CN101016175A - Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution - Google Patents
Method of eliminating magnesium sulfate from magnesium sulfate containing waste water solution Download PDFInfo
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- CN101016175A CN101016175A CN 200610042339 CN200610042339A CN101016175A CN 101016175 A CN101016175 A CN 101016175A CN 200610042339 CN200610042339 CN 200610042339 CN 200610042339 A CN200610042339 A CN 200610042339A CN 101016175 A CN101016175 A CN 101016175A
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Abstract
The invention discloses a removing method of magnesium sulfate from waste water solution with magnesium sulfate, which comprises the following steps: predisposing waste water solution with magnesium sulfate; transmitting the solution into micro-filter film device to remove micro-particle impurity; transmitting the solution into nano-filter film; obtaining percolation liquid with low-content magnesium sulfate and condensate with high-content of magnesium sulfate; freezing the condensate; extracting the solid of magnesium sulphate heptahydrate or adding calcium salt or barium salt to obtain calcium sulfate or barium sulfate; reacting magnesium salt and calcium hydroxide to produce magnesium hydroxide and calcium salt; saving the disposing cost; protecting environment; recycling magnesium sulfate.
Description
Technical field
The invention provides a kind of method of wastewater treatment, especially the treatment process of magnesium sulfate containing waste water solution.
Background technology
Can produce the waste water solution of a large amount of sulfur acid magnesium in the industrial production, the waste water that forms after heat power plant's flue gas magnesium method desulfurization is exactly like this.Describe as example below.Sulfurous gas in the coal-fired flue-gas can pollute environment, and therefore, (desulfurization) conduct that removes of sulfurous gas influences the important factor that power plant moves, and more and more obtains paying attention to.Magnesium oxide wet desulfurizing process in the sulfur removal technology is sweetening agent with magnesium oxide, and this process system is simple, and adaptability is good, therefore obtained in the last few years using very widely, and the trend that progressively replaces calcium-based desulfurization is arranged.In the magnesium oxide wet desulphurization device, magnesium oxide powder is lifted in the magnesium oxide thinning tank, feed process water, and stir, magnesium oxide dissolving back generates Mg (OH)
2Solution.After this solution is adjusted to suitable concentration with process water, be transported to the Mg (OH) that is provided with stirrer
2Storage tank.According to the pH changing conditions of sulfur dioxide in flue gas change in concentration, desulfurization index and oxidation pond and water collecting basin, regulate the magnesium hydroxide injection rate, be transported to water collecting basin and oxidation pond with the magnesium hydroxide slurry transferpump again.The flue gas of introducing from coal firing boiler induced draft fan rear end is lowered the temperature in the Venturi tube of sweetener, sends into the absorption tower after removing dust.The flue gas of discharging from sweetener is through the upper end smoke stack emission.Flow into round shape high pressure venturi tower downwards from the high-temperature flue gas of dry electric precipitation device discharging,, generate magnesium sulfite (MgSO with the abundant contact reacts of water gas/liquid in small area of the equidirectional spray of introducing of flue gas
3).With recycle pump the water in the water collecting basin is got to the nozzle spray, make desulfurization sewage form slurries, remove big dust particle and partial oxidation sulphur in this process.With recycle pump slurries are delivered in the thionizer,, absorb sulfur in smoke through the nozzle spray.Subsequently, the slurries static pressure flows into water collecting basin.One typhoon machine makes magnesium oxide and desulfurization sewage thorough mixing, magnesium sulfite (MgSO to water collecting basin bottom forced air supply
3) further be oxidized to sal epsom (MgSO
4), and prevent sedimentation of suspension.Recycle pump is squeezed into absorption tower individual layer nozzle with the desulfurization sewage in the water collecting basin, and desulfurization sewage flows into water collecting basin again.At the thionizer smoke inlet distribution plate or porous plate are set, flue gas is evenly flowed.Utilize the positive plate of specific current device and the high-voltage electric field that negative plate energising back produces, with the sulfurous gas (SO that does not remove in round shape high pressure venturi tower and the absorption tower
2), dust, the trace HCl and HF, sulphur trioxide (SO
3) wait other objectionable impurities to remove.
