
4, MgSO
4solution returns as required further as drawing liquid water inlet after ultra-filtration filters.
Present invention also offers a kind of device for above-mentioned processing method:
As shown in Figure 1, a kind ofly utilize waste water desalination to hold concurrently the device of preparation lightweight barium sulfate, described device mainly comprises forward osmosis unit 3, reaction precipitation unit 4, first precipitate and separate unit 5, resolution of precipitate unit 7 and the second precipitate and separate unit 8.
The water outlet of described forward osmosis unit 3 is communicated with described reaction precipitation unit 4 water-in, and the liquid outlet of described reaction precipitation unit 4 is connected by the water-in of slush pump with described first precipitate and separate unit 5; The clear water output on described first precipitate and separate unit 5 top is connected with reuse water pipe, and base sludge outlet is connected with resolution of precipitate unit 7 water-in; Described resolution of precipitate unit 7 liquid outlet is connected with described second precipitate and separate unit 8 water-in.
Wherein, also pretreatment unit is connected with before described forward osmosis unit 3; Described pretreatment unit is preferably set to comprise sand-bed filter 1 and immersion ultrafiltration tank 2; Described forward osmosis unit 3 specifically comprises waste water room, semipermeable partition 6 and draws room, and described waste water room and described drawing between room use semipermeable partition 6 to separate; Described semipermeable partition 6 is preferably set to polyamide composite film; Described drawing above room is connected with Adlerika filling, and below is connected with dilute sulphuric acid magnesium solution and fills with, and described dilute sulphuric acid magnesium solution is filled with and passed into described reaction precipitation unit 4.
Described reaction precipitation unit 4 is connected with barium hydroxide solution tank, and installs agitator and stir; Described resolution of precipitate unit 7 is connected with sulphuric acid soln tank, and installs agitator and stir; Described second precipitate and separate unit 8 supernatant liquor outlet is connected with immersion ultrafiltration pond 9 water-in; Described first and second precipitation unit all preferably adopt radical sedimentation basin.
embodiment 1
Advanced treatment object is the coking chemical waste water after biological treatment, TDS(total dissolved solid in waste water) be about 1000mg/L.
First waste water enter sand-bed filter 1 and filter, and then enters immersion ultrafiltration tank 2, and ultra-filtration filters precision is 0.1 micron, then enters forward osmosis unit 3; The Adlerika drawing liquid employing 60g/L of forward osmosis unit 3, after forward osmosis unit 3, waste water is concentrated to about 10g/L, and cycles of concentration is 10 times, and producing water ratio is 90%, and the waste water after concentrated is arranged outward or disposes; Adlerika after dilution flows into reaction precipitation unit 4, with Ba (OH) wherein
2solution reaction generates Mg (OH)
2precipitation and BaSO
4precipitation, is then separated by the first precipitate and separate pond 5 and obtains supernatant liquor and bed mud, and supernatant liquor saliferous is very low as producing reuse water, and bed mud enters resolution of precipitate pond 7 then by 20% H
2sO
4mg (OH) is removed in acidifying
2precipitation, the BaSO obtained
4precipitation dehydration further, dry obtained bright sulfur acid barium dust, the Adlerika obtained turns back to positive permeation unit 3 as drawing liquid water inlet.
embodiment 2
Advanced treatment object is the municipal wastewater after biological treatment, TDS(total dissolved solid in waste water) be about 500mg/L.
First waste water enter sand-bed filter 1 and filter, and then enters immersion ultrafiltration tank 2, and ultra-filtration filters precision is 0.1 micron, then enters forward osmosis unit 3; The Adlerika drawing liquid employing 16g/L of forward osmosis unit 3, after forward osmosis unit 3, waste water is concentrated to about 6g/L, and cycles of concentration is 12 times, and producing water ratio is 92%, and the waste water after concentrated is arranged outward or disposes; Adlerika after dilution flows into reaction precipitation unit 4, with Ba (OH) wherein
2solution reaction generates Mg (OH)
2precipitation and BaSO
4precipitation, then obtains supernatant liquor and bed mud by the first precipitate and separate pond 5, and supernatant liquor saliferous is very low as producing reuse water, and bed mud enters resolution of precipitate pond 7 then by 40% H
2sO
4acidifying is dissolved and is removed Mg (OH)
2precipitation, the BaSO obtained
4precipitation is filtered further, dry obtained bright sulfur acid barium dust, and the Adlerika obtained turns back to positive permeation unit 3 as drawing liquid water inlet.
embodiment 3
Advanced treatment object is the strong brine of reverse osmosis desalination water station, TDS(total dissolved solid in waste water) be about 8000mg/L.
First waste water enter sand-bed filter 1 and filter, and then enters immersion ultrafiltration tank 2, and ultra-filtration filters precision is 0.1 micron, then enters forward osmosis unit 3; The Adlerika drawing liquid employing 210g/L of forward osmosis unit 3, after forward osmosis unit 3, waste water is concentrated to about 48g/L, and cycles of concentration is 6 times, and producing water ratio is 83%, and the waste water after concentrated is arranged outward or disposes; Adlerika after dilution flows into reaction precipitation unit 4, with Ba (OH) wherein
2solution reaction generates Mg (OH)
2precipitation and BaSO
4precipitation, then mixture is separated by the first precipitate and separate pond 5 and obtains supernatant liquor and bed mud, and supernatant liquor saliferous is very low as producing reuse water, and bed mud enters resolution of precipitate pond 7 then by 30% H
2sO
4mg (OH) is removed in digestion
2precipitation, the BaSO obtained
4precipitation is filtered further, dry obtained bright sulfur acid barium dust, and the Adlerika obtained turns back to positive permeation unit 3 as drawing liquid water inlet.
