CN101407325B - Method for separating boric acid and magnesium sulphate in boric acid production mother liquor by using magnesium sulphate - Google Patents
Method for separating boric acid and magnesium sulphate in boric acid production mother liquor by using magnesium sulphate Download PDFInfo
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- CN101407325B CN101407325B CN2008102287458A CN200810228745A CN101407325B CN 101407325 B CN101407325 B CN 101407325B CN 2008102287458 A CN2008102287458 A CN 2008102287458A CN 200810228745 A CN200810228745 A CN 200810228745A CN 101407325 B CN101407325 B CN 101407325B
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- magnesium
- boric acid
- sal epsom
- mother liquor
- magnesium sulfate
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Abstract
The invention relates to a method for separating boric acid from magnesium sulfate in a boric acid-production mother liquor by using the magnesium sulfate, which comprises the steps: the boric acid-production mother liquor is heated up to 65-80 DEG C, magnesium salt is added under stirring, the temperature is preserved at 65-80 DEG C until the magnesium slat is dissolved completely, filtering is carried out by a sheet frame at 80 DEG C, filtrate becomes crystal mush containing crystal when being cooled, the crystal mush is sent to a boron-magnesium classificator for classifying, magnesium sulphata heptahydrate enters a centrifuge from the lower part of the classificator and is centrifugation separated out; and the floating mixture of the boric acid and the magnesium sulfate at the upper part of the classificator enters a settling tank for separation further to obtain a mixture containing about 60 percent of H3BO3, which is then refined to obtain boric acid product. The filtrate and thesheet frame return to boric acid production technology. The magnesium salt is the magnesium sulfate, monohydrate magnesium sulfate or the mixture thereof, or powder-shaped boron-magnesium acidification substance which contains the monohydrate magnesium sulfate and is generated by the reaction between boron-magnesium ore and sulfate, or magnesia, magnesite, brucite or the product which includes the monohydrate magnesium sulfate and is generated by the reaction between magnesium hydroxide and the sulfate.
Description
Technical field
The invention belongs to boratory technical field, also relate to the treatment technology of the waste water in its production simultaneously.
Background technology
The method that single stage method is produced boric acid is to be that decomposition agent is handled boron rock and made boric acid with sulfuric acid, and it has flow process weak point, less investment, advantage such as simple to operate.Produce mother liquor in this Technology and contain 3% the boric acid of having an appointment, owing to wherein also contain a large amount of sal epsom, the mother liquor amount that causes boric acid to be produced is very big, and producing one ton of boric acid has 6～40M approximately
3The early stage mother liquor of producing all emits, and has both polluted environment, has lost resource again, has 25% boric acid to drain with waste water approximately.In the last few years; petering out and protect environment requirement along with boron resource; many R﹠D institutions, manufacturing enterprise and institution of higher learning are purpose for the yield that improves boron; carried out technical studies such as " salting-out process ", " extraction process ", " precipitation separation ", " elutriation method ", " thickening flotation method ", obtained some progress on separating at boron, magnesium.As CN 1097810A; CN 1039112C; Xu Ning etc., boric acid is produced the Separation Research (J) of sal epsom in the mother liquor, chemical science and technology, 2003,11 (6): 30～33; CN 1251968C etc. all is that the mother liquor with different salt pair boric acid production carries out Separation Research, although the solubleness of a kind of composition in the separated mixture that can obviously reduce salting-out process reduces and separates out easily, but a large amount of dissolvings of salting-out agent and solute in the mother liquor does not reduce, other ion of bringing into makes mother liquor can't return recycle in the Production Flow Chart; And also there is bigger problem in the corrosion of equipment.As making salting-out agent with vitriol, though can not bring other impurity into, the anticorrosion of its equipment also is insoluble.In addition, concentrate the purpose that reaches recovery boron, magnesium by mother liquid evaporation, its energy consumption is very high, and manufacturing enterprise is difficult to accept.