The desulfurization wastewater that contains sal epsom that above-mentioned sulfur removal technology produces is directly outwards discharging after removing suspended substance, and therefore, desulfurization sewage can cause secondary pollution to environment again.Simultaneously, also caused the waste of the sal epsom that the value utilized is arranged.
Summary of the invention
Technical problem to be solved by this invention is to provide the method that removes the sal epsom in the magnesium sulfate containing waste water solution in a kind of industrial production, to alleviate the environmental pollution that causes, the abundant sal epsom of recycling in the waste water of while.
The present invention is achieved in that a kind of method that removes the sal epsom in the magnesium sulfate containing waste water solution, and described method is,
A, magnesium sulfate containing waste water solution is carried out pre-treatment, remove suspended substance and large granular impurity;
B, will send into the microfiltration membrane device through pretreated magnesium sulfate containing waste water solution and remove molecule impurity;
C, the magnesium sulfate containing waste water solution that will remove molecule impurity are sent into the nanofiltration membrane device through the pump pressurization and are carried out nanofiltration, obtain low penetrating fluid of sal epsom content and the high concentrated solution of sal epsom content, during nanofiltration, the concentration of sal epsom is between 1g/l～30g/l in the magnesium sulfate containing waste water solution, the temperature of magnesium sulfate containing waste water solution is controlled between 25～70 ℃, the pH value is controlled between 3～7, and working pressure is controlled between 5bar～35bar;
D, utilize after-treatment device to carry out freezing treatment the high concentrated solution of sal epsom content that obtains, therefrom extract the magnesium sulfate heptahydrate solid; Perhaps add the high concentrated solution reaction of calcium salt or barium salt and sal epsom content and generate calcium sulfate precipitation thing or barium sulfate precipitate thing, get calcium sulfate or barium sulfate, magnesium salts and calcium hydroxide reaction generate magnesium hydroxide and calcium salt.
This method that removes the sal epsom in the magnesium sulfate containing waste water solution has following advantage:
1, sulfur acid magnesium seldom can be used as process water and uses in the penetrating fluid of nanofiltration gained.
2, magnesium sulfate concentration height in the concentrated solution, quality is good, and other foreign matter content is few.
3, nanofiltration membrane plant area area is little.
4, running cost is low, and the operation of nanofiltration membrane device only consumes the required electric energy of fresh feed pump.
5, the sewage quantity of this method generation is few, helps environmental protection.
6, utilize the recyclable sal epsom that utilizes of freezing treatment, have tangible economic benefit; Add calcium salt or barium salt concentrated solution is handled, can reuse calcium salt and magnesium hydroxide, have good economic benefit and environmental benefit.
Description of drawings
Fig. 1 uses a kind of schematic representation of apparatus that specifically removes of the present invention.
The synoptic diagram of the nanofiltration membrane component in Fig. 2 nanofiltration membrane device of the present invention.
Embodiment
Further specify the present invention below.
The microfiltration membrane material that adopts in described microfiltration membrane device is a kind of in polypropylene (PP), poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene (PTFE), carbon microporous pipe, metal micro-holes pipe and the tubular ceramic membrane.
The nanofiltration membrane material that adopts in described nanofiltration membrane device is a kind of in polysulfones (PS), laminated film (TFM), cellulose acetate (CA), aromatic polyamides (PA), polyvinyl alcohol (PVA), the semi-annular jade pendant polyethersulfone (SPES).
When carrying out nanofiltration, the temperature of magnesium sulfate containing waste water solution is controlled between 40～50 ℃.
