CN105366698B - A kind of preparation method of Magnesium sulfate heptahydrate - Google Patents
A kind of preparation method of Magnesium sulfate heptahydrate Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of Magnesium sulfate heptahydrate, the method comprising the steps of：A, by sodium sulfate, magnesium chloride and fresh water according to weight ratio be 1：(3～6)：The ratio mix of (1.5～3.5) carries out decomposition and inversion reaction, obtains slip I；B, by I heat preservation settlement of the slip, then carry out solid-liquid separation, obtain the mother solution I of liquid phase；C, the mother solution I is cooled to 10～15 DEG C carries out low temperature cold crystallization, then carry out solid-liquid separation, obtain the rough Magnesium sulfate heptahydrate of solid phase, obtain the mother solution II of liquid phase；D, it is 1 according to weight ratio by the rough Magnesium sulfate heptahydrate and mother solution II and fresh water：(0.2～0.6)：The ratio of (0.2～0.6) carries out pulp washing and obtains slip II, and the slip II is carried out solid-liquid separation, obtains the wet product of refined Magnesium sulfate heptahydrate of solid phase；E, by refined Magnesium sulfate heptahydrate wet product drying, obtain the Magnesium sulfate heptahydrate.
Description
Technical field
The present invention relates to chemical field, is related to a kind of preparation method of Magnesium sulfate heptahydrate, especially one kind adopts magnesium chloride
The method that Magnesium sulfate heptahydrate is produced with sodium sulfate.
Background technology
Magnesium sulfate heptahydrate is a kind of important Inorganic Chemicals, in fields such as agricultural, industry, food, medicine, weavings all
Have a wide range of applications.At present, the method for Magnesium sulfate heptahydrate is produced mainly by following several：
First, sulfuric acid process：Ore (dolomite, magnesite, serpentine) containing magnesium oxide size-reduced or its calcination powder (also may be used
With magnesium hydroxide or magnesium carbonate) measured respectively with sulphuric acid in proportion.Clear water or wash water, mother solution are added in retort, in stirring
Lower first to add slowly breeze, adding sulphuric acid carries out acidolysis reaction.Control serosity pH=5, density is in 1.370～1.384g/
cm3, 80 DEG C are incubated, slip is filtered with leaf-type filter, and clear liquid is squeezed into crystallizer, is cooled to less than 30 DEG C and is centrifuged
(can wash in centrifuge).Wet feed is sent into into vibrated fluidized bed Magnesium sulfate heptahydrate is obtained in 50～55 DEG C of dryings.The method is produced
Product quality preferably, it is but relatively costly, products application in industries such as industry, feedstuff, food, if as Fertilizer application, base
Originally there is no economic benefit.
2nd, bittern in salt lake method：Salt lake bittern belongs to Na+, Mg2+//CI-, SO4 2-—H2O quaternary systems.Mother after production Natrii Sulfas
Liquid ρ (MgSO4)=150～200g/L, ρ (NaCl)=65～80g/L, ρ (MgCl2)=25～45g/L, commonly referred to bittern.Jing
The two seasons natural evaporation of autumn in summer, is put into crystallizing pond after bittern concentration, during to winter halogen temperature drop to 5～15 DEG C, begins with seven water sulphuric acid
Magnesium is separated out.Drain upper strata mother solution and obtain final product rough Magnesium sulfate heptahydrate.Rough Magnesium sulfate heptahydrate is added water dissolve at 80～90 DEG C for
Density is 1.370～1.384g/cm3Solution, Jing filter press remove residue, crystallisation by cooling is carried out after separation, tripodia is used
After formula centrifuge is separated, it is dried at a temperature of 50～55 DEG C, obtains final product Magnesium sulfate heptahydrate.As the method is tied naturally using natural resources
Crystalline substance, but Jing manually purifies, and product quality is preferable, cost is relatively low；But the yield of the method is relatively low, and the cycle is long.
3rd, bittern shines method again：Sea water salt pan bittern is saturation to Sodium Chloride, is undersaturated to magnesium sulfate, works as temperature
When being reduced to 5 DEG C, MgSO is just begun with4·7H2O and NaCI are separated out together.Commercial production is first to shine bittern in multiple solarization pond again
It is 1.260～1.296g/cm to density3NaCI is separated out, then top bittern is entered in halogen hole, declined by winter temperature,
MgSO47HZO crystallizations are separated out, and obtain rough Magnesium sulfate heptahydrate.Product carnallite (NaCI) content is higher, of poor quality, using washing
Method or recrystallization method purification, can be obtained Magnesium sulfate heptahydrate, and the method is relatively costly, is unfavorable for industrial mass production.
