CN108483716A - A kind of magnesium sulfate waste water processing equipment for recycling and processing method - Google Patents
A kind of magnesium sulfate waste water processing equipment for recycling and processing method Download PDFInfo
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- CN108483716A CN108483716A CN201810342090.0A CN201810342090A CN108483716A CN 108483716 A CN108483716 A CN 108483716A CN 201810342090 A CN201810342090 A CN 201810342090A CN 108483716 A CN108483716 A CN 108483716A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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Abstract
The present invention relates to a kind of magnesium sulfate waste water processing equipment for recycling and methods, belong to field of waste water treatment.In magnesium sulfate waste water, by adding quick lime, and establishes and sediment classification precipitation is achieved the effect that based on the interior circulating system that calcium ion flows back, magnesium sulfate is precipitated out with calcium sulfate and magnesium hydroxide formal classification, achievees the purpose that resource utilization utilizes.The present invention not only effectively reduces magnesium sulfate waste water salt content, is conducive to successive depths desalination, and sediment is classified the case where not promoting reagent cost and is precipitated, effective recycling.
Description
Technical field
The present invention relates to the device and methods that a kind of magnesium sulfate waste water recycling treatment recycles calcium sulfate and magnesium hydroxide, belong to
In water process and waste water resource recycling field
Background technology：
Although the processing of high-salt wastewater is not problem, a large amount of reagent consumptions or membrane filtration are generally required along with film dirt
Dye and energy consumption problem, the special higher waste water of salt content, can review the pollutant in waste water be also resource substance, effectively extract
Reuse is the processing for such magnesium sulfate waste water where problem, and main methods have evaporative crystallization and preformed precipitate+depth de-
Salt combines this two major classes, and wherein evaporative crystallization needs a large amount of energy consumptions and magnesium sulfate crystallization waste water contains plurality of impurities, including a huge sum of money
Belong to etc., so that magnesium sulfate crystallization is impure, and use scope is limited by content of beary metal, and most economical effective ways are still
Preformed precipitate reduces its salt content.
And quick lime economy, be easy to get, can be used as good precipitating reagent just, a kind of precipitating reagent be added output calcium sulfate and
Two kinds of sediments of magnesium hydroxide, will not additionally cause other a large amount of ions, but this mode causes calcium sulfate and magnesium hydroxide
It is co-precipitated output, is thoroughly mixed, solid waste is formed, and calcium sulfate and magnesium hydroxide are industrial required common objects
Matter, so this processing mode be easy to cause waste and the secondary environmental problems of resource.
The present invention purpose be while effectively reducing waste water salt content in the preformed precipitate stage by calcium flow back means will
Former mixed precipitation calcium sulfate and magnesium hydroxide are detached by fractional precipitation, generate very high environmental benefit and economic benefit.
Invention content：
The purpose of the present invention is there are many kinds of substance co-precipitation during the precipitation process for existing magnesium sulfate waste water
Phenomenon provides a kind of sediment and separates Precipitation, the device for the magnesium sulfate waste water recycling treatment that no solid waste generates
And method, apparatus of the present invention can be while reducing magnesium sulfate waste water salt content by calcium sulfate and magnesium hydroxide classification recycling profit
With, have high environmental benefit and economic benefit, achieve the purpose that recycling magnesium sulfate waste water.
To achieve the purpose of the present invention, one aspect of the present invention provides a kind of magnesium sulfate waste water processing equipment for recycling, including
First mixing reactor, the first sedimentation basin, the first centrifuge, the second mixing reactor, the second sedimentation basin, the second centrifuge are adjusted
Save pond, wherein the first mixing reactor, the first sedimentation basin, the second mixing reactor, the second sedimentation basin, regulating reservoir pass through pipeline
It is linked in sequence；Wherein regulating reservoir is also connected by pipeline with the first mixing reactor, forms solubility calcium reflux cycle；
First sedimentation basin is connected by pipeline with the first centrifuge, and the first centrifuge passes through pipeline and the second hybrid reaction
Device is connected；Second sedimentation basin is connected by pipeline with the second centrifuge, and the second centrifuge is connected by pipeline with regulating reservoir
It connects.
Its one side of regulating reservoir is for regulating and controlling phegma in the present invention, and when without centrifugal dehydration, regulating reservoir, which plays, to be deposited
Storage, regulates and controls the effect of phegma；On the other hand it is shunted, because the supernatant of the second sedimentation basin and the second centrifuge is chosen
Certain proportion flows back, reflux ratio 100%-800%, preferably 300%-500%, further preferably 400%, remaining
Part is as water outlet or enters advanced desalination.
Regulating reservoir will flow into its internal solution by pipeline and shunt, and a part is back to the first mixing by pipeline
Reactor, another part are flowed out by pipeline, carry out advanced desalination processing.
Wherein, first, second mixing reactor be thoroughly mixed stirring reactor, batch stirred reactor or
Person's semibatch stirred reactor, is preferably thoroughly mixed stirring reactor.
In particular, the sediment of the first sedimentation basin flows into the first centrifuge by pipeline, centrifugal treating is carried out, is precipitated
Object calcium sulphate dihydrate；Supernatant after centrifugal treating passes through pipeline to the second mixing reactor；The precipitation of second sedimentation basin
Object flows into the second centrifuge by pipeline, carries out centrifugal treating, obtains sediment magnesium hydroxide；Supernatant after centrifugal treating is logical
Piping is delivered to regulating reservoir, carries out advanced desalination processing.
In particular, first centrifuge is connected with the bottom of the first sedimentation basin by pipeline, the first sedimentation basin is precipitated
Lower part sediment conveying that treated carries out centrifugal treating, removes the moisture in sediment, centrifugal treating as in the first centrifuge
The stillness of night afterwards is flowed by pipeline in the second mixing reactor；The bottom of second centrifuge and the second sedimentation basin passes through pipeline
It is connected, by the lower part sediment conveying after the second sedimentation basin precipitation process as in the second centrifuge, carried out centrifugal treating, removing is heavy
Moisture in starch, the stillness of night after centrifugal treating flow into regulating reservoir by pipeline.
Another aspect of the present invention provides a kind of recycling processing method of magnesium sulfate waste water, including first to magnesium sulfate waste water
It is pre-processed, obtains solubility calcium phegma；Then soluble calcium phegma, resolution are sequentially added to magnesium sulfate waste water
Lime carries out fractional precipitation processing, obtains calcium sulfate, magnesium hydroxide, and calcium sulfate and magnesium hydroxide are recycled and utilized in classification.
Wherein, the pretreatment is the addition resolution lime into magnesium sulfate waste water, carries out coprecipitation reaction, is co-precipitated solid
Mixture removes, and supernatant is mixed as solubility calcium phegma with magnesium sulfate waste water.