The nanofiltration membrane device has adopted membrane separation technique among the present invention.Film whether the dissolved component can be separated from solution the size that depends on this component, electric charge, shape and with the interaction on film surface.Because the atomic radius of sal epsom comes the separating magnesium sulphate waste water solution with nanofiltration membrane about 0.202 nanometer, just can obtain low penetrating fluid of sal epsom content and the high concentrated solution of sal epsom content.During nanofiltration, most monovalent salts in the desulfurization wastewater and water obtain the low penetrating fluid of sal epsom content by nanofiltration membrane, flow out from the penetrating fluid outlet of nanofiltration membrane device.Divalent salts such as most of sal epsom, magnesiumcarbonate, magnesium sulfite are then repelled concentrated by nanofiltration membrane, obtain the high concentrated solution of sal epsom content, and the concentrated solution outlet on the nanofiltration membrane system flows out.
Shown in Figure 1 is a kind ofly carries out freezing treatment with the concentrated solution after the nanofiltration and obtains extracting the magnesium sulfate heptahydrate solid, and further handles the device that obtains anhydrous magnesium sulfate.This device has activated charcoal filter (2) to link to each other with Adlerika jar (1), the activated charcoal filter back is connected with security personnel's strainer (3), security personnel's strainer back is connected with nanofiltration membrane device (4), be connected with concentrated flow container (5) on the concentrated solution outlet of nanofiltration membrane device, concentrate the flow container back and be connected with pre-cooler (6), the pre-cooler back is connected with interchanger (7), and the interchanger back is connected with settling vessel (8), and the settling vessel back is connected with whizzer (9).
The principle of work of this device is, Adlerika from heat power plant's desulfurizer and other full scale plant enters big container for storing liquid (15), the processing of the filtering net in the process pretreater (14) etc., enter Adlerika jar (1) after removing large granular impurity, in this jar, adjust the pH value by adding acid or adding alkali, make it to meet the requirement of follow up device, by pump Adlerika is squeezed into activated charcoal filter (2), utilize the physical adsorption and the chemisorption of gac to remove residual free chlorine, the activated charcoal filter outlet then links to each other with microfiltration membrane device (3) import, the effect molecule impurity of microfiltration membrane device (filter core can be selected 5um or 3um as required) enters the nanofiltration membrane filtration unit, in order to avoid pollute nanofiltration membrane.Will be through the more purified Adlerika pressurization of above-mentioned processing, make it enter nanofiltration membrane filtration unit (4), most monovalent salts and water in the Adlerika pass through nanofiltration membrane, obtain the lower penetrating fluid of magnesium sulfate concentration, divalent salts such as most of sal epsom, magnesiumcarbonate, magnesium sulfite are then repelled concentrated by nanofiltration membrane, enter concentrated flow container (5) from concentrated solution outlet.The concentrated solution that comes out from concentrate flow container is squeezed into pre-cooler (6) with pump and is carried out precooling, precooling temperature is controlled at-15 ℃～0 ℃, sal epsom crystallization in the concentrated solution, then, enter in the settling vessel (8) and carry out sedimentation, clear liquid in the settling vessel is squeezed into interchanger (7) and chilled brine or liquefied ammonia by pump and is carried out heat exchange and further cool off, and the concentrated solution with precooling enters settling vessel then, can prevent the obstruction of interchanger so effectively.Flow into whizzer (9) from the effusive fluid in settling vessel bottom,, can obtain containing the magnesium sulfate heptahydrate solid by centrifugation.
Also have dissolving vessel (10) in described whizzer (9) back, the dissolving vessel back is connected with vaporizer (11), and there is another whizzer (13) the vaporizer back.The magnesium sulfate heptahydrate solid that comes out from whizzer enters dissolving vessel (10), dissolves by adding steam or hot water.Adlerika after the dissolving enters vaporizer (11) by pump, and further crystal water is removed in evaporation, and enters whizzer (13) and carry out recentrifuge, can obtain the finished product anhydrous magnesium sulfate through warm air drying, sells as finished product through packing then.
Also be connected with another vaporizer (12) in described vaporizer (11) back, another vaporizer (12) is connected on another whizzer (13).Vaporizer (11) is worked simultaneously with another vaporizer (12), can improve vaporization efficiency.