4th, the molten leaching method of high temp. salt：Sea water Exposure to Sunlight bittern, output high temp. salt when being evaporated with adding halogen method, consisting of MgSO4>
30%, NaCl<35%, MgCl2About 7%, KCl is about 0.5%.Use MgCl2(360～380g/L) and fresh water 1: 1 mix, and match somebody with somebody
Make the MgCl containing 200g/L or so2Solution is in 48 DEG C or so molten leachings.Due to NaCl dissolvings seldom MgSO4Dissolving is more, insulation
After clarification, leaching solution is separated with undissolved high temp. salt, and Magnesium sulfate heptahydrate is separated out by being cooled to below 10 DEG C.The current party
The use of method is less, is primarily due to the method relatively costly.
The production of sulphuric acid magnesium products is derived mainly from the sulfuric acid process of sulfuric acid treatment magnesite, according to statistics, domestic existing seven water
The 69% of sulphuric acid magnesium products its yield comes from sulfuric acid process (sulfuric acid treatment magnesite)；15% from the by-product sulfur such as flue gas desulfurization
Sour magnesium；With seven water that sea salt by-product (bittern or high temp. salt) and salt lake by-product (bittern in salt lake or epsomite ore deposit) are produced
Magnesium sulfate yield accounts for the 15% of total output.With the sulphuric acid magnesium products of Production By Sulfuric Acid Process Magnesium sulfate heptahydrate or different moisture content, it is somebody's turn to do
The main processes of production are：Magnesite (magnesium carbonate) makes magnesite be decomposed into magnesium oxide, release carbon dioxide through calcining,
Magnesium oxide uses sulfuric acid decomposition at a certain temperature, is allowed to change into magnesium sulfate slip, and magnesium sulfate slip is through filtering miscellaneous cooling
Crystallization separates out Magnesium sulfate heptahydrate.It is related to magnesite calcining, sulfuric acid decomposition magnesium oxide in production process, forces the techniques such as crystallisation by cooling
Process.Magnesite calcination process energy consumption is higher, can produce dust pollution and carbon dioxide atmospheric pollution；Acid hemolysis process is certain
Carry out under acid condition, equipment corrosion is serious, and production material is had an impact to environment and workers ' health.In process of production, produce
Material is acid material, and the waste material which produces is also acid material, discharges and can also produce certain cost, increased Jing after processing
The production cost of product.Secondly because raw material magnesite is associated with dolomite and other impurity, these impurity can not be with product shape
State occurs, and is processed with waste material form or is abandoned substantially in process of production, and this is also a pole to manufacturing enterprise's surrounding
Big impact, processes these waste materials and can also produce some costs, and this also will increase the production cost of sulphuric acid magnesium products.
Additionally, magnesium sulfate is a low-value product, but but has in terms of industrial and agricultural production and be extremely widely applied.
Due to the 85% of domestic magnesite ore reserves Haicheng City for being distributed in Liaoning and one band of Yingkou, other provinces and regions distributions are less, and magnesium sulfate is produced
Product major production areas is also distributed across these regions with raw material.By the sulphuric acid magnesium products fortune in northeast and east China area
Toward west area, haul distance is longer, and freight is larger, its freight or will be greater than being worth for its product itself.
The content of the invention
In order to solve the problems, such as prior art, the invention provides a kind of preparation method of Magnesium sulfate heptahydrate, to solve
Production equipment seriously corroded in certainly existing method, environmental pollution are serious, the problem more than waste by-product；And in the method
Raw material resources distribution is wide, easily obtains, reduces the production cost of sulphuric acid magnesium products.
