CN110436540A - A method of efficiently removing sulfate radical in water removal - Google Patents
A method of efficiently removing sulfate radical in water removal Download PDFInfo
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- CN110436540A CN110436540A CN201910759411.1A CN201910759411A CN110436540A CN 110436540 A CN110436540 A CN 110436540A CN 201910759411 A CN201910759411 A CN 201910759411A CN 110436540 A CN110436540 A CN 110436540A
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- Prior art keywords
- water
- sulfate radical
- passed
- sulfate
- water removal
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
Abstract
The invention discloses a kind of methods for efficiently removing sulfate radical in water removal, comprising the following steps: (1) barium carbonate is added into the water of containing sulfate radicals, is then stirred；(2) carbon dioxide gas is passed through into water while stirring makes the pH value value of mixed liquor be reduced to 6.5 or less；(3) stop stirring, stopping is passed through carbon dioxide gas, is passed through air and carries out stripping, pH value is made to be increased to 7 or more；(4) mixed liquor is staticly settled, and the sulfate ion in supernatant is efficiently removed.The present invention provides a kind of method to remove sulfate radical in drinking water or recycle-water, does not introduce other pollutants while removing sulfate radical, and the removal rate of sulfate radical can reach 99% or more, while have the advantage in cost, can widely popularize application.
Description
[technical field]
The invention belongs to technical field of waste water processing, and in particular to a method of efficiently remove sulfate radical in water removal.
[background technique]
Often containing the sulfate of high level in underground water and water, the sulfate in water easily forms colloidal with calcium ion
Calcium sulfate is one of the main component of water fouling, influences its industrial application；The water that long-term drinking contains high concentration sulfate can draw
Play the health problems such as diarrhea, function of intestinal canal disorder；And it will cause the salinization of soil in soil in irrigating using the water of high-sulfate.Cause
This, the sulfate of surface water three classes requires to meet the requirement lower than 250mg/L in " surface water quality standard " in China
Under the premise of, the presence of sulfate will not generally throw into question.
The sulfate concentration in water is reduced, common method has barium chloride method, calcium method, barium carbonate method, embrane method, absorption, life
Object method etc..Bioanalysis is usually used in sewage treatment, and sulfate radical is mainly reverted to elemental sulfur or sulphur using sulfate reducing bacteria
Ion separates elemental sulfur or sulphion again later.This method have it is at low cost, organic matter can be removed simultaneously, is high-efficient
Advantage is suitable in sewage containing organic matter and sewage has the occasion of proper temperature.
Embrane method is the ion screening capacity using nanofiltration or reverse osmosis membrane, and sulfate radical is stayed in concentrated water, thus real
The place to go of existing sulfate radical.This method is high-efficient, stability is good, but this method high investment, and the processing cost is high for concentrated water, limit
The application of this method is made.
Absorption method mainly achievees the purpose that remove sulfate ion, but overall adsorption using the selection adsorption capacity of absorption
Capacity is not high, and for the sulfate wastewater of higher concentration, operating cost is excessively high.
Barium chloride method has very high efficiency, can be realized the almost all removal of sulfate radical, but is the introduction of chloride ion,
Cause new pollution.
Calcium method refers to that calcium hydroxide or quick lime, the method, which is added, goes sulfate radical to be not thorough, and often has a large amount of sulphur after processing
Sour calcium residual, goes sulfate radical to be not thorough.
For barium carbonate method because the solubility of barium carbonate is very low, reaction efficiency is not high, it is desirable that higher temperature and longer stops
The time is stayed, practical application effect is not good enough, needs to be improved.
[summary of the invention]
The present invention provides a kind of method for efficiently removing sulfate radical in water removal, to solve the barium carbonate method of the prior art because of carbon
The solubility of sour barium is very low, and reaction efficiency is not high, it is desirable that higher temperature and longer residence time, practical application effect be not good enough
The technical issues of.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A method of efficiently removing sulfate radical in water removal, comprising the following steps:
(1) barium carbonate is added into the water of containing sulfate radicals, is then stirred；
(2) carbon dioxide gas is passed through into water while stirring makes the pH value value of mixed liquor be reduced to 6.5 or less；
(3) stop stirring, stopping is passed through carbon dioxide gas, is passed through air and carries out stripping, pH value is made to be increased to 7 or more；
(4) mixed liquor is staticly settled, and the sulfate ion in supernatant is efficiently removed.
