CN100588614C - The method for producing sodium chloride and magnesium sulfate heptahydrate with brine - Google Patents
The method for producing sodium chloride and magnesium sulfate 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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- salt
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- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 title claims abstract description 88
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 title claims abstract description 86
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 239000012267 brine Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 239000012452 mother liquor Substances 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 55
- 239000007790 solid phase Substances 0.000 claims abstract description 53
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 239000011734 sodium Substances 0.000 claims abstract description 40
- 239000011777 magnesium Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000001704 evaporation Methods 0.000 claims abstract description 32
- 230000008020 evaporation Effects 0.000 claims abstract description 31
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 30
- 239000012043 crude product Substances 0.000 claims abstract description 27
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 44
- 238000002425 crystallisation Methods 0.000 claims description 43
- 230000008025 crystallization Effects 0.000 claims description 43
- 241001131796 Botaurus stellaris Species 0.000 claims description 37
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 37
- 238000001953 recrystallisation Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 21
- 239000012047 saturated solution Substances 0.000 claims description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 18
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 2
- 239000013078 crystal Substances 0.000 description 22
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- 229960003390 magnesium sulfate Drugs 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000002360 explosive Substances 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 9
- 239000006166 lysate Substances 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 229940076230 magnesium sulfate monohydrate Drugs 0.000 description 4
- LFCFXZHKDRJMNS-UHFFFAOYSA-L magnesium;sulfate;hydrate Chemical compound O.[Mg+2].[O-]S([O-])(=O)=O LFCFXZHKDRJMNS-UHFFFAOYSA-L 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- IJJWOSAXNHWBPR-HUBLWGQQSA-N 5-[(3as,4s,6ar)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]-n-(6-hydrazinyl-6-oxohexyl)pentanamide Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)NCCCCCC(=O)NN)SC[C@@H]21 IJJWOSAXNHWBPR-HUBLWGQQSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
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Abstract
本发明公开了用卤水生产氯化钠及七水硫酸镁的方法，步骤：(1)卤水为原料，卤水中SO4 2-∶Mg2+的摩尔比为0.1～0.8，并且SO4 2-∶Na+的摩尔比为0.025～1；减压沸腾蒸发，控制压力使蒸发完成时沸点温度为75℃～50℃，并且溶液中SO4 2∶Na+摩尔比为0.4～2.5；(2)固液分离，固相用饱和氯化钠水溶液洗涤，经干燥得到氯化钠；(3)向制盐母液加水，制成混合液；(4)混合液冷却，引入到结晶器中，有结晶析出；(5)固液分离，得到固相为七水硫酸镁粗品。本发明的方法设备简单、工艺简单，氯化钠析出的充分，七水硫酸镁的纯度和收率高，过程中无除杂盐环节，实现氯化钠和七水硫酸镁的联合生产。The invention discloses a method for producing sodium chloride and magnesium sulfate heptahydrate with brine. The steps are: (1) brine is used as raw material, the molar ratio of SO 4 2- : Mg 2+ in the brine is 0.1 to 0.8, and SO 4 2- : The molar ratio of Na + is 0.025～1; boiling and evaporating under reduced pressure, the boiling point temperature is 75°C～50°C when the pressure is controlled so that the evaporation is completed, and the SO 4 2 : Na+ molar ratio in the solution is 0.4～2.5; (2) Solid-liquid separation, the solid phase is washed with a saturated sodium chloride aqueous solution, and dried to obtain sodium chloride; (3) Add water to the salt-making mother liquor to make a mixed liquor; (4) Cool the mixed liquor, introduce it into a crystallizer, and crystallize Precipitation; (5) solid-liquid separation, the solid phase obtained is the crude product of magnesium sulfate heptahydrate. The method of the invention has simple equipment, simple process, sufficient precipitation of sodium chloride, high purity and high yield of magnesium sulfate heptahydrate, no impurity salt removal link in the process, and joint production of sodium chloride and magnesium sulfate heptahydrate is realized.
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)
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| CN102030350B (en) * | 2010-11-11 | 2012-07-11 | 北京科技大学 | A kind of method that takes salt lake magnesium chloride brine as raw material to prepare magnesium sulfate heptahydrate |
| 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 | A kind of 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 | A kind of 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 |
| CN114014484A (en) * | 2021-12-06 | 2022-02-08 | 王锦富 | A Low-cost Reclaimed Water Reuse Concentrated Brine Resource Zero Discharge Treatment Process |
| CN117185322A (en) * | 2023-09-08 | 2023-12-08 | 自然资源部天津海水淡化与综合利用研究所 | A method for separating inorganic salts in sodium magnesium sulfate mixed solution |
| CN118108193A (en) * | 2024-01-19 | 2024-05-31 | 河北纽思泰伦科技发展有限公司 | A kind of sodium nitrite quality improvement process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2689041A (en) * | 1952-03-18 | 1954-09-14 | Int Minerals & Chem Corp | Beneficiation of ores containing potassium chloride and magnesium sulfate |
| CN1035096A (en) * | 1988-02-12 | 1989-08-30 | 轻工业部制盐工业科学研究所 | The method of high temp. salt system sal epsom and sodium-chlor |
| CN1084138A (en) * | 1992-09-12 | 1994-03-23 | 国家海洋局天津海水淡化与综合利用研究所 | Method for separating high-temperature salt into industrial salt and magnesium sulfate |
| CN1102600A (en) * | 1994-08-04 | 1995-05-17 | 中国石油天然气公司工程技术研究院 | Process and unit for separating sulfate from sodium chloride in high temp. salt |
| DE10256046A1 (en) * | 2002-11-30 | 2004-06-09 | Kali-Umwelttechnik Gmbh K-Utec | Production of epsomite and sodium chloride from bittern comprises adding recycled mother liquor, concentrating to crystallize sodium chloride and cooling to crystallize epsomite |
-
2008
- 2008-08-21 CN CN200810054198A patent/CN100588614C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2689041A (en) * | 1952-03-18 | 1954-09-14 | Int Minerals & Chem Corp | Beneficiation of ores containing potassium chloride and magnesium sulfate |
| CN1035096A (en) * | 1988-02-12 | 1989-08-30 | 轻工业部制盐工业科学研究所 | The method of high temp. salt system sal epsom and sodium-chlor |
| CN1084138A (en) * | 1992-09-12 | 1994-03-23 | 国家海洋局天津海水淡化与综合利用研究所 | Method for separating high-temperature salt into industrial salt and magnesium sulfate |
| CN1102600A (en) * | 1994-08-04 | 1995-05-17 | 中国石油天然气公司工程技术研究院 | Process and unit for separating sulfate from sodium chloride in high temp. salt |
| DE10256046A1 (en) * | 2002-11-30 | 2004-06-09 | Kali-Umwelttechnik Gmbh K-Utec | Production of epsomite and sodium chloride from bittern comprises adding recycled mother liquor, concentrating to crystallize sodium chloride and cooling to crystallize epsomite |
Non-Patent Citations (4)
| Title |
|---|
| 大柴旦盐湖冬季组成卤水的天然蒸发. 高世扬等.盐湖研究，第4卷第3-4期. 1996 |
| 大柴旦盐湖冬季组成卤水的天然蒸发. 高世扬等.盐湖研究，第4卷第3-4期. 1996 * |
| 浓海水利用的生态工业体系. 周桓.化工环保，第24卷. 2004 |
| 浓海水利用的生态工业体系. 周桓.化工环保，第24卷. 2004 * |
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