As shown in Figure 2, perforated base pipe (16) is arranged on the nanofiltration membrane component in the nanofiltration membrane device, the perforated base pipe outside is staggered the material layer of catchmenting (17), nanofiltration membrane (18), water conservancy diversion net (20), and outermost is outer packaging shell (19).Treat that the concentrated vitriol magnesium liquid enters in the nanofiltration membrane component along feedstock direction, most monovalent salts and water in the sal epsom liquid enter perforated base pipe by nanofiltration membrane, obtain the low penetrating fluid of sal epsom content, and the penetrating fluid outlet on the nanofiltration membrane system is flowed out.Divalent salts such as most of sal epsom, magnesiumcarbonate, magnesium sulfite are then repelled concentrated by nanofiltration membrane, obtain the high concentrated solution of sal epsom content, and the concentrated solution outlet from nanofiltration membrane component flows out.By follow-up cooling process, different according to its Tc and other divalent salts are separated sal epsom.
A plurality of (being generally 2～6) nanofiltration membrane component serial or parallel connection can be installed in the case frame, realize modularization, compact construction is easy to install, and floor space is little.The quantity of nanofiltration membrane component can be selected according to the flow of Adlerika.
Nanofiltration membrane can be passed through physics and chemical process modification, increases film surface charge enrichment degree, makes it have the good sal epsom performance of taking off.
Add calcium salt or barium salt in the high concentrated solution of the sal epsom content that obtains after, calcium salt or barium salt and sal epsom reaction generate calcium sulfate precipitation thing or barium sulfate precipitate thing, and sedimentary calcium sulfate, barium sulfate are separated, and can be used as byproduct and sell.After adding calcium salt, magnesium salts then can generate magnesium hydroxide and calcium salt with calcium hydroxide reaction, thereby reclaims Mg (OH)
2, can be in the magnesium method flue gas desulphurization device reusable Mg (OH)
2, also it can be sold as product, calcium salt also can be reused in reaction.
Described magnesium sulfate containing waste water solution is carried out pre-treatment, be meant by filtering net in the pretreater etc. and remove wherein suspended substance and large granular impurity, then waste water solution is sent into the Adlerika jar, in jar, adjust the pH value by adding acid or alkali, make it to meet the requirement of follow up device, by pump Adlerika is squeezed into activated charcoal filter, utilize the physical adsorption of gac and chemisorption to remove residual free chlorine.
Described after-treatment device comprises concentrated flow container (5), pre-cooler (6), interchanger (7), settling vessel (8), whizzer (9).
The present invention is further illustrated below by embodiment.
In each embodiment, step a, b, d are all identical, promptly all magnesium sulfate containing waste water solution are carried out pre-treatment, remove suspended substance and large granular impurity; And will send into the microfiltration membrane device through pretreated magnesium sulfate containing waste water solution and remove molecule; Send into the nanofiltration membrane device then and carry out nanofiltration; Carry out freezing treatment after the nanofiltration, extract the magnesium sulfate heptahydrate solid, or in concentrated solution, add calcium salt or barium salt.Therefore, only the situation of step c is described.
In an embodiment, the permeation flux of sal epsom, rejection definition and calculation formula are as follows:
Following table is the situation of the step c of each embodiment.