In particular, the additive amount of the resolution lime in preprocessing process is 45-55g/L, preferably 50g/L, i.e. every liter of sulphur
The amount that lime is added in sour magnesium waste water raw water is 45-55g, preferably 50g.
Especially, the resolution lime is prepared by the following method：According to mass ratio it is 1 by quick lime and water:(2-
10) ratio is mixed and stirred for uniformly.
In particular, the mass ratio of the quick lime and water is preferably 1：2.5.
Especially, further include that solid-liquid separation treatment is carried out to the slurry of coprecipitation reaction, obtain co-precipitation solid mixture
And supernatant, wherein co-precipitation solid mixture removal, supernatant is as the solubility calcium phegma.
Wherein, the ratio between volume of the solubility calcium phegma and magnesium sulfate waste water is (1-8)：1, preferably (3-5)：1,
Further preferably 4:1.
In particular, the amount of the resolution lime added in the fractional precipitation processing procedure is 45-55g/L, preferably 50g/
L, the i.e. amount that resolution lime is added in every liter of magnesium sulfate waste water raw water are 45-55g, preferably 50g.
Another aspect of the present invention provides a kind of recycling processing method of magnesium sulfate waste water, includes the following steps：
1) resolution lime is added into magnesium sulfate waste water, carries out co-precipitation pretreatment, obtains solubility calcium phegma；
2) solubility calcium phegma is added to magnesium sulfate waste water and carries out the first precipitation reaction, obtain calcium sulfate precipitation and the
One supernatant；
3) resolution lime is added into the first supernatant, carries out the second precipitation reaction, obtains magnesium hydrate precipitate and second
Supernatant.
Wherein, the magnesium sulfate waste water is the magnesium sulfate waste water of output during rare-earth smelting, preferably rare earth acid system smelting
Refine the magnesium sulfate waste water generated in the process；It is stripped since back extraction hydrochloric acid is utilized in rare-earth smelting, causes to generate useless
Contain chlorion in liquid.
Contain chlorion in heretofore described magnesium sulfate waste water, is magnesium sulfate and magnesium chloride mixed liquor.
The method of the present invention is also applied for common magnesium sulfate waste liquid, and calcium chloride, waste water are added in the first mixing reactor
It is precipitated with raw water and generates calcium sulfate, then mud-water separation, the first supernatant add resolution lime again, then carry out mud-water separation and obtain the
Two supernatants are also chlorination calcium form, can also be flowed back in this way, and circular response, this method is still possible, only this
Sample needs additional supplement calcium chloride.
In particular, the resolution lime is prepared by the following method：According to mass ratio it is 1 by quick lime and water:(2-
10) ratio is mixed and stirred for uniformly.
Especially, the mass ratio of the quick lime and water is preferably 1：2.5.
Wherein, the addition that lime is cleared up described in step 1) is that 45-55g/L (adds in i.e. every 1 liter of magnesium sulfate waste water raw water
The amount of the resolution lime entered is 45-55g, preferably 50g)；Hydraulic detention time is controlled in the co-precipitation preprocessing process is
15-45min, preferably 30min.
In particular, further including carrying out solid-liquid separation treatment to the mixed slurry of coprecipitation reaction, it is mixed to obtain co-precipitation solid
Object and supernatant are closed, wherein co-precipitation solid mixture removal, supernatant is as the solubility calcium phegma.
Especially, the solid-liquid separation treatment includes the sedimentation of the slurry progress pretreatment stage first to coprecipitation reaction
Processing, the supernatant of settlement treatment is as the solubility calcium phegma.
In particular, the sedimentation time of the settlement treatment of the pretreatment stage is 2-4h, preferably 3h.
Especially, further include that the mud mixture for obtaining settlement treatment carries out the centrifugal treating of pretreatment stage, centrifugation
The solid of processing is the co-precipitation solid mixture, and the supernatant of centrifugal treating merges one with the supernatant of settlement treatment
It rises, as the solubility calcium phegma.
In particular, the centrifugation rate of the centrifugal treating of the pretreatment stage is 2000-5000r/min, preferably
3000r/min；Centrifugation time is 3-5min, preferably 3min.
Wherein, the ratio between volume of solubility calcium phegma described in step 2) and magnesium sulfate waste water is 1-8：1, preferably
(3-5):1, further preferably 4:1；The additive amount that lime is cleared up described in step 3) is 45-50g/L, and preferably 50g/L is (i.e.
The amount for the resolution lime being added in every 1 liter of magnesium sulfate waste water raw water is 45-50g, preferably 50g, that is to say, that clear up lime
The quality of addition is 45-50g/L, preferably 50g/L with the ratio between the volume of magnesium sulfate waste water raw water in step 2)).
In particular, the first precipitation reaction process is carried out in step 2) under stirring；It is being stirred in step 3)
Second precipitation reaction is carried out under state.
Especially, hydraulic detention time 0.5-2.0h, preferably 1.0- during the first precipitation reaction described in step 2)
1.5 hour；The stirring intensity of reaction is 25-150/s, preferably 25-50/s；Water during second precipitation reaction described in step 3)
Power residence time 15-45min, preferably 30min；Stirring intensity is 25-150/s, preferably 25-50/s.
In particular, further including step 2A), the first settlement treatment is carried out to the mixed slurry after the first precipitation reaction, is obtained
The calcium sulfate precipitation and the first sedimentation supernatant；Further include step 3A) mixed slurry after the second precipitation reaction is carried out
Second settlement treatment obtains the magnesium hydroxide and the second sedimentation supernatant.
Especially, the sedimentation time of first settlement treatment is 1-2h, preferably 1.5h；Second settlement treatment
Sedimentation time is 2-4h, preferably 3h.
In particular, further include that the first centrifugal treating is carried out to the mud mixture after the first settlement treatment, centrifugal treating
Solid is the calcium sulphate dihydrate, and the supernatant of centrifugal treating is the first centrifuged supernatant, the first centrifuged supernatant and first
The supernatant of settlement treatment merges into the first supernatant；Further include to after the second settlement treatment mud mixture carry out second from
Heart processing, the solid of centrifugal treating are the magnesium hydroxide, and the supernatant of centrifugal treating is the second centrifuged supernatant, second from
The supernatant of supernatant and the second settlement treatment merges into the second supernatant.
Especially, the centrifugation rate of first, second centrifugal treating is 2000-5000r/min, preferably 3000r/
min；Centrifugation time is 3-5min, preferably 3min.