Present invention process method prepares lightweight barium sulfate while achieving waste water desalination, it uses equipment simple, easy to operate, greatly reduce production cost and time cost prepared by barium sulfate, the waste liquid produced still can return as drawing liquid water inlet, the resource utilization really achieving waste water reclaims, and has good market outlook.
Finally it should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted; although with reference to preferred embodiment to invention has been detailed description; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement; and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the protection domain of claim of the present invention.
Claims (9)
1. utilize waste water desalination to hold concurrently and prepare a method for lightweight barium sulfate, it is characterized in that, described technique adopts Adlerika as drawing liquid, is permeated the water molecules drawn in waste water by forward osmosis unit; Obtain adding barium hydroxide solution reaction in the Adlerika after diluting, obtain the mixed precipitation suspended substance containing magnesium hydroxide and barium sulfate, described suspended substance obtains mixed precipitation and clear water through precipitate and separate, described clear water carries out reuse, described mixed precipitation adds sulfuric acid acidation reaction dissolving removal magnesium hydroxide and obtains the pure barium sulfate of lightweight, and the Adlerika that sulfuric acid dissolution magnesium hydroxide obtains returns as drawing liquid.
2. the method for claim 1, is characterized in that, the described Adlerika concentration as drawing liquid is greater than raw material waste water total dissolved solid concentration.
3. the method as described in claim arbitrary in claim 1 or 2, is characterized in that, the described Adlerika concentration as drawing liquid is 16 ~ 250g/L, is preferably 60g/L.
4. the method as described in claim arbitrary in claim 1-3, is characterized in that, first waste water enter pretreatment unit carries out pre-treatment and remove suspended substance and colloid, then enters forward osmosis unit; Magnesium sulfate in forward osmosis unit draws the liquid water drawn in waste water and is formed and draw liquid water outlet and flow into reaction precipitation unit and barium hydroxide solution and react and generate magnesium hydroxide and barium sulfate mixture suspension, described mixture suspension obtains mixed sediment and clear water through precipitate and separate, described clear water carries out reuse, described mixed sediment dissolves removal magnesium hydroxide by sulfuric acid acidation reaction and obtains the pure barium sulfate of lightweight, and the Adlerika that sulfuric acid dissolution magnesium hydroxide obtains returns as drawing liquid water inlet after ultra-filtration filters;
Preferably, described sulfuric acid adopts mass concentration to be the sulfuric acid of 20 ~ 40%.
5. one kind realizes the device of method as described in claim arbitrary in claim 1-4, it is characterized in that, described device comprises forward osmosis unit, reaction precipitation unit, the first precipitate and separate unit, resolution of precipitate unit and the second precipitate and separate unit, the water outlet of described forward osmosis unit is communicated with described reaction precipitation unit water-in, and the liquid outlet of described reaction precipitation unit is connected by the water-in of slush pump with described first precipitate and separate unit; The clear water output on described first precipitate and separate unit top is connected with reuse water pipe, and base sludge outlet is connected with resolution of precipitate unit water-in; Described resolution of precipitate unit liquid outlet is connected with described second precipitate and separate unit water-in.
6. device as claimed in claim 5, is characterized in that, be connected with pretreatment unit before described forward osmosis unit;
Preferably, described pretreatment unit comprises sand-bed filter and immersion ultrafiltration tank.
7. the device as described in claim 5 or 6, is characterized in that, described forward osmosis unit comprises waste water room, semipermeable partition and draws room, and described waste water room and described drawing between room use semipermeable partition to separate;
Preferably, described semipermeable partition is polyamide composite film.
8. device as claimed in claim 7, is characterized in that, described in draw and be connected with Adlerika above room and fill with, below is connected with dilute sulphuric acid magnesium solution and fills with, and described dilute sulphuric acid magnesium solution is filled with and passed into described reaction precipitation unit.
9. the device as described in claim arbitrary in claim 5-8, is characterized in that, described reaction precipitation unit is connected with barium hydroxide solution tank, and installs agitator and stir; Described resolution of precipitate unit is connected with sulphuric acid soln tank, and installs agitator and stir; Described second precipitate and separate unit supernatant liquor outlet is connected with immersion ultrafiltration pond water-in;
Preferably, described first and second precipitation unit all adopt radical sedimentation basin.
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| CN201410452970.5A CN104229856B (en) | 2014-09-09 | 2014-09-09 | A kind of method and device thereof utilizing waste water desalination to hold concurrently to prepare lightweight barium sulfate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130075333A1 (en) * | 2011-09-22 | 2013-03-28 | Randall B. Pruet | Apparatus and Process for Treatment of Water |
| CN103288252A (en) * | 2013-06-24 | 2013-09-11 | 北京赛科康仑环保科技有限公司 | A wastewater desalination process with a high water yielding rate and a device thereof |
| EP2692417A1 (en) * | 2012-07-31 | 2014-02-05 | Hydration Systems, Llc | Organic forward osmosis system |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130075333A1 (en) * | 2011-09-22 | 2013-03-28 | Randall B. Pruet | Apparatus and Process for Treatment of Water |
| EP2692417A1 (en) * | 2012-07-31 | 2014-02-05 | Hydration Systems, Llc | Organic forward osmosis system |
| CN103288252A (en) * | 2013-06-24 | 2013-09-11 | 北京赛科康仑环保科技有限公司 | A wastewater desalination process with a high water yielding rate and a device thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李海军 等: "对称正渗透制备及膜性能表征", 《环境科学与技术》 * |
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