CN100588614C - Method for preparing sodium chloride and magnesium sulphate heptahydrate with brine - Google Patents
Method for preparing sodium chloride and magnesium sulphate heptahydrate with brine Download PDFInfo
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- CN100588614C CN100588614C CN200810054198A CN200810054198A CN100588614C CN 100588614 C CN100588614 C CN 100588614C CN 200810054198 A CN200810054198 A CN 200810054198A CN 200810054198 A CN200810054198 A CN 200810054198A CN 100588614 C CN100588614 C CN 100588614C
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- magnesium sulfate
- sulfate heptahydrate
- mother liquor
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- bittern
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Abstract
The invention discloses a method for using brine to produce sodium chloride and heptahydrate magnesium sulfate, comprising the steps that: (1) brine is taken as a raw material, the molar ratio of SO4<2->:Mg<2+> in the brine is 0.1-0.8, and the molar ratio of SO4<2->:Na<+> is 0.025-1; and the pressure is decreased for boiling evaporation, the pressure is controlled to make the boiling temperature be 75 DEG C to 50 DEG C after the evaporation, and the molar ratio of SO4<2>:Na<+> in the solution is 0.4-2.5; (2) solid-liquid separation is implemented, and the solid phase is washed with saturated sodium chloride aqueous solution and is then dried for obtaining the sodium chloride; (3) a mother liquid of salt production is added with water to prepare a mixture; (4) the mixture is cooled and guided into a crystallizer, then crystals are separated out; and (5) solid-liquid separation is carried out for obtaining a crude product having a solid phase of heptahydrate magnesium sulfate. The methodhas advantages of simple equipment, simple process, complete separation of sodium chloride, high purity and yield of heptahydrate magnesium sulfate, having no miscellaneous salt removing link in theprocess, and realizable joint production of sodium chloride and heptahydrate magnesium sulfate.
Description
Technical field
The present invention relates to the salt manufacturing field, particularly relate to a kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern.
Background technology
Bittern salt manufacturing extensively adopts the beach to shine evaporation salt manufacturing at present, or saturated bittern vacuum salt etc. is shone on the beach.The salt-making mother liquor of existing salt manufacturing mode, perhaps discharging, perhaps the traditional method of Li Yonging fully utilizes.It is disagreeableness to environment adopting the mode of discharging.Tradition comprehensive utilization mode is core with the producing potassium chloride by halogen conversion method, and main products has Repone K, magnesium chloride (halogen sheet, halogen powder), sodium sulfate, bromine etc.Salt-making mother liquor is that the bromine mother liquor of carrying of main component makes the concentration ratio of sal epsom and magnesium chloride in the bittern reduce (dropping to about 0.35 about from 0.45) through being blended into the magnesium chloride, the ratio of magnesium chloride and Repone K improves (bringing up to more than 10 from about 7.7) simultaneously, convert mixing halogen after the halogen in evaporation more than 100 ℃, sodium-chlor and sal epsom are fully separated out, settlement separate to go out with sodium-chlor and magnesium sulfate monohydrate be the mixing salt of main component through being incubated, and is commonly called as high and tow temperature salt.Clear liquor further cooling is separated out carnallitite, and carnallitite decomposes production Repone K again.Carnallite mother solution is then further carried bromine and is produced magnesium chloride.
High and tow temperature salt only begins afterwards it to be carried out the separation of produced magnesium sulfate monohydrate as abraum salt.Separation method adopt the dissolving cold method, or thermosol is invaded method in the eighties of last century 60-70 age.The 80-90 age, utilize magnesium sulfate monohydrate and the significant difference of sodium-chlor on grain size number in the high and tow temperature salt, adopt physics method such as concussion method, press over system and swirler method etc., the mixed salt that high temperature evaporation is separated out is separated into magnesium sulfate monohydrate slurry (magnesia magma) and sodium-chlor slurry, resulting sal epsom and sodium-chlor quality are low, contain a large amount of sodium-chlor in the sal epsom.Ox contented (1994) is developed the production technique with swirler and settling centrifuge separating high-temp salt.The magnesia magma that obtains after the mixing salt slurry separates based on sal epsom, but contains fine grain sodium-chlor and mother liquid evaporation, and with its direct filtration, water pushes away the mother liquor in the magnesia magma again, but makes the sal epsom loss very big because sal epsom dissolves easily.