Another aspect of the invention provides a kind of recycling processing method of magnesium sulfate waste water, includes the following steps：
1) resolution lime is added into magnesium sulfate waste water, carries out co-precipitation pretreatment, obtains solubility calcium phegma；
2) solubility calcium phegma is added to magnesium sulfate waste water and carries out the first precipitation reaction, obtain calcium sulfate precipitation and the
One supernatant；
3) resolution lime is added into the first supernatant, carries out the second precipitation reaction, obtains magnesium hydrate precipitate and second
Supernatant；
4) reflux of the second supernatant is added to magnesium sulfate waste water and carries out the first precipitation reaction, obtain calcium sulfate precipitation and the
One supernatant；
5) resolution lime, is added into the first supernatant, carries out the second precipitation reaction, obtains magnesium hydrate precipitate and second
Supernatant；
6), circulating repetition step 4), 5), until magnesium sulfate waste water processing is completed.
Wherein, the resolution lime is prepared by the following method：According to mass ratio it is 1 by quick lime and water:(2-
10) ratio is mixed and stirred for uniformly.
In particular, the mass ratio of the quick lime and water is preferably 1：2.5.
Wherein, the addition that lime is cleared up described in step 1) is that 45-55g/L (adds in i.e. every 1 liter of magnesium sulfate waste water raw water
The amount of the resolution lime entered is 45-55g, preferably 50g)；Hydraulic detention time is controlled in the co-precipitation preprocessing process is
15-45min, preferably 30min.
In particular, further including carrying out solid-liquid separation treatment to the mixed slurry of coprecipitation reaction, it is mixed to obtain co-precipitation solid
Object and supernatant are closed, wherein co-precipitation solid mixture removal, supernatant is as the solubility calcium phegma.
Especially, the solid-liquid separation treatment includes the sedimentation of the slurry progress pretreatment stage first to coprecipitation reaction
Processing, the supernatant of settlement treatment is as the solubility calcium phegma.
In particular, the sedimentation time of the settlement treatment of the pretreatment stage is 2-4h, preferably 3h.
Especially, further include that the mud mixture for obtaining settlement treatment carries out the centrifugal treating of pretreatment stage, centrifugation
The solid of processing is the co-precipitation solid mixture, and the supernatant of centrifugal treating merges one with the supernatant of settlement treatment
It rises, as the solubility calcium phegma.
In particular, the centrifugation rate of the centrifugal treating of the pretreatment stage is 2000-5000r/min, preferably
3000r/min；Centrifugation time is 3-5min, preferably 3min.
Wherein, the ratio between volume of solubility calcium phegma described in step 2) and magnesium sulfate waste water is 1-8：1, preferably 3-
5:1, further preferably 4:1；The additive amount that lime is cleared up described in step 3) is 45-50g/L, preferably 50g/L (i.e. every 1
The amount for rising the resolution lime being added in magnesium sulfate waste water raw water is 45-50g, preferably 50g, that is to say, that clears up the addition of lime
Quality and step 2) in the ratio between the volume of magnesium sulfate waste water raw water be 45-50g/L, preferably 50g/L).
Wherein, the ratio between volume of the second supernatant and magnesium sulfate waste water that flow back described in step 4) is (1-8：1, preferably
For 3-5:1, further preferably 4:1；The additive amount that lime is cleared up described in step 5) is 45-50g/L, and preferably 50g/L is (i.e.
The amount for the resolution lime being added in every 1 liter of magnesium sulfate waste water raw water is 45-50g, preferably 50g, that is to say, that clear up lime
The quality of addition is 45-50g/L, preferably 50g/L with the ratio between the volume of magnesium sulfate waste water raw water in step 4)).
In particular, under stirring, carry out step 2), 4) described in the first precipitation reaction process；In stirring
Under, carry out step 3), 5) described in the second precipitation reaction.
Especially, step 2), 4) described in the first precipitation reaction during hydraulic detention time 0.5-2.0h, preferably
1.0-1.5 hour；The stirring intensity of reaction is 25-150/s, preferably 25-50/s；Step 3), 5) described in the second precipitation reaction
Hydraulic detention time 15-45min in the process, preferably 30min；Stirring intensity is 25-150/s, preferably 25-50/s.
In particular, further including step 2A), 4A), to after the first precipitation reaction mixed slurry carry out the first settlement treatment,
Obtain the calcium sulfate precipitation and the first sedimentation supernatant；Further include step 3A), 5A) to the mixing after the second precipitation reaction
Slurry carries out the second settlement treatment, obtains the magnesium hydroxide and the second sedimentation supernatant.
Especially, the sedimentation time of first settlement treatment is 1-2h, preferably 1.5h；Second settlement treatment
Sedimentation time is 2-4h, preferably 3h.
In particular, further include that the first centrifugal treating is carried out to the mud mixture after the first settlement treatment, centrifugal treating
Solid is the calcium sulphate dihydrate, and the supernatant of centrifugal treating is the first centrifuged supernatant, the first centrifuged supernatant and first
The supernatant of settlement treatment merges into the first supernatant；Further include to after the second settlement treatment mud mixture carry out second from
Heart processing, the solid of centrifugal treating are the magnesium hydroxide, and the supernatant of centrifugal treating is the second centrifuged supernatant, second from
The supernatant of supernatant and the second settlement treatment merges into the second supernatant.
Especially, the centrifugation rate of first, second centrifugal treating is 2000-5000r/min, preferably 3000r/
min；Centrifugation time is 3-5min, preferably 3min.
Further aspect of the present invention provide it is a kind of using above-mentioned magnesium sulfate waste water processing equipment for recycling to magnesium sulfate waste water into
The method of row recycling treatment, includes the following steps：
1) magnesium sulfate waste water is flowed into successively first above-mentioned magnesium sulfate waste water processing unit the first mixing reactor, first
Sedimentation basin flows into the second mixing reactor, while the addition resolution lime into the second mixing reactor, carries out being co-precipitated pre- place
Reason；Then pretreated mixed slurry will be co-precipitated and be delivered to the second sedimentation basin, pretreatment stage precipitation process is carried out, be total to
Precipitate mud mixture and supernatant；Then co-precipitation mud mixture is sent into the second centrifuge and carries out pretreatment stage centrifugation
Processing, centrifuged supernatant are incorporated as pretreatment solubility calcium phegma with co-precipitation supernatant；
2) pretreatment solubility calcium phegma is back to the first mixing reactor, in the first mixing reactor of inflow
Magnesium sulfate waste water carries out the first precipitation reaction；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carries out the
One settlement treatment obtains the first sedimentation mud mixture and the first sedimentation supernatant；Then the first sedimentation mud mixture is sent
Enter and carry out the first centrifugal treating in the first centrifuge, obtain sulfate dihydrate calcium precipitate, the first centrifuged supernatant is settled with first
Clear liquid merges into the first supernatant；
3) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out
Second precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain second
Settle mud mixture and the second sedimentation supernatant；Then the second sedimentation mud mixture is sent into the second centrifuge, carries out the
Two centrifugal treatings, obtain magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
4) the second supernatant fraction is back to the first mixing reactor, gives up with the magnesium sulfate flowed into the first mixing reactor
Water carries out the first precipitation reaction；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carried out at the first sedimentation
Reason obtains the first sedimentation mud mixture and the first sedimentation supernatant；Then by first sedimentation mud mixture be sent into first from
The first centrifugal treating is carried out in scheming, obtains sulfate dihydrate calcium precipitate, and the first centrifuged supernatant merges with the first sedimentation supernatant
For the first supernatant；
5) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out
Second precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain second
Settle mud mixture and the second sedimentation supernatant；Then the second sedimentation mud mixture is sent into the second centrifuge, carries out the
Two centrifugal treatings, obtain magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
6) circulating repetition step 4), 5), until having handled magnesium sulfate waste water.