For achieving the above object, present invention employs following technical scheme：
A kind of preparation method of Magnesium sulfate heptahydrate, the method comprising the steps of：A, by sodium sulfate, magnesium chloride and fresh water according to weight
Amount is than being 1：(3～6)：The ratio mix of (1.5～3.5) carries out decomposition and inversion reaction, obtains slip I；Wherein, the sulfur
Sour sodium is Matrii Sulfas Exsiccatus or Natrii Sulfas, and the magnesium chloride is bischofite (MgCl2·6H2) or old halogen (magnesium chloride saturated liquid) O；B, general
I heat preservation settlement of the slip, then carries out solid-liquid separation, obtains the mother solution I of liquid phase；C, the mother solution I is cooled to into 10～15
DEG C low temperature cold crystallization is carried out, then carry out solid-liquid separation, obtain the rough Magnesium sulfate heptahydrate of solid phase, obtain the mother solution II of liquid phase；
D, it is 1 according to weight ratio by the rough Magnesium sulfate heptahydrate and mother solution II and fresh water：(0.2～0.6)：The ratio of (0.2～0.6)
Carry out pulp washing and obtain slip II, the slip II is carried out into solid-liquid separation, obtain the wet product of refined Magnesium sulfate heptahydrate of solid phase
Product；E, by refined Magnesium sulfate heptahydrate wet product drying, obtain the Magnesium sulfate heptahydrate.
Preferably, in step A, after sodium sulfate, magnesium chloride and fresh water are mixed in proportion, load in normal pressure reactor 40
Decomposition and inversion reaction is carried out at a temperature of～70 DEG C, the time of decomposition and inversion reaction is 0.5～2.0 hour.
Preferably, in step B, by the slip I at a temperature of 60～70 DEG C heat preservation settlement.
Preferably, solid phase and the fresh water for solid-liquid separation in step B being obtained is 1 according to weight ratio：0.5～1.0 ratio
Washed, be then separated by filtration, the solid-phase chlorination sodium for obtaining is used as Nacl, the cleaning mixture I for obtaining liquid phase is added to
In mix in step A.
Preferably, in step C, the mother solution I passes through natural cooling or pressure is cooled to 10～15 DEG C and carries out low temperature cold junction
It is brilliant.
Preferably, the mother solution II is further reclaimed into rough seven water by being positioned over salt pan natural evaporation or forced evaporation
Magnesium sulfate, the evaporation mother solution after evaporation are added in the mix in step A.
Preferably, in step D, carrying out controlling slurry temperature during pulp washing for 10～25 DEG C, wash time is 0.5～
1.0 hour.
Preferably, in step D, the slip II is carried out after solid-liquid separation, to obtain the mother solution III of liquid phase；The mother solution III
A part be used to replacing the mother solution II in step D to carry out pulp washing, another part by be positioned over salt pan natural evaporation or
Forced evaporation further reclaims rough Magnesium sulfate heptahydrate, and the evaporation mother solution after evaporation is added in the mix in step A.
Compared with prior art, the preparation method of Magnesium sulfate heptahydrate provided in an embodiment of the present invention, mainly using magnesium chloride
It is waste Magnesium sulfate heptahydrate with sodium sulfate, little to equipment corrosion in its technical process, environmental pollution is relatively low；Technique mistake
The by-product produced in journey can also be recycled, and garbage is few.
In raw material used by which, sodium sulfate can be thenardite (Matrii Sulfas Exsiccatus) or aqueous Natrii Sulfas；Magnesium chloride is salt lake magnesium
Salt, can be bischofite (MgCl2·6H2) or old halogen (magnesium chloride saturated liquid) O.There are abundant mirabilite resource, mirabilite ore in China
Produce resource distribution extensively, rich reserves, about 17,800,000,000 t of explored reserves, if generally investigated or detailed survey and do not count
Also count, it is contemplated that Chinese Natrii Sulfas class mineral products sodium sulfate total resources is up to 30,000,000,000 t, occupies first place in the world.The Natrii Sulfas of China
Ore deposit is distributed in 14 provinces, autonomous regions, and salt lake type mirabilite ore is mainly distributed on Xinjiang, Qinghai, Gansu, Inner Mongol, 5 provinces and regions of Shanxi, calcium
Mirabilite ore is mainly distributed on Sichuan, Hunan, Qinghai, Yunnan, 5 province of Hubei, and underground mirabilite ore is mainly distributed on Jiangsu Province.China
Salt lake magnesium salt resource is mainly distributed on Cha Er Han Salt Lake, Tibetan Salt Lakes and the Xinjiang Lop Nur salt lake of Chaidamu Basin, Qinghai Province.Bavin
Magnesium salt reserves up to tub ground account for the whole nation and have found out more than the 90% of magnesium salt reserves, the identified magnesium salt storage in current Caidamu Basin
Amount is more than 6,000,000,000 tons.Accordingly, with respect to magnesite is adopted in sulfuric acid process, the raw material used by the preparation method of the present invention is wider
It is general, especially for China's western region, its abundant mirabilite resource and magnesium salt resource, can be to be provided with magnesium chloride and sodium sulfate
Source is that raw material production Magnesium sulfate heptahydrate and its series of products provide abundant raw material, using magnesium chloride and mirabilite resource western raw
Magnesium sulfate fertilizer and its series of products are produced, is used for west area industrial and agricultural production, sale cost of transportation will be greatly reduced.