Glassett (1970) with the Exposure to Sunlight method with evaporation of seawater to the mass concentration of magnesium greater than 4%, add 10% clear water of bittern volume, be cooled to-15 ℃, produce sal epsom.
Fernandez-Lozano (1974) is the Exposure to Sunlight bittern of 1.30g/l to proportion, and the adding volume ratio is 5% clear water, is cooled to-5 ℃, 70% sal epsom in the recovery bittern.The sal epsom cold water washing, 70 ℃ of dryings, the content of magnesium sulfate heptahydrate is 96%.
Arakel (1993) is different with the method for Fernandez-Lozano, is the Exposure to Sunlight bittern of 1.28-1.30g/l to proportion, is cooled to 0 ℃ to-5 ℃ and obtains thick sal epsom, all with the hot water dissolving and to be evaporated to proportion be that 1.28-1.30g/l is again 20-25 ℃ of crystallization.
The patent DE10256046 of BACH JUERGEN (2004) utilizes bittern to produce sodium-chlor and magnesium sulfate heptahydrate.Adopt two covers two to imitate evaporation unit.Add circulating mother liquor and make the ratio of sal epsom and magnesium chloride bring up to 0.25～0.5, saturated to sal epsom with the first covering device evaporation concentration, the sodium-chlor of separation evaporative crystallization is as the refined salt product.Complete evaporation of liquid adds water-cooled and freezes brilliant magnesium sulfate heptahydrate.Freezing mother liquor continues to utilize the second cover evaporation unit, carries out dual circulation, removes impurity salt and makes mother liquor purification, and the mother liquor after the purification follows back adjustment sal epsom and the magnesium chloride ratio in the raw material converted, about 1: 1 of the ratio of mother liquor amount and material quantity.In this invention, need be provided with the dual circulation crystallizer that a cover is specifically designed to out the low-quality carnallite.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern is provided, comprise the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio be 0.1～0.8, and SO
4 2-: Na
+Mol ratio be 0.025～1; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 75 ℃～50 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Mol ratio is 0.4～2.5;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) in described salt-making mother liquor, add the water of 0.05～0.2 times of described salt-making mother liquor quality, or add the magnesium sulfate heptahydrate recrystallization mother liquor of 0.5～4 times of described salt-making mother liquor quality, or the saturated solution of magnesium sulfate that adds 0.5～4 times of described salt-making mother liquor quality is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 40～20 ℃, is incorporated in the crystallizer that contains 0～-10 ℃ of crystal solution, has crystallization to separate out, and described crystal solution is one of following situation when first production: a) saturated solution of magnesium sulfate; B) directly freezing crystallization is separated out to 0～-10 ℃ with the described mixed solution of described step (3), the liquid after crystallization is removed; When continuous production, the part feed liquid of being retained in the crystallizer;
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates SO in the raw brine
4 2-: Mg
2+Mol ratio, all the other discharge systems.
Can also comprise the steps: that be that 1: 0.3～0.5 ratio adds water with described magnesium sulfate heptahydrate crude product in mass ratio, rising temperature for dissolving, or add the magnesium sulfate heptahydrate recrystallization mother liquor of 0.8～2 times of quite described magnesium sulfate heptahydrate crude product quality, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20～0 ℃, there is crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
SO in described step (1) raw brine
4 2-: Mg
2+Mol ratio be preferably 0.1～0.5, and SO
4 2-: Na
+Mol ratio be 0.025～1.
SO when evaporation is finished in the described step (1)
4 2: Na
+Mol ratio is preferably 1～2.5.
Method equipment of the present invention is simple, technology is simple, in process of production sodium-chlor separate out fully, the high and yield height of the purity of magnesium sulfate heptahydrate does not have the carnallite link of removing, the combination producing of realization sodium-chlor and magnesium sulfate heptahydrate in the process.
Description of drawings
Fig. 1 the present invention produces the process flow sheet of the method for sodium-chlor and magnesium sulfate heptahydrate with bittern.
Among the figure: the 1-vacuum vaporation system, be generally multiple-effect evaporation, or other forms of reduction vaporization; The 2-mixing tank; The 3-crystallizer; The 4-dissolving tank; The 5-recrystallizer.