Wherein, it is co-precipitated in preprocessing process described in step 1), the amount of the resolution lime of addition is 45-55g/L (i.e. every
The amount for the resolution lime being added in 1 liter of magnesium sulfate waste water raw water is 45-55g, preferably 50g).
In particular, the sedimentation time of the settlement treatment of the pretreatment stage is 2-4h, preferably 3h；The pretreatment rank
The centrifugation rate of the centrifugal treating of section is 2000-5000r/min, preferably 3000r/min；Centrifugation time is 3-5min, preferably
For 3min.
Wherein, the ratio between volume of solubility calcium phegma described in step 2) and magnesium sulfate waste water is (1-8):1, preferably
(3-5):1, further preferably 4:1；The sedimentation time of first settlement treatment is 1-2h, preferably 1.5h；Described first
The centrifugation rate of centrifugal treating is 2000-5000r/min, preferably 3000r/min；Centrifugation time is 3-5min, preferably
3min。
Wherein, the additive amount that lime is cleared up described in step 3) is that 45-50g/L (adds in i.e. every 1 liter of magnesium sulfate waste water raw water
The amount of the resolution lime entered is 45-50g, preferably 50g, that is to say, that the quality for clearing up the addition of lime is flowed into step 2)
The ratio between volume of magnesium sulfate waste water raw water in first mixing reactor is 45-50g/L, preferably 50g/L)；Described second is heavy
The sedimentation time of drop processing is 2-4h, preferably 3h；The centrifugation rate of second centrifugal treating is 2000-5000r/min, excellent
It is selected as 3000r/min；Centrifugation time is 3-5min, preferably 3min.
Wherein, the ratio between volume of the second supernatant and magnesium sulfate waste water described in step 4) is (1-8：1, preferably (3-
5):1, further preferably 4:1；The sedimentation time of first settlement treatment is 1-2h, preferably 1.5h；First centrifugation
The centrifugation rate of processing is 2000-5000r/min, preferably 3000r/min；Centrifugation time is 3-5min, preferably 3min.
Wherein, the additive amount that lime is cleared up described in step 5) is that 45-50g/L (adds in i.e. every 1 liter of magnesium sulfate waste water raw water
The amount of the resolution lime entered is 45-50g, preferably 50g, that is to say, that the quality for clearing up the addition of lime is flowed into step 4)
The ratio between volume of magnesium sulfate waste water raw water in first mixing reactor is 45-50g/L, preferably 50g/L)；Described second is heavy
The sedimentation time of drop processing is 2-4h, preferably 3h；The centrifugation rate of second centrifugal treating is 2000-5000r/min, excellent
It is selected as 3000r/min；Centrifugation time is 3-5min, preferably 3min.
The method of the present invention obtains calcium sulphate dihydrate and two kinds of sediments of magnesium hydroxide respectively in such a way that priority precipitates.Sulphur
The reaction process of sour calcium does not have side reaction progress, therefore can obtain high-purity sulfuric acid calcium；Simultaneously as calcium sulfate slightly soluble,
When entering the first sedimentation basin after being reacted in one mixing reactor, sulfate radical cannot be removed completely, therefore part of sulfuric acid root
Ion with the first sedimentation basin supernatant flow into the second mixing reactor, during carrying out second of precipitation reaction understand into
Enter magnesium hydrate precipitate process, calcium sulfate ionic product changes when adding quick lime, necessarily causes new calcium sulfate to generate, calcium sulfate
Precipitation reaction become the side reaction of magnesium hydrate precipitate in the second mixing reactor, cause magnesium hydroxide purity under
Drop.
Compared with prior art, processing unit and processing method of the present invention have the advantages that：
Compared to traditional coprecipitation process, forms mixing and discard sediment, cause sediment that cannot detach, cannot carry out
Subsequent recycling, and processing unit of the present invention and processing method neither change additive amount of medicament nor change adding for medicament
Medicine form, in the case where not increasing treatment agent cost, the internal circulation system by establishing soluble calcium reflux (passes through
Regulation and control calcic supernatant is back to the first mixing reactor), output high-purity sulphuric acid calcium, and the hydrogen containing a small amount of sulfuric acid calcium impurities
Magnesium oxide precipitation object, solid sediment are able to effective recycling, to the utilization that magnesium sulfate waste water is repeated, environmentally friendly valence
Value and economic benefit are apparent.
The present invention can effectively reduce the same of magnesium sulfate waste water salt content by introducing resolution lime into magnesium sulfate waste water
When, calcium sulfate is precipitated respectively in two steps with magnesium hydroxide by the method that calcium flows back and detaches (i.e. magnesium sulfate waste water mixed precipitation
Pretreatment obtains supernatant, and regulation and control supernatant is back to the first mixing reactor, is reacted with magnesium sulfate waste water raw water and generate two water
Calcium sulfate, mixed liquor obtain sulfate dihydrate calcium precipitate after free sedimentation and centrifugal dehydration, and the first sedimentation supernatant flows into the
The milk of lime of resolution is added in the second mixing reactor, magnesium hydroxide is obtained after precipitation reaction for two mixing reactors), solution
Coprecipitation Problem in chemical precipitation method of having determined recycles original solid castoff specification, " turning waste into wealth ".
Magnesium sulfate waste water in the present invention is that rare-earth smelting carries out back extraction generation due to the use of back extraction hydrochloric acid in the process
The magnesium sulfate waste water containing chlorion, essence is the mixing of magnesium sulfate and magnesium chloride, clears up lime adding resolution lime/hydrogen
Calcium sulfate is generated with after magnesium hydroxide, matched according to anion-cation balance and chlorion in water outlet is exactly calcium ion, is exactly returned
Flow liquid main component；By the reflux of soluble calcium supernatant, calcium sulfate and magnesium hydroxide crystal can be detached.