Description of the drawings
Fig. 1 is the process chart of the Magnesium sulfate heptahydrate of the potassium sulfate that the specific embodiment of the invention is provided.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawings to concrete reality of the invention
The mode of applying is described in detail.The example of these preferred implementations is illustrated in the accompanying drawings.Shown in accompanying drawing and according to
What the embodiments of the present invention of Description of Drawings were merely exemplary, and the present invention is not limited to these embodiments.
Refering to the process chart of Fig. 1, the preparation method of the Magnesium sulfate heptahydrate provided in the embodiment of the present invention mainly includes
Step：
Step A, by sodium sulfate, magnesium chloride and fresh water according to weight ratio be 1：(3～6)：The ratio mixing of (1.5～3.5)
Dispensing carries out decomposition and inversion reaction, obtains slip I；Wherein, the sodium sulfate can be thenardite (Matrii Sulfas Exsiccatus) or aqueous awns
Nitre；The magnesium chloride is salt lake magnesium salt, can be bischofite (MgCl2·6H2) or old halogen (magnesium chloride saturated liquid) O.Specifically
Ground, in the step, after sodium sulfate, magnesium chloride and fresh water are mixed in proportion, carries out decomposition and inversion in loading normal pressure reactor anti-
Should, the time of decomposition and inversion reaction is 0.5～2.0 hour.Magnesium chloride, sodium sulfate, water are mutually chemical according to the system salt-water system
Theoretical and chemical reaction equilibrium principle carries out dispensing, and it is anti-that material completes decomposition and inversion in the reaction temperature for requiring and in the response time
Should.Decomposition and inversion reaction will be carried out when being set in 40～70 DEG C, higher transformation efficiency can be kept, raw material availability is improved.
Step B, by I heat preservation settlement of the slip, then carry out solid-liquid separation, obtain the mother solution I of liquid phase.In the step,
Complete decomposition and inversion reaction slip I filtered under keeping warm mode, by reaction formed Sodium Chloride by sedimentation filtration with
Solid phase form isolates system, and magnesium sulfate is then stayed in the liquid phase in the form of an ion, so as to realize that this reactive chemistry is balanced to sulphuric acid
Magnesium forms direction movement.Preferably, by the slip I at a temperature of 60～70 DEG C heat preservation settlement, the technique for accelerating sedimentation
Speed and the separation of Sodium Chloride can be made more thorough.Further, the solid phase that acquisition is separated in the step mainly includes chlorination
Sodium, is 1 according to weight ratio by detached solid phase and fresh water：0.5～1.0 ratio is washed, and is then separated by filtration, and is obtained
Solid-phase chlorination sodium is used as Nacl, and the cleaning mixture I for obtaining liquid phase is added in the mix in step A, can be promoted
The decomposition and inversion reaction entered in step A.
Step C, the mother solution I is cooled down (can be natural cooling or force cooling) low temperature cold junction is carried out to 10～15 DEG C
Crystalline substance, then carries out solid-liquid separation, obtains the rough Magnesium sulfate heptahydrate of solid phase, obtains the mother solution II of liquid phase.In the step, mother solution I
In magnesium sulfate be allowed to separate out by way of crystallisation by cooling, obtain Magnesium sulfate heptahydrate crude product, reach with magnesium chloride, sodium sulfate
For the purpose of waste Magnesium sulfate heptahydrate.Wherein, the mother solution II of acquisition can be by being positioned over salt pan natural evaporation or pressure
Rough Magnesium sulfate heptahydrate is further reclaimed in evaporation, and the evaporation mother solution after evaporation is added in the mix in step A, can be promoted
The decomposition and inversion reaction entered in step A.