The a-salt-making mother liquor; The b-mixed solution; C-magnesium sulfate heptahydrate crude product; D-magnesium sulfate heptahydrate dissolving crude product liquid.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps (see figure 1):
Stock liquid enters vacuum vaporation system 1, if adopt multiple-effect evaporation, then should adopt the following current marker method, and the temperature of salt-making mother liquor a is not more than 75 ℃ when bringing the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is 0.4～2.5; Feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor; Salt-making mother liquor adds suitable quantity of water or an amount of magnesium sulfate heptahydrate recrystallization mother liquor or saturated solution of magnesium sulfate and makes mixed solution b in mixing tank 2; Mixed solution cools off in crystallizer 3 has crystallization to separate out, obtain magnesium sulfate heptahydrate crude product c after the separation, the magnesium sulfate heptahydrate crude product is through after the centrifuge dehydration, in dissolving tank 4, add entry or magnesium sulfate heptahydrate recrystallization mother liquor, be warmed up to and be dissolved into magnesium sulfate heptahydrate dissolving crude product liquid d about 70 ℃, magnesium sulfate heptahydrate dissolving crude product liquid is in recrystallizer 5, be cooled to crystallization again below 20 ℃ once more, separate through whizzer, solid phase be not higher than 70 ℃ of gas dryings, obtain refining magnesium sulfate heptahydrate, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Get 1000ml and contain potassium bittern, form concentration KCl:15.0g/l, MgCl
2: 81.0g/l, MgSO
4: 93.0g/l, NaCl:183.0g/l, H
2O:890.0g/l, wherein SO
4 2-: Na
+Mol ratio=0.25, SO
4 2-: Mg
2+Mol ratio=0.48, electricity consumption heating jacket heating in there-necked flask, there-necked flask connects vacuum pump, makes feed liquid 55 ℃ of explosive evaporatoins by control pressure, evaporates 395g water, this moment liquid phase SO
4 2-: Na
+Mol ratio is about 1.8, carries out solid-liquid separation, and solid phase is washed with saturated sodium-chloride water solution, obtains 153g sodium-chlor after the drying, and purity is 99.5%; Salt-making mother liquor adds 80g water, be pre-chilled to and be added to (crystal solution is a saturated solution of magnesium sulfate) in the crystallizer that contains crystal solution after 30 ℃, the temperature of crystallizer is-5 ℃, treat sufficient crystallising after, carry out solid-liquid separation, solid phase adds the magnesium sulfate heptahydrate recrystallization mother liquor and is warmed to 70 ℃ of dissolvings, and lysate is cooled to 0 ℃ again, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase is washed with saturated solution of magnesium sulfate, obtains 136g magnesium sulfate heptahydrate elaboration after the drying, and purity is 99.6%.
Get 1000ml salt lake intercrystalline bittern, composition concentration is MgCl
2: 120.0g/l, MgSO
4: 118.0g/l, NaCl:140g/l, H
2O:818.0g/l, wherein SO
4 2-: Na
+Mol ratio=0.41, SO
4 2-: Mg
2+Mol ratio=0.44, electricity consumption heating jacket heating in there-necked flask, there-necked flask connects vacuum pump, makes feed liquid 60 ℃ of explosive evaporatoins by control pressure, evaporates 218.6g water, SO in the liquid phase
4 2-: Na
+Mol ratio be 1.77, carry out solid-liquid separation, solid phase is washed with saturated sodium-chloride water solution, obtains 55g sodium-chlor after the drying, purity is 99.5%; After salt-making mother liquor adds 80g water, be added to again in-5 ℃ the crystallizer that contains crystal solution (crystal solution is a saturated solution of magnesium sulfate), treat sufficient crystallising after, separating obtained solid phase, solid phase adds 20 ℃ saturated solution of magnesium sulfate, is made into 70 ℃ sal epsom near saturated solution, and it is cooled to 0 ℃ again, there is crystallization to separate out, carry out solid-liquid separation, the gained solid phase is washed with saturated solution of magnesium sulfate, washs with saturated solution of magnesium sulfate, obtain 145g magnesium sulfate heptahydrate elaboration after the solid phase drying, purity is 99.5%.
