CN1032742C - Prodn. technique for prepn. of white magnesium chloride using bitter - Google Patents
Prodn. technique for prepn. of white magnesium chloride using bitter Download PDFInfo
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- CN1032742C CN1032742C CN 93109924 CN93109924A CN1032742C CN 1032742 C CN1032742 C CN 1032742C CN 93109924 CN93109924 CN 93109924 CN 93109924 A CN93109924 A CN 93109924A CN 1032742 C CN1032742 C CN 1032742C
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- bittern
- brine
- white magnesium
- liquid
- magnesium dichloride
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Abstract
The present invention relates to a technological method for preparing white magnesium chloride by seawater brine. Seawater is desalted, potassium chloride and bromine of bittern are extracted, and the prepared mother liquor is raw brine which is used as raw material. The present invention carries out processing steps: neutralization by adding alkali, desulfurization by adding calcium, slag removal, bleaching, vacuum evaporation, sheet manufacture, etc., and thus, white magnesium chloride can be prepared. The white magnesium chloride can be widely applied to industries of metallurgy, building materials, chemical industry, cotton spinning, foods, etc. The present invention has the advantages of simple operation and stable technique, enhances the yield and the quality of products, and reduces the environment pollution.
Description
The present invention relates to the preparation of magnesium chloride, it is the processing method of being produced white Magnesium dichloride hexahydrate by bittern.
The white Magnesium dichloride hexahydrate is important chemical material and additive, it is widely used in metallurgy, building materials, chemical industry, industry such as cotton spinning and food, especially the main raw material of senior chemical composite material for decoration is used and is made in the gluing of spinning, magnesium chloride was colourless originally, because the suitability for industrialized production of magnesium chloride is as basic raw material with raw brine, and raw brine to be seawater concentrate, the final product of the less various salt after separatings of solubleness, contain organic substance in the bittern, it is dark brown that the pyrolytic decomposition charing makes that Magnesium dichloride hexahydrate becomes, in order to obtain white Magnesium dichloride hexahydrate, the magnesium chloride that promptly decolours must add SYNTHETIC OPTICAL WHITNER and decolour.
The method of manufacturing technology of existing decolouring Magnesium dichloride hexahydrate generally is that the mother liquor behind bittern extraction Repone K, the bromine is a raw material after evaporating brine with seawater,, slagging-off heavy clear, crystallisation by cooling moulding (work such as Wang Zonglu through evaporation, neutralization, bleaching, insulation, salt chemical engineering technology, the Light Industry Press, in December, 1988).There is following shortcoming in this producing and manufacturing technique: (1) raw brine evaporation terminal point is higher than 155 ℃, is that the evaporation equipment thermo-efficiency of carrier is low with the steam, and energy consumption is big; (2) evaporation is finished feed liquid when carrying out chemical treatment, and mordant obnoxious flavour is emitted, and causes equipment corrosion serious and environmental pollution is serious; (3) the feed liquid slagging-off is finished in evaporation, temperature of charge height and concentration height, and easy condensation blocking pipe when discharging, band mistake rate height, operation easier is big; (4) the material slag that feed liquid is discharged through chemical treatment is finished in evaporation, because temperature is higher, and easy condensation-crystallization when temperature reduces, difficult separation and recycling, thus influence yield, and bring severe contamination to environment.
The preparation production technique that the purpose of this invention is to provide a kind of improved white Magnesium dichloride hexahydrate is used for overcoming the shortcoming that existing production technique exists, and the present invention is simple to operate, save energy, improve product yield and quality, reduce environmental pollution, stable process conditions.
The present invention is basic raw material with the raw brine, at first bittern is carried out chemical treatment, through consecutive steps such as neutralization, sulphur removal, slagging-off and the bleaching liquid that obtains finishing dealing with, evaporates then, film-making, can obtain qualified white Magnesium dichloride hexahydrate product.
Specific embodiments of the present invention 1 is described as follows in conjunction with the accompanying drawings:
Fig. 1 is the technological process of production figure that bittern prepares white Magnesium dichloride hexahydrate.
Add raw brine in neutralizing well, the mother liquor after promptly seawater is evaporated brine behind the bittern extraction Repone K adds alkali lye (sodium hydroxide or potassium hydroxide solution) neutralization then, and the control pH value is during the bittern after 6 θ, 75 neutralization reactions is called and bittern.