D, it is 1 according to weight ratio by the rough Magnesium sulfate heptahydrate and mother solution II and fresh water：(0.2～0.6)：(0.2～
0.6) ratio carries out pulp washing and obtains slip II, and the slip II is carried out solid-liquid separation, obtains refined seven water of solid phase
The wet product of magnesium sulfate.In the ratio provided by the step, the yield and purity of magnesium sulfate can be preferably taken into account, wherein, compared with
It is good, slurry temperature is controlled when carrying out pulp washing and is controlled to 10～25 DEG C, wash time is controlled to 0.5～1.0 hour.Enter
One step ground, the slip II is carried out the mother solution III of liquid phase is obtained after solid-liquid separation；A part for the mother solution III is used to replace
Mother solution II in this step carries out pulp washing, and another part is further returned by being positioned over salt pan natural evaporation or forced evaporation
Rough Magnesium sulfate heptahydrate is received, the evaporation mother solution after evaporation is added in the mix in step A, in can promoting step A
Decomposition and inversion is reacted.It is to be understood that when technique just starts, first mother solution II being used in the technique of step D, working as step
After the technique of D is carried out, by the mother solution III produced by step D in cycle applications and step D, now, mother solution II is mainly used in leading to
Pervaporation further reclaims rough Magnesium sulfate heptahydrate.
E, by refined Magnesium sulfate heptahydrate wet product drying, (technological process of Fig. 1 is not shown to obtain the Magnesium sulfate heptahydrate
The step).
As among the existing magnesium sulfate production technology told about in aforementioned background art, from the environmentally friendly situation of production process and
For the green level of product itself, the technology of bittern method and high temp. salt method production Magnesium sulfate heptahydrate is worth recommending the most.But
Both approaches are not become larger production scale, it is impossible to be promoted because limiting by raw material sources, secondly in inland basin
Area produces, and the crystallization process of Magnesium sulfate heptahydrate need to rely on pressure crystallisation by cooling mode to be carried out, and energy consumption is higher.As provided above seven
The preparation method of water magnesium sulfate, mainly with regional salt lake magnesium chloride and sodium sulfate resource as raw material, converts (40～70 using middle temperature
DEG C), middle temperature separate, low temperature cold crystallization processes production Magnesium sulfate heptahydrate product, raw materials for production all from natural mineral resources,
Main chemical reactions involved by production process are the decomposition and inversion course of reaction between inorganic salt, strong to production equipment and workman
Kang Buhui is produced and is had a strong impact on, and the waste material produced in production process is mainly Sodium Chloride, and Sodium Chloride can be with after refinement treatment
Use as Nacl, or store stand-by among returning to salt lake.The raw material and production process used by whole technique is all right
It is eco-friendly, there is no magnesite calcining, the magnesite acidolysis involved during sulfuric acid treatment magnesite, force crystallisation by cooling
Deng high pollution, the production link of highly energy-consuming.
Secondly, the raw material used by the preparation method of the present invention is more extensive, and especially for China's western region, which enriches
Mirabilite resource and magnesium salt resource, it is that raw material production Magnesium sulfate heptahydrate and its series are produced with magnesium chloride and sodium sulfate resource that can be
Product provide abundant raw material, using magnesium chloride and mirabilite resource in western production magnesium sulfate fertilizer and its series of products, for western ground
Area's industrial and agricultural production is used, and will greatly reduce sale cost of transportation.Also, for China's western region, crystallisation by cooling mistake
The characteristics of journey can utilize west area weather day and night temperature big greatly reduces energy consumption using salt field process realization.
The preparation method of Magnesium sulfate heptahydrate provided in an embodiment of the present invention, compared to prior art, is a kind of brand-new side
Method, the raw material and production process used by whole technique are all environment amenable, with little to equipment corrosion, dirty to environment
Contaminate the few advantage of relatively low, garbage.It is previously mentioned the certain situation for China's western region, it should be understood that the present invention is carried
For Magnesium sulfate heptahydrate preparation method when China's western region is implemented with bigger advantage, the present invention provides seven water sulphuric acid
The preparation method of magnesium is not limited to only be embodied as in China's western region.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, on the premise of without departing from the application principle, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as the protection domain of the application.