Further, the molar ratio for the sulfate radical in barium carbonate and water being added in step (1) is 1 to 1.5.
Further, the barium carbonate includes the suspension formed after barium carbonate dry powder or barium carbonate are mixed with water.
Further, stirring can be completed with being passed through for carbon dioxide gas in closed container in step (2).
Further, barium carbonate and water mix to form suspension during be passed through carbon dioxide gas, to improve slurries
In barium ions concentration.
Further, the process control reaction temperature of carbon dioxide gas is passed through at 22 DEG C or less.
Further, the process that barium carbonate and water mix the suspension to be formed can be completed in the direct draught of 0.01-0.6mPa.
Further, carbon dioxide gas passes through micro-hole aerator and forms small bubble in water in step (2).
Further, anion-polyacrylamide, the precipitation process of accelerating step (3) are added before precipitation process.
Further, the stripping process of step (3) can be replaced using lime is added.
The present invention has following effects:
The present invention provides a kind of method to remove sulfate radical in drinking water or recycle-water, while removing sulfate radical
Other pollutants are not introduced, and the removal rate of sulfate radical can reach 99% or more, while have the advantage in cost, can push greatly
Wide application.
[Detailed description of the invention]
Fig. 1 is the method flow schematic diagram of the invention for efficiently removing sulfate radical in water removal.
[specific embodiment]
To facilitate a better understanding of the present invention, it is illustrated by the following examples, these examples belong to protection of the invention
Range, but do not limit the scope of the invention.
In embodiment, the method for efficiently removing sulfate radical in water removal, comprising the following steps:
(1) suspension formed after barium carbonate dry powder or barium carbonate and water mixing is added into the water containing sulfate, adds
The molar ratio of the sulfate radical in barium carbonate and water entered is 1 to 1.5, is followed by stirring for；
(2) carbon dioxide gas is passed through into water while stirring makes the pH value value of mixed liquor be reduced to 6.5 hereinafter, being passed through
The purpose of carbon dioxide gas is to reduce pH value to dissolve out the barium ions in barium carbonate into water, which exists
22 DEG C hereinafter, the carbon dioxide gas forms small bubble by micro-hole aerator in water；
(3) stop stirring, stopping is passed through carbon dioxide gas, is then passed through air and carries out stripping, which can use
Lime is added to replace, pH value is made to be increased to 7.6 or more, anion-polyacrylamide (PAM) is added before being passed through air in stopping, adding
Fast precipitation process；
(4) mixed liquor is separated by solid-liquid separation, and efficient removal can be realized in the sulfate ion in supernatant.
Below by more specifically examples illustrate the present invention.
Embodiment 1
A method of efficiently removing sulfate radical in water removal, comprising the following steps:
(1) it is the waste water 1L of 1500mg/L sulfate ion containing concentration in beaker, 4.6g is then added into beaker
Barium carbonate powder (1.5 times of theoretical dosages), is followed by stirring for；
(2) stirring in beaker is maintained, stirring while is passed through carbon dioxide gas into water, controls pH value of reaction system
For 6.4-6.5, the purpose for being passed through carbon dioxide gas is the barium ions dissolution promoted in barium carbonate, the process control reaction temperature
It is 22 DEG C, the carbon dioxide gas forms small bubble by micro-hole aerator in water；
(3) stopping stirring after reacting 4 hours, stopping is passed through carbon dioxide gas, and lime is added, pH value is made to be increased to 7.8,
Anion-polyacrylamide (PAM) is added into reaction solution, accelerates precipitation process；
(4) mixed liquor is separated by solid-liquid separation, and is precipitated and supernatant, gained precipitating are filtered using 0.45um film, gained
Filter cake barium sulfate content is more than 98%；Gained filtered fluid sulphate-containing ion concentration is 4.5mg/L, the removal of this method sulfate radical
Rate can reach 99.7%.