Squeeze into preheater with bittern in inciting somebody to action, be heated to 35～125 ℃, the bittern after the preheating is pre-hot brine.
In filling the sulphur removal groove of pre-hot brine, add calcium chloride solution, wherein mole such as sulfate radical in calcium ion and the bittern.To add calcium brine then squeezes in the insulation groove, keep in 40～100 ℃ of temperature ranges, make sulphur removal bittern settlement separate more than 1.5 hours, the bittern clear liquid that obtains enters bleaching tank, gypsum slurry enters separator, parting liquid is returned the insulation subsider, and isolated calcium slag (gypsum) is stored, and carries out aftertreatment.
Add SYNTHETIC OPTICAL WHITNER in the bleaching tank of the bittern clear liquid after filling sulphur removal, SYNTHETIC OPTICAL WHITNER can be selected clorox, Losantin, magnesium chlorate, sodium chlorate, Potcrate or Textone for use, and the present invention generally selects for use clorox as SYNTHETIC OPTICAL WHITNER.
Bittern clear liquid after bleaching is called the liquid of finishing dealing with, change in the vacuum-evaporator, under normal pressure, be evaporated to 165～170 ℃, or under 0.06～0.07MPa vacuum tightness, be evaporated to 135～140 ℃, obtain complete evaporation of liquid, send into the pelleter film-making then, can obtain white Magnesium dichloride hexahydrate finished product.
The present invention can be according to the requirement difference of user to sulfur-bearing acid group in the white Magnesium dichloride hexahydrate, can shorten production technique, be that raw brine is not when sulfate radical just can meet the demands, production craft step changes neutralization-bleaching-evaporation-film-making into, wherein neutralization and blanching step can carry out in same reactor simultaneously, also can carry out blanching step earlier, and then carry out neutralization reaction.
The following processing parameter of the optional usefulness of the present invention:
In and bittern pH value 6～7.5
Give 50～70 ℃ of hot brine temperature
45～60 ℃ of insulation settling temperature
Evaporation vacuum tightness 0.06～0.07MPa
Under the evaporation termination boiling point normal pressure, 165～170 ℃
0.06～0.07MPa，135～140℃
The concentration parameter of various materials is as follows among the present invention:
Raw brine (contains MgCl
2) 20～34%
Alkali lye (in HaOH) 5～30%
Calcium liquid is (with CaCl
2) 10～40%
SYNTHETIC OPTICAL WHITNER (containing available chlorine) 6～9.5%
Carry out the preparation of white Magnesium dichloride hexahydrate according to the present invention, new technology has following beneficial effect:
The first, carry out sulphur removal owing to before evaporation, add calcium solution, the gypsum slurry that obtains is through separating recyclable liquid phase material wherein, thereby can improve product yield 1.5～2%;
The second, because bleaching, slagging-off operation are placed on before the evaporation, the evaporation termination boiling point is hanged down 20～30 ℃ than existing technology evaporation termination boiling point, but so save energy 4～6%;
The 3rd, the present invention handles material at a lower temperature, and no material splashes and has poison gas to overflow, thereby avoids occurring the emitting of scald, burn and obnoxious flavour in the material treating processes, reduced pollution, guaranteed operator's safety surrounding environment.
The 4th, in the deliming slag of the present invention, easily cause the feed liquid blocking pipe that condenses when having avoided high-temperature high concentration material deslagging, thereby simplified operation.
The 5th, stable process conditions of the present invention, simple to operate, quality product improves.Table 1 is that the white Magnesium dichloride hexahydrate quality product of the present invention and existing prepared compares.
Advance of the present invention and outstanding substantive distinguishing features can be embodied by following examples.
Example 1.