Claims (8)
1. a kind of preparation method of Magnesium sulfate heptahydrate, it is characterised in that including step：
A, by sodium sulfate, magnesium chloride and fresh water according to weight ratio be 1：(3～6)：The ratio mix of (1.5～3.5) is carried out
Decomposition and inversion is reacted, and obtains slip I；Wherein, the sodium sulfate is Matrii Sulfas Exsiccatus or Natrii Sulfas, and the magnesium chloride is bischofite or old
Halogen；
B, by I heat preservation settlement of the slip, then carry out solid-liquid separation, obtain the mother solution I of liquid phase；
C, the mother solution I is cooled to 10～15 DEG C carries out low temperature cold crystallization, then carry out solid-liquid separation, obtain the rough of solid phase
Magnesium sulfate heptahydrate, obtains the mother solution II of liquid phase；
D, it is 1 according to weight ratio by the rough Magnesium sulfate heptahydrate and mother solution II and fresh water：(0.2～0.6)：(0.2～0.6)
Ratio carries out pulp washing and obtains slip II, and the slip II is carried out solid-liquid separation, obtains the refined Magnesium sulfate heptahydrate of solid phase
Wet product；
E, by refined Magnesium sulfate heptahydrate wet product drying, obtain the Magnesium sulfate heptahydrate.
2. the preparation method of Magnesium sulfate heptahydrate according to claim 1, it is characterised in that in step A, by sodium sulfate, chlorine
After change magnesium and fresh water are mixed in proportion, loading in normal pressure reactor carries out decomposition and inversion reaction at a temperature of 40～70 DEG C, point
The time of solution conversion reaction is 0.5～2.0 hour.
3. the preparation method of Magnesium sulfate heptahydrate according to claim 1, it is characterised in that in step B, by the slip I
The heat preservation settlement at a temperature of 60～70 DEG C.
4. the preparation method of the Magnesium sulfate heptahydrate according to claim 1 or 3, it is characterised in that by solid-liquid separation in step B
The solid phase of acquisition and fresh water are 1 according to weight ratio：0.5～1.0 ratio is washed, and is then separated by filtration, the solid phase for obtaining
Sodium Chloride is used as Nacl, and the cleaning mixture I for obtaining liquid phase is added in the mix in step A.
5. the preparation method of Magnesium sulfate heptahydrate according to claim 1, it is characterised in that in step C, the mother solution I are led to
Cross natural cooling or pressure is cooled to 10～15 DEG C and carries out low temperature cold crystallization.
6. the preparation method of Magnesium sulfate heptahydrate according to claim 1 or 5, it is characterised in that the mother solution II is passed through
It is positioned over salt pan natural evaporation or forced evaporation further reclaims rough Magnesium sulfate heptahydrate, the evaporation mother solution after evaporation is added to step
In mix in rapid A.
7. the preparation method of Magnesium sulfate heptahydrate according to claim 1, it is characterised in that in step D, carry out pulp washing
When control slurry temperature for 10～25 DEG C, wash time is 0.5～1.0 hour.
8. the preparation method of the Magnesium sulfate heptahydrate according to claim 1 or 7, it is characterised in that in step D, by the material
Slurry II obtains the mother solution III of liquid phase after carrying out solid-liquid separation；A part for the mother solution III is used to replace the mother solution II in step D
Pulp washing is carried out, another part further reclaims rough seven water sulphuric acid by being positioned over salt pan natural evaporation or forced evaporation
Magnesium, the evaporation mother solution after evaporation are added in the mix in step A.
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| CN101343071A (en) * | 2008-08-21 | 2009-01-14 | 天津科技大学 | Method for preparing sodium chloride and magnesium sulphate heptahydrate with brine |
| CN102030350A (en) * | 2010-11-11 | 2011-04-27 | 北京科技大学 | Method for preparing magnesium sulfate heptahydrate by taking magnesium chloride bittern from salt lake as raw material |
| CN102757072A (en) * | 2012-08-02 | 2012-10-31 | 化工部长沙设计研究院 | Process for preparing magnesium sulfate heptahydrate |
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| CN101343071A (en) * | 2008-08-21 | 2009-01-14 | 天津科技大学 | Method for preparing sodium chloride and magnesium sulphate heptahydrate with brine |
| CN102030350A (en) * | 2010-11-11 | 2011-04-27 | 北京科技大学 | Method for preparing magnesium sulfate heptahydrate by taking magnesium chloride bittern from salt lake as raw material |
| CN102757072A (en) * | 2012-08-02 | 2012-10-31 | 化工部长沙设计研究院 | Process for preparing magnesium sulfate heptahydrate |
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