The processing of boron rock production mother liquor and the problem of utilization are not still had very good maturation method so far, and this also is the biggest problem that influences the boric acid production cost.
Summary of the invention
The present invention is directed to the defective that prior art exists, provide a kind of boron, magnesium that boric acid is produced in the mother liquor to be separated, can production unit not corroded again, and the effective processing method of non-environmental-pollution.
The principle of technical basis of the present invention is: sal epsom has the crystal water of different numbers in the mother liquid of boric acid in different solubility under the different temperature and generation sal epsom crystallization under different temperature, utilize sal epsom under differing temps, to have the characteristic of modal difference, boron, magnesium are separated.Solubleness and crystal water state such as the following table of sal epsom under differing temps:
Solubleness and the crystal water state of table 1 sal epsom under obstructed temperature
| Temperature ℃ | Solubleness weight % | Solid phase sal epsom contains the state of crystal water |
| —2.5 | 17.0 | MgSO 4·7H 2O |
| 0 | 16.0 | ″ |
| 10 | 22.0 | ″ |
| 20 | 25.2 | ″ |
| 25 | 26.7 | ″ |
| 30 | 28.0 | ″ |
| 35 | 29.3 | ″ |
| 40 | 30.8 | ″ |
| Temperature ℃ | Solubleness weight % | Solid phase sal epsom contains the state of crystal water |
| 45 | 32.3 | ″ |
| 48 | 33.0 | MgSO 4·7H 2O、MgSO 4·6H 2O |
| 50 | 33.4 | MgSO 4·6H 2O |
| 60 | 35.3 | ″ |
| 65 | 36.3 | ″ |
| 69 | 37.1 | MgSO 4·6H 2O、MgSO 4·H 2O |
| 80 | 35.8 | MgSO 4·H 2O |
| 90 | 34.6 | ″ |
| 100 | 33.4 | ″ |
| 120 | 30.0 | ″ |
| 140 | 24.0 | ″ |
| 160 | 13.0 | ″ |
| 170 | 8.0 | ″ |
| 180 | 5.0 | ″ |
As can be seen from the above table: along with the rising of temperature, its sal epsom solubleness strengthens, and a flex point is arranged about about 69 ℃, and promptly solubleness reduces on the contrary with the temperature rising.Simultaneously the number of the crystal water of sal epsom raises with temperature and reduces: rising to 50 ℃ by initial 7 water magnesium sulfates to temperature becomes 6 water magnesium sulfates, becomes magnesium sulfate monohydrate more than the temperature rise to 70 ℃.The present invention utilizes this characteristic to finish boric acid to produce the isolating of boron, magnesium in the mother liquor.
Concrete technical scheme of the present invention is: boric acid is produced 65～80 ℃ of mother liquor intensifications make sal epsom reach maximum solubleness, at this moment sal epsom is undersaturated in the solution, add and a certain amount ofly contain magnesium salts or its mixture of sal epsom, magnesium sulfate monohydrate and make its dissolving, then solution is lowered the temperature, separating out magnesium sulfate monohydrate greater than 67.5 ℃, 67.5 separate out six water magnesium sulfates for～48.0 ℃, what separate out below 48.0 ℃ is magnesium sulfate heptahydrate.Owing to added sal epsom, in case lower the temperature then mother liquid of boric acid becomes hypersaturated state for sal epsom just separates out the sal epsom that has seven crystal water, thereby owing to taken the water the solution out of to seven water magnesium salts, can reach supersaturation in the mother liquor and separate out the sal epsom that more has seven crystal water from a water magnesium salts.In the time of 80 ℃ through Plate Filtration, become during the filtrate cooling and contain the crystalline magma, magma is delivered to boron magnesium classifier, magnesium sulfate heptahydrate enters whizzer from the classifier bottom, centrifugation goes out magnesium sulfate heptahydrate, so just the sal epsom in the mother liquor can be reclaimed.And classifier top buoyant boric acid, sal epsom mixture enters subsider and further separates, and obtains containing H
3BO