Get 1 liter of raw brine, (wherein contain magnesium chloride 375.99 grams, sal epsom 12.51 grams) put into 1500 ml beakers, the caustic soda soln that adds 30 milliliter 10%, stir, pH value with bittern in recording is 6.1, electric furnace is heated to 100 ℃ and becomes and give hot brine, 24 milliliters of the calcium chloride solutions of adding 36% in giving hot brine, stir, adding the calcium brine temperature is 82 ℃, and it is 52 ℃ that the insulation sedimentation added the calcium brine temperature in 1.5 hours later on, supernatant liquid does not have solid formation after the sedimentation, supernatant liquid is isolated, and the pulpous state feed liquid after the sedimentation is carried out vacuum filtration, and solid formation 29 grams must wet, totally 980 milliliters of filtrate and sedimentation supernatant liquors, the chlorine bleach liquor's (available chlorine 9.3%) who adds 15 milliliters in clear liquid stirs, heating evaporation to 168 ℃, film-making, get white plates Magnesium dichloride hexahydrate finished product 742 grams, product yield 95.12% is pressed the check of GB8453-87 method.The chemical constitution of white Magnesium dichloride hexahydrate finished product is:
No. 30, whiteness
MgCl
2 48.20％
SO
4 2- 0.23％
Alkali metal chloride is (with Cl
-Meter) 0.58%
Water-insoluble 0.03%
Ca
2+ 0.13％
PH value 7.1
Example 2.
The control raw brine (contains MgCl
2365.2 grams per liter) flow is 12 cubic metres/hour, alkali lye (15%NaOH) flow is 240 liters/hour and adds neutralizing well, stir, in obtaining and bittern, pH value 6.2, give heat and enter the sulphur removal groove to 55 ℃ through splitting tube heat-exchanger, in the sulphur removal groove, add calcium solution (25% industrial calcium chloride solution) with 500 liters/hour flows and must add calcium brine, adding calcium brine enters the insulation settling vessel to isolate clear liquid is sulphur removal bittern, the settling vessel temperature is 48 ℃, and the clear liquid after the gypsum slurry centrifugation enters settling vessel.Sulphur removal bittern enters bleaching tank, SYNTHETIC OPTICAL WHITNER (clorox of available chlorine at least 9.3%) with 180 liters of/hour flows is advanced bleaching tank, feed liquid behind the bleaching action is the liquid of finishing dealing with, the liquid vacuum-evaporation to 135 ℃ under 0.066MPa vacuum tightness of will finishing dealing with then, the complete evaporation of liquid that obtains enters pelleter, per hour get 8.5 tons of white magnesium chloride finished products, product yield 91.70%.Press the check of GB8453-87 method, the chemical constitution of white Magnesium dichloride hexahydrate finished product is:
No. 40, whiteness
MgCl
2 47.28％
SO
4 2- 0.24％
Alkali metal chloride is (with Cl
-Meter) 0.59%
Water-insoluble 0.09%
Ca
2+ 0.13％
PH value 8
Example 3.
White Magnesium dichloride hexahydrate is produced in not sulphur removal of raw brine
The control raw brine (contains MgCl
2363.4 grams per liter) flow is 15 cubic metres/hour, alkali lye (15%NaOH) flow is 280 liters/hour and adds neutralizing wells, stir the back deserved in and bittern, pH value 6.1.In and bittern advance bleaching tank, bleach instead with the SYNTHETIC OPTICAL WHITNER (available chlorine is 9% chlorine bleach liquor) of 250 liters of/hour flows, obtain the liquid of finishing dealing with, vacuum-evaporation to 135 ℃ under 0.066MPa vacuum tightness then, the complete evaporation of liquid that obtains enters pelleter, obtain white Magnesium dichloride hexahydrate product, 10.5 tons of hourly outputs, product yield are 94.23%.Press the check of GB8453-87 method, the chemical constitution of Magnesium dichloride hexahydrate finished product is:
No. 35, whiteness
MgCl
2 48.92％
SO
4 2- 1.43％
Alkali metal chloride is (with Cl
-Meter) 0.56%
Ca
2+ 0.14％
PH value-
Water-insoluble-
Table one:
| GB (GB8453-87) | Existing technology | The present invention | |
| Whiteness MgCl 2SO 4 2-Alkali metal chloride is (with Cl -Meter) water-insoluble Ca 2+PH value | ≤ No. 50 〉=46%≤1.0%≤0.6%≤0.2%≤0.14%- | ≤ No. 50 〉=46%≤1.0%≤0.6%≤0.2%≤0.14%- | ≤ No. 45 〉=47%≤0.48%≤0.6%≤0.1%≤0.13%＞6 |