Embodiment 2
A method of efficiently removing sulfate radical in water removal, comprising the following steps:
(1) it is the waste water 0.5L of 1500mg/L sulfate ion containing concentration in beaker, 4.6g is then added into beaker
Barium carbonate powder, is followed by stirring for；
(2) mixed liquor of stirring is passed through in reaction tank, stirring while is passed through carbon dioxide gas into water, and control is anti-
Answering system pH is 6.4-6.5, which is 22 DEG C, which is to complete in closed container, and maintain
What the positive pressure of 0.4MPa carried out, the carbon dioxide gas forms small bubble by micro-hole aerator in water；
(3) stopping stirring after reacting 30 minutes, stopping is passed through carbon dioxide gas, reaction solution is passed into flocculation basin,
The waste water that 0.5L sulfate ion concentration is 1500mg/L is added to be mixed 30 minutes, is then passed through air and carries out stripping, make
PH value is increased to 7.6, followed by addition anion-polyacrylamide (PAM.；
(4) mixed liquor is separated by solid-liquid separation, and is precipitated and supernatant, and supernatant is through detecting, sulphate-containing ion concentration
For 12.2mg/L, the removal rate of this method sulfate radical can reach 99.19%, and gained precipitating, under a reducing atmosphere calcination obtains sulphur
Change barium.
(5) barium sulfide solution being obtained after barium sulphide washing, is passed through carbon dioxide gas, white precipitate is formed on solution bottom,
Barium carbonate can be obtained after precipitating dehydration, barium carbonate purity is up to 95% or more.
Embodiment 3
A kind of method for efficiently removing sulfate radical in water removal as shown in Figure 1:, comprising the following steps:
(1) waste water for the use of pipe-line mixer being 1500mg/L by the barium carbonate suspension of 10% content and sulphates content
Mixing, wastewater flow 5m3/ h, the flow of barium carbonate suspension are 230L/h (1.5 times of theoretical dosages), enter reaction later
Pond；
(2) reaction tank is equipped with mixing plant and carbon dioxide micro-pore aeration equipment, using industrial carbon dioxide as gas source,
The reaction tank residence time is 6h；Waste water maintains reaction tank blender continued operation after entering reaction tank, and maintains carbon dioxide gas
The aeration of body, the aeration intensity of regulation of carbon dioxide make the control of reaction tank tail end pH value below 6.5；
(3) entering pH value and adjust back pond, pH value is adjusted back the pond residence time 1 hour, and it is 7.6-8 that milk of lime, which is added, and adjusts pH value,
The PAM solution that concentration is 2/1000ths is added later；
(4) enter rectangular sedimentation tank, the supernatant sulfate concentration after precipitating is lower than 15.4mg/L.
Technical principle of the invention:
Barium carbonate is directly put into water, since the solubility of barium carbonate is very low, sulfate radical and barium carbonate in water it is anti-
Answer speed very slow, barium carbonate is added according to 1.5 molar ratio in experiment discovery, and after impregnating three days under room temperature, the sulfate radical in water is gone
Except rate still is below 60%.
After barium sulfate is put into water, then it is lasting into water be passed through carbon dioxide gas, and maintain to stir, may make one
The barium carbonate of solid is divided to be converted into dissolved state barium bicarbonate, barium bicarbonate is in water with the shape of barium ions and bicarbonate ion
Formula exists, and barium ions can form the extremely low barium sulfate of solubility in conjunction with sulfate ion, thus by sulphur in the form of precipitating
Acid ion removal.When sulfate ion concentration is 1500mg/L in water, the amount for the barium carbonate dry powder being added into 1L water is
When 4.6g, aeration and stirring are maintained, pH value is improved using air stripping or addition lime after stopping stirring, is clarified later
Processing, the removal rate of supernatant sulfate radical can reach 99% or more, it is seen that the present invention can efficiently remove sulfate radical in water removal.