Get 1000g preparing salt by working up seawater beach and shine saturated bittern, composition concentration is Ca
2+: 0.038%, Mg
2+: 2.599%, K
+: 0.711%, Na
+: 7.86%, Cl
-: 17.2%, SO
2- 4: 4.116%, H
2O:67.6%, wherein SO
4 2-: Na
+Mol ratio=0.127, SO
4 2-: Mg
2+Mol ratio=0.40, electricity consumption heating jacket heating in there-necked flask, there-necked flask connects vacuum pump, makes feed liquid 60 ℃ of explosive evaporatoins by control pressure, evaporates 380.g water, SO in the liquid phase
4 2-: Na
+Mol ratio 2.05 is carried out solid-liquid separation, and solid phase is washed with saturated sodium-chloride water solution, obtains 170g sodium-chlor after the drying, and purity is 99.5%; After salt-making mother liquor adds 80g water, be added in-5 ℃ the crystallizer that contains crystal solution (crystal solution is a saturated solution of magnesium sulfate), treat sufficient crystallising after, separating obtained solid phase, add the magnesium sulfate heptahydrate recrystallization mother liquor, be made into 70 ℃ saturated solution of magnesium sulfate, be cooled to 0 ℃ again, have crystallization to separate out, carry out solid-liquid separation, the gained solid phase is washed with saturated solution of magnesium sulfate, obtains 74g magnesium sulfate heptahydrate elaboration after the solid phase drying, and purity is 99.5%.
Getting 1000g preparing salt by working up seawater mother liquor (bittern) composition concentration is Ca
2+: 0.019%, Mg
2+: 5.249%, K
+: 1.466%, Na
+: 4.77%, Cl
-: 19.61%, SO
2- 4: 5.853%, H
2O:63.02%, wherein SO
4 2-: Na
+Mol ratio=0.299, SO
4 2-: Mg
2+Mol ratio=0.282, electricity consumption heating jacket heating in there-necked flask, there-necked flask connects vacuum pump, makes feed liquid 60 ℃ of explosive evaporatoins by control pressure, evaporates 77g water, SO in the liquid phase
4 2-: Na
+Mol ratio is 2.4, carry out solid-liquid separation, solid phase is washed with saturated sodium-chloride water solution, obtain 84g sodium-chlor after the drying, purity is 99.6%, after salt-making mother liquor adds water, joins in-5 ℃ the crystal solution, after treating sufficient crystallising, separating obtained solid phase adds the magnesium sulfate heptahydrate recrystallization mother liquor, is made into 70 ℃ saturated solution of magnesium sulfate, be cooled to 0 ℃ again, have crystallization to separate out, carry out solid-liquid separation, the gained solid phase is washed with saturated solution of magnesium sulfate, obtain 104g magnesium sulfate heptahydrate elaboration after the solid phase drying, purity is 99.4%.
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio=0.1 and SO
4 2-: Na
+Molar ratio 0.025; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 50 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is near 2.5;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) water that adds 0.05 times of described salt-making mother liquor quality in described salt-making mother liquor is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 30 ℃, is incorporated in the crystallizer that contains-5 ℃ of crystal solution, and the amount of crystal solution makes in the reinforced process, and feed temperature is no more than 0 ℃, has crystallization to separate out, (crystal solution is a saturated solution of magnesium sulfate);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the gained liquid phase is discharged system.
Present embodiment can also increase a step:
(6) be that 1: 0.4 ratio adds water with the magnesium sulfate heptahydrate crude product in mass ratio, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 10 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Embodiment 6
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio=0.1, and SO
4 2-: Na
+Molar ratio 0.5; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 75 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is near 2.5;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) in described salt-making mother liquor, add the water of 0.2 times of described salt-making mother liquor quality, make mixed solution;
(4) mixed solution that described step (3) is made is cooled to 40 ℃, is incorporated in the crystallizer that contains-10 ℃ of crystal solution, has crystallization to separate out (crystal solution is that directly freezing crystallization is separated out to 0 ℃ with the mixed solution of step (3), the liquid after crystallization is removed);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the gained liquid phase is discharged system.
Present embodiment can also increase a step:
(6) described magnesium sulfate heptahydrate crude product is that 1: 0.3 ratio adds water in mass ratio, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 0 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Embodiment 7
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio=0.5, and SO
4 2-: Na
+Molar ratio 0.025; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 50 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio reaches 1;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) in described salt-making mother liquor, add the water of 0.1 times of described salt-making mother liquor quality, make mixed solution;
(4) mixed solution that described step (3) is made is cooled to 20 ℃, is incorporated in the crystallizer that contains-5 ℃ of crystal solution, has crystallization to separate out (when crystal solution is meant continuous production, the part feed liquid of being retained in the crystallizer);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates SO in the bittern
4 2-: Mg
2+Molar ratio, all the other discharge systems.