Claims (2)
1. one kind is the production technique of feedstock production white Magnesium dichloride hexahydrate by bittern, it is characterized in that comprising following process steps:
(1) raw brine is added in the neutralizing well, the alkali lye that adds 5-30% carries out neutralization reaction, and the control pH value is 6-7.6, in obtaining and bittern;
(2) pre-thermo-neutrality bittern is to 35-125 ℃;
(3) add the 10-40% calcium chloride solution in pre-hot brine, mole such as the calcium ion of adding and the sulfate radical in the raw brine stirs;
(4) sedimentation was isolated upper strata bittern clear liquid more than 1.5 hours under 40-100 ℃ of temperature, and settled gypsum slurry is separated, and parting liquid returns the insulation subsider;
(5) bleaching action is carried out in the sodium hypochlorite bleaching agent that adds available chlorine 6-9.5% in sulphur removal bittern clear liquid;
(6) the bittern clear liquid after will bleaching is evaporated to 165-170 ℃ or be evaporated to 135-140 ℃ under 0.06-0.07MPa vacuum tightness under normal pressure, obtains complete evaporation of liquid;
(7) cooling film-making promptly obtains the Magnesium dichloride hexahydrate finished product.
2. according to the production technique of the white Magnesium dichloride hexahydrate of the described preparation of claim 1, it is characterized in that described material and processing parameter are:
The sodium hydroxide solution of alkali lye 10-15%
Calcium chloride solution 25-36%
The chlorine bleach liquor of SYNTHETIC OPTICAL WHITNER 9-9.3%
50-70 ℃ of preheating brine temperature
45-60 ℃ of insulation settling temperature
Evaporation vacuum tightness 0.06-0.07MPa
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109924 CN1032742C (en) | 1993-08-19 | 1993-08-19 | Prodn. technique for prepn. of white magnesium chloride using bitter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109924 CN1032742C (en) | 1993-08-19 | 1993-08-19 | Prodn. technique for prepn. of white magnesium chloride using bitter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1099008A CN1099008A (en) | 1995-02-22 |
| CN1032742C true CN1032742C (en) | 1996-09-11 |
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ID=4987842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93109924 Expired - Fee Related CN1032742C (en) | 1993-08-19 | 1993-08-19 | Prodn. technique for prepn. of white magnesium chloride using bitter |
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|---|---|
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102674412A (en) * | 2012-06-20 | 2012-09-19 | 天津长芦海晶集团有限公司 | Preparation method of magnesium chloride hexahydrate |
| CN103626212A (en) * | 2012-08-28 | 2014-03-12 | 天津长芦汉沽盐场有限责任公司 | Food-grade magnesium chloride production method |
| CN106044807B (en) * | 2016-04-26 | 2018-03-20 | 中国科学院青海盐湖研究所 | The preparation method of edible magnesium chloride |
| CN105905927B (en) * | 2016-06-20 | 2017-10-31 | 中盐金坛盐化有限责任公司 | A kind of Galuber's salt type brine removes the bittern purifying device and method of strontium element |
| CN106082278A (en) * | 2016-06-20 | 2016-11-09 | 中盐金坛盐化有限责任公司 | A kind of Galuber's salt type brine removes the purification method of strontium element |
| CN107879364B (en) * | 2017-12-04 | 2019-05-03 | 大连盐化集团有限公司 | A kind of preparation method of food-grade magnesium chloride hexahydrate |
| CN111533101A (en) * | 2020-04-07 | 2020-08-14 | 天津长芦海晶集团有限公司 | Method for preparing magnesium hydrogen phosphate trihydrate from brine |
| CN111777084A (en) * | 2020-07-27 | 2020-10-16 | 潍坊硕邑化学有限公司 | Production process of food-grade magnesium chloride |
| CN114560480A (en) * | 2022-03-01 | 2022-05-31 | 天津长芦海晶集团有限公司 | Multi-element extraction method of bittern after desulfurization by calcium method |
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- 1993-08-19 CN CN 93109924 patent/CN1032742C/en not_active Expired - Fee Related
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|---|---|
| CN1099008A (en) | 1995-02-22 |
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