340～60% mixture, this mixture is the boric acid product through making with extra care.Thereby the continuation of all filtrates is heated up, adds magnesium salts, Plate Filtration, cools, classification is constantly taken out of sal epsom and water in the mother liquid of boric acid with separating down, setting up till new boron, the magnesium homeostasis point when reaching low temperature.Heat up, add sal epsom or magnesium sulfate monohydrate and make its dissolving carry out next one circulation as continuing again, circulation like this is gone down and just sal epsom in the mother liquid of boric acid and boric acid is separated the purpose that reclaims boric acid and sal epsom to reach.By this separation, the mother liquor amount can reduce 29～49%.Certainly, when reaching new boron, magnesium homeostasis point in the mother liquid of boric acid, the mother liquor that contains boric acid and sal epsom can be returned the production that participates in boric acid in the process of boracic acid production.All filtrations, the filtrate after separating, and the sheet frame washing lotion can be returned in the Production Flow Chart of boric acid and uses.Composition in all mother liquors all can obtain separating and reclaiming, and does not have hazardous emission.Rising to 70.0～75.0 ℃ for well, filtrate was cooled to 20～25 ℃ for well when mother liquor heated up on above-mentioned processing condition, and the amount of adding sal epsom or magnesium sulfate monohydrate is to reach capacity to good.
Equally, can utilize the characteristic that generates different crystal water sal epsom under different solubilities and the differing temps under differing temps, boric acid is produced mother liquor be warming up to sal epsom maxima solubility (as 70～75 ℃), making boric acid produce mother liquor becomes the unsaturated solution state, the surplus water that comes out can dissolve the salt that other contains magnesium.What should be mentioned that especially is that employed magnesium salts can be the powdery boron magnesium acidulants (technology described in ZL 03101382.1) that contains magnesium sulfate monohydrate that boron magnesium ore deposit and sulfuric acid reaction generate, also can be the product that contains magnesium sulfate monohydrate that magnesium oxide, magnesite, brucite mineral or magnesium hydroxide and sulfuric acid reaction generate, it utilizes effect very desirable.
The boric acid production history is long but the processing production mother liquor is a difficult problem always, is not that arbitrarily discharging is exactly to deposit.If deposit, the time one, the long container corrosion mother liquor for the treatment of was still missed loss, and this problem can not obtain properly and for a full due solving for a long time.And this technology of the present invention has solved this difficult problem satisfactoryly: add homo-ion magnesium salts or boron magnesium salts in the mother liquor, its high-temperature digestion low temperature is separated out, utilize the different principle of the different contained crystal water of sal epsom of temperature, make the sal epsom that has a plurality of crystal water separate out the moisture that reduces in the mother liquid of boric acid by variation of temperature and reach boric acid and separate effectively with sal epsom.
Compared with prior art the outstanding advantage that has of the present invention is: (1) technological line is reasonable in design, ingenious, feasible.Take magnesium sulfate heptahydrate-the reach purpose of separating boron and magnesium out of with " opposition thinking "-add magnesium sulfate monohydrate.(2) production technique is simple, and is workable, low equipment investment, and corrodibility is little.(3) boric acid production mother liquor all reclaims, and boron, magnesium in the boron resource is fully used, thereby has reduced the boric acid production cost.Low-grade boron ore also can obtain utilizing.(4) do not have prior art to need a large amount of energy to be used for the evaporation of mother liquor like that, the present invention only uses low-yield heating, and production energy consumption is low.(5) no any harmful gas, water, slag discharging, environment protecting is good.