Present embodiment can also increase a step:
(6) be that 1: 0.5 ratio adds water with described magnesium sulfate heptahydrate crude product in mass ratio, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Embodiment 8
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio be 0.5, and SO
4 2-: Na
+Molar ratio 1.0; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 65 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is about 2.0;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) the magnesium sulfate heptahydrate recrystallization mother liquor that adds 0.5 times of described salt-making mother liquor quality in described salt-making mother liquor is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 20 ℃, be incorporated in the crystallizer that contains-10 ℃ of crystal solution, there is crystallization to separate out (crystal solution is meant that directly freezing crystallization is separated out to-10 ℃ with the described mixed solution of step (3), the liquid after crystallization is removed);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates SO in the bittern
4 2-: Mg
2+Mol ratio, all the other discharge systems.
Present embodiment can also increase a step:
(6) the magnesium sulfate heptahydrate crude product is added the magnesium sulfate heptahydrate recrystallization mother liquor of 0.8 times of quite described magnesium sulfate heptahydrate crude product quality, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Embodiment 9
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio be 0.8, and SO
4 2-: Na
+Molar ratio 1.0; It is an amount of to be blended into the liquid that step (5) produced in raw brine, makes SO
4 2-: Mg
2+Mol ratio reach 0.1～0.5 scope, can be blended into an amount of magnesium chloride solution when producing for the first time and make SO
4 2-: Mg
2+Mol ratio reach 0.1～0.5 scope, to having adjusted SO
4 2-: Mg
2+The explosive evaporatoin of reducing pressure of the liquid of mol ratio, boiling temperature was 55 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is about 2.0;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) the magnesium sulfate heptahydrate recrystallization mother liquor that adds 4 times of described salt-making mother liquor quality in described salt-making mother liquor is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 30 ℃, is incorporated in the crystallizer that contains-5 ℃ of crystal solution, has crystallization to separate out, (crystal solution is meant the mixed solution of step (3), and directly freezing crystallization is separated out to-5 ℃, the liquid after crystallization is removed);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates bittern SO
4 2-: Mg
2+Mol ratio, all the other discharge systems.
Present embodiment can also increase a step:
(6) the magnesium sulfate heptahydrate crude product is added the magnesium sulfate heptahydrate recrystallization mother liquor of 2 times of quite described magnesium sulfate heptahydrate crude product quality, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Embodiment 10
A kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern comprises the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio be 0.8, and SO
4 2-: Na
+Molar ratio 0.025; At first raw brine is evaporated, separate out part sodium-chlor after, it is an amount of to be blended into the liquid that step (5) produced in the bittern, makes SO
4 2-: Mg
2+Mol ratio reaches 0.1～0.5 scope, can be blended into an amount of magnesium chloride solution when producing for the first time and make SO
4 2-: Mg
2+Mol ratio reaches 0.1～0.5 scope, to having adjusted SO
4 2-: Mg
2+The explosive evaporatoin of reducing pressure of the liquid of mol ratio, boiling temperature was 75 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2: Na
+Molar ratio is near 2.5;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) saturated solution of magnesium sulfate that adds 0.5 times of described salt-making mother liquor quality in described salt-making mother liquor is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 30 ℃, is incorporated in the crystallizer that contains 0 ℃ of crystal solution, has crystallization to separate out (crystal solution is meant the part feed liquid of being retained in the crystallizer when continuous production);
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates the SO in the bittern
4 2-: Mg
2+Mol ratio, all the other discharge systems.