| Feeding liquid | Penetrating fluid | Concentrated solution | Permeation flux L/m 2.h | Magnesium sulfate rejection rate % | |||||
| PH value | Temperature ℃ | Flow L/h | Pressure MPa | Magnesium sulfate concentration g/l | Magnesium sulfate concentration g/l | Magnesium sulfate concentration g/l | |||
| Embodiment 1 | 6.5 | 25 | 186 | 0.5 | 1.8 | 0.08 | 2.15 | 17 | 95.5 |
| Embodiment 2 | 6.8 | 25 | 196 | 0.7 | 2.1 | 0.05 | 2.41 | 18 | 97.6 |
| Embodiment 3 | 7 | 30 | 903 | 1 | 16.8 | 0.46 | 18.23 | 25.2 | 97.26 |
| Embodiment 4 | 4.5 | 42 | 2205 | 1.4 | 8.8 | 0.85 | 13.5 | 16.0 | 90.3 |
| Embodiment 5 | 4.5 | 40 | 2110 | 1.4 | 8.19 | 0.77 | 12.6 | 15.7 | 90.6 |
Claims (4)
1, a kind of method that removes the sal epsom in the magnesium sulfate containing waste water solution is characterized in that, described method is,
A, magnesium sulfate containing waste water solution is carried out pre-treatment, remove suspended substance and large granular impurity;
B, will send into the microfiltration membrane device through pretreated magnesium sulfate containing waste water solution and remove molecule impurity;
C, the magnesium sulfate containing waste water solution that will remove molecule impurity are sent into the nanofiltration membrane device through the pump pressurization and are carried out nanofiltration, obtain low penetrating fluid of sal epsom content and the high concentrated solution of sal epsom content, during nanofiltration, the concentration of sal epsom is between 1g/l～30g/l in the magnesium sulfate containing waste water solution, the temperature of magnesium sulfate containing waste water solution is controlled between 25～70 ℃, the pH value is controlled between 3～7, and working pressure is controlled between 5bar～35bar;
D, utilize after-treatment device to carry out freezing treatment the high concentrated solution of sal epsom content that obtains, therefrom extract the magnesium sulfate heptahydrate solid; Perhaps add the high concentrated solution reaction of calcium salt or barium salt and sal epsom content and generate calcium sulfate precipitation thing or barium sulfate precipitate thing, get calcium sulfate or barium sulfate, magnesium salts and calcium hydroxide reaction generate magnesium hydroxide and calcium salt.
2, the method that removes the sal epsom in the magnesium sulfate containing waste water solution as claimed in claim 1, it is characterized in that the microfiltration membrane material that adopts is a kind of in polypropylene (PP), poly(vinylidene fluoride) (PVDF), polytetrafluoroethylene (PTFE), carbon microporous pipe, metal micro-holes pipe and the tubular ceramic membrane in described microfiltration membrane device.
3, the method that removes the sal epsom in the magnesium sulfate containing waste water solution as claimed in claim 1 or 2, it is characterized in that the nanofiltration membrane material that adopts is a kind of in polysulfones (PS), laminated film (TFM), cellulose acetate (CA), aromatic polyamides (PA), polyvinyl alcohol (PVA), the semi-annular jade pendant polyethersulfone (SPES) in described nanofiltration membrane device.
4, the method that removes the sal epsom in the magnesium sulfate containing waste water solution as claimed in claim 1 or 2 is characterized in that, when carrying out nanofiltration, the temperature of magnesium sulfate containing waste water solution is controlled between 40～50 ℃.
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| CN106396234A (en) * | 2016-11-25 | 2017-02-15 | 洁海瑞泉膜技术（天津）有限公司 | Zero-discharge treatment method for reverse osmosis concentrated water |
| CN107098366A (en) * | 2017-04-25 | 2017-08-29 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
| CN107098366B (en) * | 2017-04-25 | 2018-12-04 | 中国恩菲工程技术有限公司 | The method for handling magnesium-containing waste solution |
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| CN108101079A (en) * | 2018-02-12 | 2018-06-01 | 山东奥美环境股份有限公司 | Embrane method dechlorination method, apparatus and magnesium sulfate production system |
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| CN109095732A (en) * | 2018-10-30 | 2018-12-28 | 华北电力大学（保定） | A kind of technique based on magnesium processes desulfurization wastewater high-purity magnesium hydroxide |
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Denomination of invention: A method for removing magnesium sulfate from wastewater solution containing magnesium sulfate Effective date of registration: 20231205 Granted publication date: 20111005 Pledgee: Binzhou Bincheng Branch of China Construction Bank Co.,Ltd. Pledgor: BEFAR GROUP Co.,Ltd. Registration number: Y2023980069546 |
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