Embodiment
Embodiment 1
Add the mother liquor that 1000Kg boric acid is produced in the reactor, heat temperature raising to 75～80 ℃, stir and add the 200Kg magnesium sulfate monohydrate down, the temperature that keeps 75～80 ℃ (sal epsom solubleness maximums under this temperature) is to making it dissolve the postcooling cooling fully, sal epsom is separated out with magnesium sulfate heptahydrate, when treating that temperature drops to 20～25 ℃, slurry is sent in the classifier, the magnesium sulfate heptahydrate crystallization enters whizzer from the classifier bottom, and centrifugation goes out magnesium sulfate heptahydrate 530kg as agricultural.Boric acid is because its hydrophobicity that has enters subsider from minute machine top and tells boric acid, sal epsom mixture, and the only surplus 510kg of mother liquid of boric acid returns and produces in the boric acid flow process.
Embodiment 2
Add 1000Kg boric acid in the reactor and produce mother liquor, heat temperature raising to 75～80 ℃, stir and add 200Kg sal epsom down, make it dissolve the postcooling cooling fully, magnesium sulfate heptahydrate is separated out from mother liquor gradually in temperature-fall period, when the mother liquor temperature reaches 20～25 ℃, will have magnesium sulfate heptahydrate crystalline mother liquor slurry and send as in the classifier, the magnesium sulfate heptahydrate crystallization enters whizzer from the classifier bottom, and centrifugation goes out magnesium sulfate heptahydrate 650kg.Classifier top buoyant boric acid and sal epsom separate obtaining this mixture.
Embodiment 3
Produce acidulants with the described method of ZL03101382.1.Get and contain 13%B
2O
3Boron magnesium slag 1000Kg insert in the reactor, add the 550Kg mother liquid of boric acid, stirring down, adding 640Kg sulfuric acid (concentration 40～75%) carries out acidification reaction, its temperature of reaction is controlled at more than 80 ℃, the magnesium that is magnesium in the mother liquid of boric acid and boron magnesium ore deposit generates magnesium sulfate monohydrate, it is dry and comfortable powder that question response finishes to stack nature cooling back acidulants, and it consists of B
2O
35.41%, MgSO
4H
2O72.6%.This acidulants is produced the isolating material of boron magnesium in the mother liquor as boric acid.
Get the 1000kg mother liquid of boric acid and (contain MgSO
424.0%, B
2O
32.5%) puts into reactor, heat temperature raising to 75～80 ℃ are stirred and are added above-mentioned acidulants 200kg down, and reaction solution keeps 75～80 ℃, after treating the whole dissolvings of boron magnesium in the acidulants, under 80 ℃, behind Plate Filtration, obtain limpid boron magnesium crystal solution 1145kg and (contain H
3BO
33.86%, MgSO
431.97%), when cooling was cooled to 20～25 ℃, this magma was through boron magnesium classifier, and magnesium sulfate heptahydrate enters whizzer from the classifier bottom, and centrifugation goes out magnesium sulfate heptahydrate 400kg and (contains H
3BO
3＜1.5%).Enter subsider from classifier top buoyant boric acid, sal epsom mixture and further separate, obtain containing H
3BO
3About 60% mixture 30kg.Mother liquid of boric acid reduces to 710kg from 1000kg.In addition, the waste sludge discharge after washing of the filtration residue on the sheet frame, washing lotion is returned and is sent boric acid production to use.
Embodiment 4
Get the 1000kg mother liquid of boric acid and (contain MgSO
424.0%, B
2O
32.5%) put into reactor, be warming up to 75～80 ℃, stir and to add above-mentioned acidulants 300kg down, reaction is protected 75～80 ℃, treats that boron magnesium in the acidulants all after the dissolving, obtains limpid boron magnesium crystal solution 1220kg and (contains H under 80 ℃ behind Plate Filtration
3BO
34.40%MgSO
435.25%), when cooling was cooled to 20～25 ℃, this magma was through boron magnesium classifier, and magnesium sulfate heptahydrate enters whizzer from the classifier bottom, and centrifugation goes out magnesium sulfate heptahydrate 620kg.Classifier top buoyant boric acid, sal epsom mixture enter subsider further to be separated, and obtains containing H
3BO
3About 60% mixture 50kg is the boric acid product through making with extra care.Mother liquid of boric acid reduces to 530kg from 1000kg, and it consists of: MgSO
424.0%, B
2O
32.5%.