Present embodiment can also increase a step:
(6) the magnesium sulfate heptahydrate crude product is added the magnesium sulfate heptahydrate recrystallization mother liquor of 1 times of quite described magnesium sulfate heptahydrate crude product quality, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20 ℃, has crystallization to separate out, carry out solid-liquid separation, the gained solid phase with saturated magnesium sulfate solution washing, obtains the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
Claims (4)
1. a method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern is characterized in that comprising the steps:
(1) to contain Na
+, Mg
2+, Cl
-, SO
4 2-Bittern be raw material, SO in the described bittern
4 2-: Mg
2+Mol ratio be 0.1～0.8, and SO
4 2-: Na
+Mol ratio be 0.025～1; To the raw material explosive evaporatoin of reducing pressure, boiling temperature was 75 ℃～50 ℃ when control pressure brought the evaporation to completion, and SO in the solution
4 2-: Na
+Mol ratio is 0.4～2.5;
(2) feed liquid after the evaporation is carried out solid-liquid separation, obtain solid phase and salt-making mother liquor, described solid phase is washed with saturated sodium-chloride water solution, and the solid drying after the washing obtains sodium-chlor;
(3) in described salt-making mother liquor, add the water of 0.05～0.2 times of described salt-making mother liquor quality, or add the magnesium sulfate heptahydrate recrystallization mother liquor of 0.5～4 times of described salt-making mother liquor quality, or the saturated solution of magnesium sulfate that adds 0.5～4 times of described salt-making mother liquor quality is made mixed solution;
(4) mixed solution that described step (3) is made is cooled to 40～20 ℃, is incorporated in the crystallizer that contains 0～-10 ℃ of crystal solution, has crystallization to separate out, and described crystal solution is one of following situation when first production: a) saturated solution of magnesium sulfate; B) directly freezing crystallization is separated out to 0～-10 ℃ with the described mixed solution of described step (3), the liquid after crystallization is removed; When continuous production, the part feed liquid of being retained in the crystallizer;
(5) will carry out solid-liquid separation through the product that step (4) make, obtaining solid phase is the magnesium sulfate heptahydrate crude product, and the part in the gained liquid phase is returned in the step (1), regulates SO in the raw brine
4 2-: Mg
2+Mol ratio, all the other discharge systems.
2. a kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern according to claim 1, it is characterized in that comprising the steps: that be that 1: 0.3～0.5 ratio adds water with described magnesium sulfate heptahydrate crude product in mass ratio, rising temperature for dissolving, or add the magnesium sulfate heptahydrate recrystallization mother liquor of 0.8～2 times of quite described magnesium sulfate heptahydrate crude product quality, rising temperature for dissolving, lysate is joined in the recrystallizer of recrystallization, the crystallization control temperature is 20～0 ℃, there is crystallization to separate out, carries out solid-liquid separation, the gained solid phase, with saturated magnesium sulfate solution washing, obtain the magnesium sulfate heptahydrate elaboration after the drying, the gained liquid phase is the magnesium sulfate heptahydrate recrystallization mother liquor.
3. a kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern according to claim 1 is characterized in that SO in described step (1) raw brine
4 2-: Mg
2+Mol ratio be 0.1～0.5, and SO
4 2-: Na
+Mol ratio be 0.025～1.
4. a kind of method of producing sodium-chlor and magnesium sulfate heptahydrate with bittern according to claim 1 is characterized in that the SO when evaporation is finished in the described step (1)
4 2-: Na
+Mol ratio is 1～2.5.
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| CN102030350B (en) * | 2010-11-11 | 2012-07-11 | 北京科技大学 | Method for preparing magnesium sulfate heptahydrate by taking magnesium chloride bittern from salt lake as raw material |
| CN101966998B (en) * | 2010-11-26 | 2012-07-04 | 南风化工集团股份有限公司 | New process for preparing magnesium chloride hexahydrate by using high-magnesium brine |
| CN102659148B (en) * | 2012-04-17 | 2013-10-30 | 中国科学院青海盐湖研究所 | Method for preparing magnesium sulfate from tailings produced in extraction of potassium of magnesium sulfate subtype salt lake brine |
| CN105366698B (en) * | 2015-12-14 | 2017-03-29 | 中国科学院青海盐湖研究所 | A kind of preparation method of Magnesium sulfate heptahydrate |
| CN106435227B (en) * | 2016-09-09 | 2018-10-02 | 中国科学院青海盐湖研究所 | The enrichment method of uranium element in a kind of brine |
| CN107814398B (en) * | 2017-11-28 | 2019-12-06 | 中国科学院青海盐湖研究所 | Preparation method of magnesium sulfate heptahydrate |
| CN109437243B (en) * | 2018-10-25 | 2021-07-27 | 中国中轻国际工程有限公司 | High-salt COD wastewater recovery process |
| CN111646488B (en) * | 2020-06-23 | 2022-08-09 | 天津科技大学 | Separation device and separation method for mixed salt solution of sodium sulfate and magnesium sulfate with multiple specific gravity concentrations |
| CN112591775A (en) * | 2020-12-30 | 2021-04-02 | 国投新疆罗布泊钾盐有限责任公司 | Method for extracting magnesium sulfate monohydrate and industrial salt from mixed salt of sodium chloride and magnesium sulfate |
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