After magnesium sulfate waste water is mixed with quick lime, while two following precipitation reaction occur, specifically such as formula (1), (2) institute
Show：
Mg2++2OH-=Mg (OH)2↓(1)
Ca2++SO4 2-=CaSO4↓(2)
It generates calcium sulfate to mix with magnesium hydroxide co-precipitation, due to containing the chlorion coexisted with calcium, co-precipitation in raw water
After reaction, the main component calcium chloride of supernatant, meanwhile, the sediment of generation is separated by solid-liquid separation
Phegma (mixed precipitation obtained by calcium ion supernatant enter after regulating reservoir according to required reflux ratio) is back to the
One mixing reactor determines that reflux ratio (backflow water yield and processing system inflow ratio) is 100%- according to different quality situation
800%, preferably 300-500%, calcium ion is sent out with the sulfate ion in the raw water for flowing into the first mixing reactor in phegma
Raw calcium sulfate precipitation, the first mixing reactor are to be thoroughly mixed stirring reactor, and phegma is synchronized mixes (raw water with raw water
It is added by same multiplying power according to reflux ratio with phegma, for example reflux ratio is 4, raw water flow 1, phegma flow is 4) to carry out
First precipitation reaction, hydraulic detention time 0.5-2.0h of the waste water in the first mixing reactor, preferably 1.0-1.5 hours；Instead
The stirring intensity answered be 25-150/s, preferably 25-50/s, i.e. hydraulic detention time 0.5-2.0h during the first precipitation reaction,
It is preferred that 1.0-1.5 hours；The stirring intensity of reaction is 25-150/s, preferably 25-50/s.
Magnesium sulfate waste water (i.e. raw water) is inputted in the first mixing reactor, after being stirred, SO in raw water4 2-With reflux
Ca in liquid2+The muddy water mixed solution that crystalline deposit reaction generates calcium sulfate, the first precipitation reaction generates occurs and flows into the by pipeline
One sedimentation basin carries out the first settlement treatment, mud-water separation, and the sedimentation time in the first sedimentation basin is 1-2h；After settlement treatment
First sedimentation supernatant (SO4 2-After the removal of the first mixing reactor, supernatant main component becomes magnesium chloride) to flow into second mixed
Close reaction tank, the first sedimentation basin bottom precipitation generate wet mud centrifuged into the first centrifuge by pipeline, dehydration,
The first centrifuged supernatant water outlet after centrifugation enters the second mixed reaction pond by pipeline, the purpose is to improve system producing water ratio,
Wet mud is the lower calcium sulphate dihydrate of moisture content after dehydration, and centrifuge running parameter rotating speed is 2000-5000rpm, preferably
3000rpm；
Quick lime is mixed with water, resolution lime is made, the wherein mass ratio of quick lime and water is 1：(2-10), it is excellent
It is selected as 1:2.5, resolution lime is added in the second mixing reactor, wherein the addition speed of resolution lime is the 5%- of inflow
20%, preferably 10%；Second mixing reactor is to be thoroughly mixed stirring reactor, and waste water is in the second mixing reactor
The second precipitation reaction is carried out, hydraulic detention time 15-45min, preferably 30min during the second precipitation reaction；Stirring intensity
For 25-150/s, preferably 25-50/s.
Because sulfate ion with after calcium ion hybrid reaction, obtained in the first sedimentation basin it is most of removal (because
Composition for phegma is calcium chloride, and magnesium sulfate is contained in raw water ingredient, there is calcium sulfate generation after mixing, remaining magnesium chloride, with
Ionic state is dissolved in the water), therefore the sediment generated in the second sedimentation basin is mainly magnesium hydroxide, sediment (calcium sulfate, hydrogen
Magnesia) it is detached by priority fractional precipitation.
The magnesium hydrate precipitate generated in the second mixing reactor, the muddy water mixed solution for reacting end enter the second precipitation
Pond, sedimentation basin settlement treatment 2-4h, preferably 3h；The supernatant of second sedimentation basin flows into balancing tank, is deposited in the hydrogen of bottom
The wet mud of magnesia is dehydrated by pipeline into the second centrifuge, and Centrifugal Effluent Treatment flows into balancing tank, to improve present invention dress
The producing water ratio of system is set, the wet mud after the second centrifuge dewatering is the lower magnesium hydroxide of moisture content, and centrifuge running parameter turns
Speed is 2500-5000rpm, preferably 3000rpm；
The solution flowed into balancing tank is calcium chloride solution, is shunted in balancing tank, and it is de- that water outlet can carry out depth
Salt, part solution phegma, moves in circles, and substep recycles sulfate radical, magnesium ion, and magnesium sulfate waste water is turned waste into wealth.
In order to quickly start, can also originally directly added into magnesium sulfate raw water soluble calcium salt (such as：Calcium chloride
Deng), because needing first to carry out raw water co-precipitation pretreatment to obtain the supernatant containing calcium chloride, purpose is exactly on obtaining
Clear liquid is first reacted with raw water after being flowed back generates calcium sulfate, and milk of lime is then added in mixing reactor 2 generates hydroxide
Magnesium；Therefore medicament calcium chloride can be added directly in mixing reactor 1, precipitation reaction occurs with raw water magnesium sulfate, then proceed to
The step of below, thus eliminates the preprocessing process of co-precipitation, can directly carry out fractional precipitation technique, quite
In the quick startup of technique.
Description of the drawings
Fig. 1 is the structural schematic diagram of magnesium sulfate waste water processing equipment for recycling of the present invention；
Fig. 2 is the flow chart of magnesium sulfate waste water recycling treatment of the present invention.
Reference sign
1, the first mixing reactor；2, the first sedimentation basin；3, the second mixing reactor；4, the second sedimentation basin；5, regulating reservoir；
6, the first centrifuge；7, the second centrifuge；8, pipeline.
Specific implementation mode：
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary for these, and it is not intended to limit the scope of the present invention in any way.People in the art
Member it should be understood that without departing from the spirit and scope of the invention can to the details of technical solution of the present invention and form into
Row modifications or substitutions, but these modifications and replacement are each fallen in protection scope of the present invention.
With reference to the accompanying drawings 1,2, detailed description implements the processing unit and profit of magnesium sulfate waste water recycling of the present invention
The specific embodiment of the processing method of recycling is carried out to magnesium sulfate waste water with the processing unit.