Application of the invention:
It has been industrial mature technology that barium sulfate, which produces barium carbonate, produces barium carbonate per ton and needs anthracite 200-
250kg, carbon dioxide 300kg, electric 30kw, removes the raw material cost of barium sulfate, and overall cost can be controlled in 300 yuan/ton or less.This
When technology practical application, barium carbonate factory can be established at the scene, directly converts barium carbonate for barium sulfate, operating cost can
To control at 300 yuan/ton or less.
As sulfate ion concentration 1500mg/L in water, barium carbonate is added according to 1.3 times of theoretical addition amounts, then it is per ton
The medicament dosage of water is 4kg, and medicament expense is about 1.2 yuan, and the carbon dioxide of water treatment portion consumption is about 3kg, and cost is about
0.6 yuan, rest part cost is no more than 0.2 yuan, then water running cost per ton is about 1.9 yuan.And the prior art is using reverse osmosis
Technical treatment same volume with concentration sulphate-containing ion waste water when, nondepreciable water running cost per ton is about 5.6 yuan, high
In 1.95 times of cost of the present invention, it is seen that cost can be substantially reduced using processing method of the invention.
In addition, this technique can realize recycling for barium salt resource, only have a small amount of waste residue to produce during removing sulfate
It is raw, in addition, sulfate is completely converted into vulcanized sodium or thiocarbamide with higher utility value, it is at the more environmentally-friendly water of one kind
Reason technology.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, In
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention by
The scope of patent protection that the claims submitted determine.
Claims (10)
1. a kind of method for efficiently removing sulfate radical in water removal, which comprises the following steps:
(1) barium carbonate is added into the water of containing sulfate radicals, is then stirred；
(2) carbon dioxide gas is passed through into water while stirring makes the pH value value of mixed liquor be reduced to 6.5 or less；
(3) stop stirring, stopping is passed through carbon dioxide gas, is passed through air and carries out stripping, pH value is made to be increased to 7 or more；
(4) mixed liquor is staticly settled, and the sulfate ion in supernatant is efficiently removed.
2. efficiently going the method for sulfate radical in water removal as described in claim 1, which is characterized in that the carbon being added in step (1)
The molar ratio of sulfate radical in sour barium and water is 1 to 1.5.
3. efficiently going the method for sulfate radical in water removal as claimed in claim 2, which is characterized in that the barium carbonate includes carbonic acid
The suspension that barium dry powder or barium carbonate and water are formed after mixing.
4. efficiently going the method for sulfate radical in water removal as described in claim 1, which is characterized in that stirring and two in step (2)
Being passed through for carbon oxide gas can be completed in closed container.
5. efficiently going the method for sulfate radical in water removal as claimed in claim 3, which is characterized in that barium carbonate mixes to be formed with water
Carbon dioxide gas is passed through during suspension, to improve the barium ions concentration in suspension.
6. efficiently going the method for sulfate radical in water removal as claimed in claim 5, which is characterized in that be passed through carbon dioxide gas
Process control reaction temperature is at 22 DEG C or less.
7. efficiently going the method for sulfate radical in water removal as claimed in claim 6, which is characterized in that barium carbonate mixes to be formed with water
The process of suspension can be completed in the direct draught of 0.01-0.6mPa.
8. efficiently going the method for sulfate radical in water removal as described in claim 1, which is characterized in that carbon dioxide in step (2)
Gas forms small bubble by micro-hole aerator in water.
9. the method as described in claim 1 for efficiently removing sulfate radical in water removal, which is characterized in that add before terminating in step (2)
Enter anion-polyacrylamide, the precipitation process of accelerating step (3).
10. efficiently going the method for sulfate radical in water removal as described in claim 1, which is characterized in that the stripping process of step (3)
It can be replaced using lime is added.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111924862A (en) * | 2020-08-31 | 2020-11-13 | 江西云锂材料股份有限公司 | Novel method for preparing lithium carbonate by using lithium sulfate |
| CN112010330A (en) * | 2020-09-09 | 2020-12-01 | 何传冰 | A novel process for extracting lithium from a lithium sulfate solution containing one or more other alkali metal sulfates |
| CN112794555A (en) * | 2020-12-23 | 2021-05-14 | 联合环境技术(天津)有限公司 | Novel method for treating wastewater by reinforced coagulation |
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