Embodiment 5
Get the 1000kg mother liquid of boric acid and put into reactor, be warming up to 75～80 ℃, stir to add down and react and the acidulants that obtains (contains B by low levels boron rock and sulfuric acid acidation
2O
32%, MgSO
4H
2O70%) powder 260kg dissolves and obtains limpid boron magnesium crystal solution 1200kg through Plate Filtration under back 80 ℃ and (contain H
3BO
34.1%, MgSO
433.6%) as follows embodiment 4 operations: magma classification, centrifugation obtain magnesium sulfate heptahydrate 500kg, classifier top buoyant boric acid, sal epsom mixture 40kg.Mother liquid of boric acid reduces to 610kg from 1000kg.
Claims (3)
1. separate the method that boric acid is produced mother liquor mesoboric acid and sal epsom with sal epsom, it is characterized in that processing step is:
(1) boric acid is produced mother liquor and is warming up to 65～80 ℃, stirs to add magnesium salts down, keeps 65～80 ℃ all to dissolve to magnesium salts;
Through Plate Filtration, become during the filtrate cooling and contain the crystalline magma in the time of (2) 80 ℃, when filtrate is cooled to 20～25 ℃ magma is delivered to boron magnesium classifier, magnesium sulfate heptahydrate enters whizzer from the classifier bottom, and centrifugation goes out magnesium sulfate heptahydrate;
(3) classifier top buoyant boric acid, sal epsom mixture enter subsider and further separate, and obtain containing H
3BO
340～60% mixture;
(4) filtrate and sheet frame washing lotion are returned the boric acid production technique;
Described magnesium salts is: sal epsom, magnesium sulfate monohydrate or its mixture.
2. separate the method that boric acid is produced mother liquor mesoboric acid and sal epsom according to claim 1 is described with sal epsom, it is characterized in that described magnesium salts is: the product that contains magnesium sulfate monohydrate that magnesium oxide, magnesite, brucite mineral or magnesium hydroxide and sulfuric acid reaction generate.
3. separate the method that boric acid is produced mother liquor mesoboric acid and sal epsom according to claim 1 is described with sal epsom, it is characterized in that described step (1) mesoboric acid produces mother liquor and be warming up to 75～80 ℃, stir adding magnesium salts down, keep 75～80 ℃ all to dissolve to magnesium salts.
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| CN2008102287458A CN101407325B (en) | 2008-11-11 | 2008-11-11 | Method for separating boric acid and magnesium sulphate in boric acid production mother liquor by using magnesium sulphate |
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|---|---|---|---|
| CN2008102287458A CN101407325B (en) | 2008-11-11 | 2008-11-11 | Method for separating boric acid and magnesium sulphate in boric acid production mother liquor by using magnesium sulphate |
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| CN101407325B true CN101407325B (en) | 2010-06-16 |
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| CN105329923B (en) * | 2015-11-17 | 2017-01-25 | 朱冲 | Crystallization process of magnesium method flue gas desulfurization by-product magnesium sulfate |
| RU2712737C1 (en) * | 2018-12-13 | 2020-01-30 | Закрытое Акционерное Общество "МагнийПром" | Processing method of magnesium-containing material |
| CN110357119A (en) * | 2019-08-26 | 2019-10-22 | 东北大学 | A kind of new method using magnesium sulfate in non-evaporative crystallization method removing boric acid solution |
| CN112723933A (en) * | 2021-01-18 | 2021-04-30 | 辽宁华昇金玛生态工程有限公司 | Method for preparing secondary element water-soluble fertilizer by using mother liquor water-free method |
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