As shown in Figure 1, the device of the magnesium sulfate waste water recycling of the present invention includes the first mixing reactor 1, first
Sedimentation basin 2, the second mixing reactor 3, the second sedimentation basin 4, regulating reservoir 5, the first centrifuge 6, the second centrifuge 7 and connecting pipe
8, wherein the first mixing reactor, the first sedimentation basin, the second mixing reactor, the second sedimentation basin, regulating reservoir pass through pipeline sequence
Connection, regulating reservoir are connected with the first mixing reactor by pipeline, and solubility calcium reflux cycle is formed；First sedimentation basin passes through
Pipeline is connected with the first centrifuge, and the first centrifuge is connected by pipeline with the second mixing reactor；Second sedimentation basin is logical
Piping is connected with the second centrifuge, and the second centrifuge is connected by pipeline with regulating reservoir；Regulating reservoir will be flowed by pipeline
Enter its internal solution shunt, a part is back to the first mixing reactor by pipeline, forms calcium ion phegma, another portion
Divide and pass through pipeline outflow, carries out advanced desalination processing.
There is blender in first, second mixing reactor, be stirred, at mixing to entering the aqueous in reactor
It manages, the first, second mixing reactor in the specific embodiment of the invention, which is selected as, is thoroughly mixed stirring reactor, in addition to complete
Complete to be mixed except formula reactor, other mixing reactors as known in the art are suitable for the present invention, such as intermittent
Reactor or semibatch reactor.
The first, second centrifuge in the specific embodiment of the invention selects horizontal centrifuge, in addition to horizontal centrifuge it
Outside, other centrifuges are suitable for the present invention.
The operation principle of processing unit of the present invention is as follows：
1) magnesium sulfate waste water (containing chlorion) generated in rare earth acid system smelting process is flowed into the present invention successively first
The first mixing reactor, the first sedimentation basin of the processing unit of magnesium sulfate waste water recycling flow into the second mixing reactor,
The addition resolution lime into the second mixing reactor simultaneously, carries out co-precipitation pretreatment；Then pretreated mixing will be co-precipitated
Slurry is delivered to the second sedimentation basin, carries out pretreatment stage precipitation process, obtains co-precipitation mud mixture and supernatant；Then
Co-precipitation mud mixture is sent into the second centrifuge and carries out pretreatment stage centrifugal treating, centrifuged supernatant and co-precipitation supernatant
Liquid is incorporated as pretreatment solubility calcium supernatant；
2) pretreatment solubility calcium supernatant is back to the first mixing reactor, in the first mixing reactor of inflow
Magnesium sulfate waste water carries out the first precipitation reaction；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carries out the
One settlement treatment obtains the first sedimentation mud mixture and the first sedimentation supernatant；Then the first sedimentation mud mixture is sent
Enter and carry out the first centrifugal treating in the first centrifuge, obtain sulfate dihydrate calcium precipitate, the first centrifuged supernatant is settled with first
Clear liquid merges into the first supernatant；
3) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out
Second precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain second
Settle mud mixture and the second sedimentation supernatant；Then the second sedimentation mud mixture is sent into the second centrifuge, carries out the
Two centrifugal treatings, obtain magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
4) the second supernatant fraction is back to the first mixing reactor, gives up with the magnesium sulfate flowed into the first mixing reactor
Water carries out the first precipitation reaction；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carried out at the first sedimentation
Reason obtains the first sedimentation mud mixture and the first sedimentation supernatant；Then by first sedimentation mud mixture be sent into first from
The first centrifugal treating is carried out in scheming, obtains sulfate dihydrate calcium precipitate, and the first centrifuged supernatant merges with the first sedimentation supernatant
For the first supernatant；
5) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out
Second precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain second
Settle mud mixture and the second sedimentation supernatant；Then the second sedimentation mud mixture is sent into the second centrifuge, carries out the
Two centrifugal treatings, obtain magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
6) circulating repetition step 4), 5), until having handled magnesium sulfate waste water.
Embodiment 1
The magnesium sulfate waste water of recycling Inner Mongol factory of Baogang north rare-earth wet method (acid system) metallurgy output.
The magnesium sulfate waste water raw water quality index such as table 1 of Inner Mongol factory of Baogang north rare-earth wet method metallurgy output.
1 magnesium sulfate waste water raw water quality of table
| pH | 3.68 | Conductivity (m s) | 63.4 |
| SO4 2-(mg/L) | 51810 | Mg2+(mg/L) | 19000 |
| Cl-(mg/L) | 15000 |
1, co-precipitation pretreatment
1-1), quick lime is uniformly mixed with water, is made and clears up lime, the mass ratio of quick lime and water is 1:2.5 (usually
It is 1:2-10)；
It 1-2) takes part of sulfuric acid magnesium waste water and medicament resolution lime is added thereto, carry out coprecipitation reaction, waste water generates
Calcium sulfate and magnesium hydroxide are co-precipitated slurry, wherein the dosage of medicament is 50g/L (being usually 45~55g/L), that is, clears up stone
The addition of ash is 45-55g/L, preferably 50g/L, i.e. the amount that resolution lime is added in every liter of magnesium sulfate waste water raw water is 45-
55g, preferably 50g)；
The resolution lime of resolution reacts with magnesium sulfate in raw water：MgSO4+Ca(OH)2=CaSO4↓+Mg(OH)2↓, sulphur
Sour calcium is co-precipitated output with magnesium hydroxide；
Pretreated co-precipitation slurry 1-3) is carried out to the settlement treatment of pretreatment stage, wherein sedimentation time 4h is (usually
For 2-4h), the sedimentation supernatant and pretreatment stage that pretreatment stage is made settle mud mixture；The sedimentation of pretreatment stage
Supernatant is delivered in regulating reservoir, due to SO in the sedimentation supernatant of pretreatment stage4 2-, Mg2+Precipitation mainly contains calcium
Ion and chlorion；
1-4) pretreatment stage sedimentation mud mixture is sent into the second centrifuge, at the centrifugation for carrying out pretreatment stage
Reason, wherein centrifugation rate are 3000r/min (being usually 2000-5000r/min), and centrifugation time 3min (is usually 3-
5min)；Sediment after centrifugal treating is the calcium sulfate and magnesium hydroxide mixture (discarded) of bottom, supernatant after centrifugation and
Pretreatment stage sedimentation supernatant is delivered to balancing tank 5 together, and is returned regulating reservoir inside points solution as solubility calcium
Flow liquid is back to the first mixing reactor and is mixed with magnesium sulfate waste water raw water, wherein the volume of phegma and magnesium sulfate waste water raw water
Than being 4:1 (is usually 1-8：1).
The water quality of pretreatment supernatant after centrifugal treating is as shown in table 2.
Table 2 pre-processes supernatant water quality
| pH | 1 1.64 | Conductivity | 3 8.9ms/cm |
| SO4 2-(mg/L) | 703.03 | Mg2+(mg/L) | 19.75 |
| Ca2+(mgl/L) | 8120.88 | Cl-(mg/L) | 15000 |
Pretreated supernatant mainly contain calcium chloride (because containing chlorion in magnesium sulfate waste water raw water, waste water with
Lime coprecipitation reaction is cleared up, chlorion is not involved in reaction).
SO in preprocessing process in magnesium sulfate waste water4 2-、Mg2+Removal rate reach 98% or more.
2, sulfate radical is recycled
2-1), solubility calcium phegma is back in the first mixing reactor, is mixed with magnesium sulfate waste water raw water, stirring,
Carry out the first precipitation reaction, i.e. Ca2++SO4 2-=CaSO4↓, reaction generates calcium sulfate precipitation, the first slurry is made, wherein solvable
Property calcium phegma and magnesium sulfate waste water raw water the ratio between volume be 4:1 (is usually 1-8：1, preferably 3-5:1)；When hydraulic retention
Between for 1h (be usually 0.5-2.0h, preferably 1.0-1.5h)；The stirring intensity of reaction be 50/s (be usually 25-150/s, it is excellent
It is selected as 25-50/s)；Stir speed (S.S.) is 3000rpm (being usually 2000-5000rpm)；
2-2), the first slurry flows into the first sedimentation basin, carries out the first settlement treatment, wherein the sedimentation in the first sedimentation basin
Time is 1.5h, and (being usually 1-2h) is made the first sedimentation supernatant and is mixed with the first muddy water for falling to the first sedimentation basin lower part
Close object；First sedimentation supernatant is delivered in the second mixing reactor, since calcium ions precipitate is precipitated in the first sedimentation supernatant,
Mainly contain magnesium ion and chlorion；
2-3), the first mud mixture is sent into the first centrifuge, carries out the first centrifugal treating, obtain two water sulphur of solid
Sour calcium and the first centrifuged supernatant, the first centrifuged supernatant merge into the first supernatant with the first sedimentation supernatant, are delivered to the
In two mixing reactors, wherein the centrifugation rate of the first centrifugal treating is 3000r/min (being usually 2000-5000r/min), from
The heart time is 3min, (being usually 3-5min).
Using national standard method《GB 1886.6-2016, food additives calcium sulfate》The purity of calcium sulphate dihydrate is measured, is surveyed
It is 96% to determine result, and purity reaches 95% or more, reaches considerably beyond national standard BT/B 21371-2008《For the work in cement
Industry by-product gypsum》In 75% or more purity requirement；According to national standard GB/T 5483-2008《The natural gypsum》Have reached superfine stone
The standard of cream (purity is more than 95%).
3, magnesium ion is recycled
3-1), resolution lime is added into the second mixing reactor, and (quick lime and water are 1 according to mass ratio:2.5 ratio
Example is uniformly mixed, and the mass ratio of quick lime and water is usually 1:2-10), the second precipitation reaction, i.e. Mg are carried out2++2OH-=Mg
(OH)2↓, reaction generates magnesium hydrate precipitate, and the second slurry is made, wherein it (is usually 45 that the addition of resolution lime, which is 50g/L,
~50g/L), stir speed (S.S.) is 3000rpm (being usually 2000-5000rpm) in the second mixing reactor；Hydraulic detention time is
30min (being usually 15-45min)；Stirring intensity is 50/s (being usually 25-150/s, preferably 25-50/s)；
The additions quality of the resolution lime is with the ratio between the volume of magnesium sulfate waste water in the first mixing reactor of inflow
For 45~50g/L, preferably 50g/L, i.e., often flow up the magnesium sulfate waste water in the first mixing reactor) in be added resolution lime
45-55g。
3-2), the second slurry flows into the second sedimentation basin, carries out the second settlement treatment, wherein the sedimentation in the first sedimentation basin
Time is 3h, and (being usually 2-4h) is made the second sedimentation supernatant and falls to the second muddy water mixing of the second sedimentation basin lower part
Object；Second settlement treatment upper back second sedimentation supernatant be delivered in regulating reservoir, second sedimentation supernatant in due to magnesium from
Sub- Precipitation, mainly contains calcium ion and chlorion；
3-3), the second mud mixture is sent into the second centrifuge, carries out the second centrifugal treating, obtain solid hydroxide
Magnesium and the second centrifuged supernatant, the second centrifuged supernatant merge into the second supernatant with the second sedimentation supernatant, are delivered to adjusting
In pond, wherein the centrifugation rate of the second centrifugal treating is 3000rpm (being usually 2000-5000rpm)；Centrifugation time is 3min
(being usually 3-5min).
Foundation《HGT 3607-2007, industrial magnesium hydroxide》The purity for measuring magnesium hydroxide is 77-80%.
The purity of the magnesium hydroxide prepared in the method for the present invention reaches 77-80%, and major impurity is calcium sulfate, accounting 15%
~20%.
The water quality of the supernatant of regulating reservoir is delivered to after 2 supernatant of sedimentation basin and the producing water water quality of centrifuge 2 and pretreatment
It is essentially identical, back flow reaction next time can be carried out, through multiple circulation experiment, the circulatory system is stablized, product qualities, phegma index
It is not widely varied.
Claims (10)
1. a kind of magnesium sulfate waste water processing equipment for recycling, including the first mixing reactor, the first sedimentation basin, the first centrifuge,
Second mixing reactor, the second sedimentation basin, the second centrifuge, regulating reservoir, characterized in that first mixing reactor, first
Sedimentation basin, the second mixing reactor, the second sedimentation basin, regulating reservoir are linked in sequence by pipeline；Wherein regulating reservoir also passes through pipeline
It is connected with the first mixing reactor, forms solubility calcium reflux cycle；First sedimentation basin passes through pipeline and the first centrifuge phase
Connection, the first centrifuge are connected by pipeline with the second mixing reactor；Second sedimentation basin passes through pipeline and the second centrifuge
It is connected, the second centrifuge is connected by pipeline with regulating reservoir.
2. processing unit as described in claim 1, characterized in that first, second mixing reactor is thoroughly mixed stirring
Formula reactor, batch stirred reactor or semibatch stirred reactor.
3. processing unit as described in claim 1, characterized in that the bottom of first sedimentation basin by pipeline and first from
Scheming is connected, and the first mud mixture that the first sedimentation basin lower part settlement treatment obtains is delivered to the first centrifuge, is carried out
First centrifugal treating；The top of first centrifuge is connected by pipeline with the second mixing reactor, by the first centrifuge
Supernatant after centrifugal treating is delivered to the second mixing reactor, carries out the second reaction.
4. a kind of recycling processing method of magnesium sulfate waste water, characterized in that including being pre-processed first to magnesium sulfate waste water,
Obtain solubility calcium phegma；Then solubility calcium phegma, resolution lime are sequentially added to magnesium sulfate waste water, it is heavy carries out substep
Shallow lake is handled, and obtains calcium sulfate, magnesium hydroxide, and calcium sulfate and magnesium hydroxide are recycled and utilized in classification.
5. a kind of recycling processing method of magnesium sulfate waste water, characterized in that include the following steps：
1) resolution lime is added into magnesium sulfate waste water, carries out co-precipitation pretreatment, obtains solubility calcium phegma；
2) solubility calcium phegma is added to magnesium sulfate waste water and carries out the first precipitation reaction, obtained on calcium sulfate precipitation and first
Clear liquid；
3) resolution lime is added into the first supernatant, carries out the second precipitation reaction, obtains magnesium hydrate precipitate and the second supernatant
Liquid；
4) by the second supernatant of part reflux be added to magnesium sulfate waste water carry out the first precipitation reaction, obtain calcium sulfate precipitation and
First supernatant；
5) resolution lime, is added into the first supernatant, carries out the second precipitation reaction, obtains magnesium hydrate precipitate and the second supernatant
Liquid；
6), circulating repetition step 4), 5), until magnesium sulfate waste water processing is completed.
6. processing method as claimed in claim 5, characterized in that be co-precipitated in preprocessing process, be added described in step 1)
The amount of resolution lime be 45-55g/L, (what is be added in i.e. every 1 liter of magnesium sulfate waste water raw water clears up lime to preferably 50g/L
Amount is 45-55g, preferably 50g).
7. processing method as claimed in claim 5, characterized in that solubility calcium phegma described in step 2) is useless with magnesium sulfate
The ratio between volume of water is (1-8):1；The ratio between volume of the second supernatant and magnesium sulfate waste water that flow back described in step 4) is (1-
8):1。
8. processing method as claimed in claim 5, characterized in that step 3), 5) described in resolution lime additive amount be 45-
50g/L。
9. processing method as claimed in claim 5, characterized in that further include step 2A), 4A), after the first precipitation reaction
Mixed slurry carries out the first settlement treatment, obtains the calcium sulfate precipitation and the first supernatant；Further include step 3A), 5A) it is right
Mixed slurry after second precipitation reaction carries out the second settlement treatment, obtains the magnesium hydroxide and the second supernatant.
10. a kind of method that recycling treatment being carried out to magnesium sulfate waste water using the processing unit as described in claim 1-3 is any,
It is characterized in that including the following steps：
1) magnesium sulfate waste water is delivered to above-mentioned magnesium sulfate waste water processing unit first, flows into the first mixing reactor, successively
One sedimentation basin flows into the second mixing reactor, while the addition resolution lime into the second mixing reactor, carries out being co-precipitated pre- place
Reason；Then pretreated mixed slurry will be co-precipitated and be delivered to the second sedimentation basin, pretreatment stage precipitation process is carried out, be total to
Precipitate mud mixture and supernatant；Then co-precipitation mud mixture is sent into the second centrifuge and carries out pretreatment stage centrifugation
Processing, centrifuged supernatant are incorporated as pretreatment calcium ion supernatant with co-precipitation supernatant；
2) pretreatment calcium ion supernatant is back to the first mixing reactor, with the magnesium sulfate in the first mixing reactor of inflow
Waste water carries out the first precipitation reaction；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carries out the first sedimentation
Processing obtains the first sedimentation mud mixture and the first sedimentation supernatant；Then the first sedimentation mud mixture is sent into first
The first centrifugal treating is carried out in centrifuge, obtains sulfate dihydrate calcium precipitate, and the first centrifuged supernatant is closed with the first sedimentation supernatant
And it is the first supernatant；
3) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out second
Precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain the second sedimentation
Mud mixture and the second sedimentation supernatant；Then by second sedimentation mud mixture be sent into the second centrifuge, carry out second from
Heart processing, obtains magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
4) the second supernatant fraction is back to the first mixing reactor, with flow into the first mixing reactor in magnesium sulfate waste water into
The first precipitation reaction of row；Then the mixed slurry of the first precipitation reaction is flowed into the first sedimentation basin, carries out the first settlement treatment, obtains
Obtain the first sedimentation mud mixture and the first sedimentation supernatant；Then the first sedimentation mud mixture is sent into the first centrifuge
The first centrifugal treating is carried out, sulfate dihydrate calcium precipitate is obtained, the first centrifuged supernatant merges into first with the first sedimentation supernatant
Supernatant；
5) the first supernatant flows into the second mixing reactor, while resolution lime is added into the second mixing reactor and carries out second
Precipitation reaction；Then the second precipitation reaction mixture is flowed into the second sedimentation basin, carries out the second settlement treatment, obtain the second sedimentation
Mud mixture and the second sedimentation supernatant；Then by second sedimentation mud mixture be sent into the second centrifuge, carry out second from
Heart processing, obtains magnesium hydrate precipitate, and the second centrifuged supernatant merges into the second supernatant with the second sedimentation supernatant；
6) circulating repetition step 4), 5), until having handled magnesium sulfate waste water.
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| CN201810342090.0A CN108483716A (en) | 2018-04-17 | 2018-04-17 | A kind of magnesium sulfate waste water processing equipment for recycling and processing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810342090.0A CN108483716A (en) | 2018-04-17 | 2018-04-17 | A kind of magnesium sulfate waste water processing equipment for recycling and processing method |
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ID=63316200
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115465970A (en) * | 2022-09-27 | 2022-12-13 | 江西江铜银珠山矿业有限公司 | Production process for degrading zinc content in wastewater by comprehensively stirring lime and zinc-containing wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002316121A (en) * | 2001-04-19 | 2002-10-29 | Fuji Kikai Kk | Treatment method of incinerator fly ash and incinerator fly ash washing solution |
| US6790352B1 (en) * | 1996-03-11 | 2004-09-14 | Stephen Ray Wurzburger | Process for treating acid mine water with moderate to high sulfate content |
-
2018
- 2018-04-17 CN CN201810342090.0A patent/CN108483716A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6790352B1 (en) * | 1996-03-11 | 2004-09-14 | Stephen Ray Wurzburger | Process for treating acid mine water with moderate to high sulfate content |
| JP2002316121A (en) * | 2001-04-19 | 2002-10-29 | Fuji Kikai Kk | Treatment method of incinerator fly ash and incinerator fly ash washing solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115465970A (en) * | 2022-09-27 | 2022-12-13 | 江西江铜银珠山矿业有限公司 | Production process for degrading zinc content in wastewater by comprehensively stirring lime and zinc-containing wastewater |
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