CN103896314A - Method for preparing high-purity magnesium oxide by using boron-removed salt lake old brine as raw material - Google Patents
Method for preparing high-purity magnesium oxide by using boron-removed salt lake old brine as raw material Download PDFInfo
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- CN103896314A CN103896314A CN201210588257.4A CN201210588257A CN103896314A CN 103896314 A CN103896314 A CN 103896314A CN 201210588257 A CN201210588257 A CN 201210588257A CN 103896314 A CN103896314 A CN 103896314A
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- purity magnesium
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Abstract
The invention discloses a method for preparing high-purity magnesium oxide by using boron-removed salt lake old brine as a raw material, relating to the field of inorganic chemical industry. The preparation method comprises the steps of filtering the salt lake old brine after boron removal, and removing solid suspended impurities in the salt lake old brine to obtain filtrate A; by using organic amine B as a precipitant, adding organic amine B into the filtrate A, filtering to obtain a filter residue and filtrate C, and washing and drying the filter residue C to obtain a high-purity magnesium hydroxide product; mixing the filtrate C with lime solid or slurry to obtain organic amine B floating above liquid and slurry D floating below the liquid; separating out organic amine B through phase splitting, and enabling organic amine B to be subjected to a next cyclic process; filtering and washing the slurry D to obtain filtrate E and a filter residue E, wherein the filter residue E includes a small amount of impurities in the lime and waste residues; evaporating and concentrating the filtrate E to obtain calcium chloride crystals; calcining obtained high-purity magnesium hydroxide to obtain high-purity magnesium oxide. The method disclosed by the invention greatly reduces the energy consumption and saves the cost.
Description
Technical field:
The present invention relates to field of inorganic chemical engineering, be specifically related to a kind of to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material.
Background technology:
Magnesium salts is important inorganic raw material, and magnesium hydroxide and magnesium oxide are topmost products wherein, and magnesium hydroxide is mainly used in industrial acid-bearing wastewater processing; Industry heavy metal ions removal; Flue gas desulfurization; Printing and dyeing water decolorization; Fire retardant; Other magnesium salts raw materials for production.Particularly magnesium hydroxide for fire retardant, development space is larger.
There is magnesite (MgCO containing the main mineral of magnesium in the world
3) and tachyhydrite (CaCl
2.2MgCl
2.12H
2o) secondly approximately 12,000,000,000 tons and 4,000,000,000 tons respectively of total reservess are exactly seawater and salt lake brine containing the essential mineral of magnesium on the earth.The salt lake magnesium resource of China is abundant, and only the magnesium resource of Chaidamu Basin, Qinghai Province just reaches 2,700,000,000 tons.Potash fertilizer will produce a large amount of magnesium chlorides in producing, and will have influence on the normal production of potash fertilizer as do not resolved utilization and processing problem, produces magnesium evil.
The method of extracting at present magnesium hydroxide from seawater and salt lake brine mainly contains 3 kinds: 1). milk of lime process; 2). ammonia process; 3). sodium hydroxide method.Milk of lime process is to utilize bittern and milk of lime direct reaction to obtain magnesium hydroxide and calcium chloride, and its advantage is that raw material is easy to get, and technique is simple.Shortcoming is filtration washing difficulty, and quality product is not high.Be applicable to production environmental protection magnesium hydroxide.Ammonia process is to utilize ammonia or ammoniacal liquor to react with bittern to obtain magnesium hydroxide and ammonium chloride, then by lime causticization ammonia still process, ammonia is recycled.Its advantage is that quality product is high, is easy to filter and washing, and shortcoming is that cost is higher, and energy consumption is high, the volatile environmental influence that causes of ammonia.Sodium hydroxide method is to utilize sodium hydroxide and bittern reaction to generate magnesium hydroxide, and advantage is that technique is simple, and final product quality is suitable with ammonia process, and shortcoming is that cost is high, and product filterableness is poor, generally should not adopt.So adopt a new economical rationality technique, utilize seawater and salt lake brine to extract high purity magnesium hydroxide, be the crux that solves Salt Lake Potash production and comprehensive utilization of resources bottleneck.
Organic amine, particularly can be water-soluble and the organic amine of slightly soluble water, in the aqueous solution, can provide OH
-, can play lime, the effect that ammonia is the same with sodium hydroxide.About utilizing organic amine to remove SO in flue gas
2, utilize organic amine to reclaim the carbonic acid gas in industrial gaseous waste, and utilize Manufacturing Soda by Amine Process etc., in numerous documents and patent, all report for work.Illustrate that it is feasible utilizing the basicity of organic amine to precipitate metal.But the solubleness of the organic amine described in its patent in the aqueous solution is all larger, still can only be by extraction so reclaim organic amine, the modes such as distillation reclaim, and energy consumption is larger.
Summary of the invention:
The object of this invention is to provide a kind of to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material, it changes seawater and salt lake brine extraction magnesium hydroxide technique in the past, utilize a part of organic amine to be slightly soluble in water in high alkalinity situation, in low basicity situation, can form with monovalence inorganic acid radical ion the characteristic of soluble salt, realize organic amine recycling under normal temperature state, reduce the distilation steps of amine, can also under normal temperature state, precipitate magnesium simultaneously, and strainability is good, good product quality, reduce greatly energy consumption, saved cost.
In order to solve the existing problem of background technology, the present invention is by the following technical solutions:
1), will obtain filtrate A by the solid suspension impurity removing by filter wherein except the old halogen in salt lake after boron;
2), taking organic amine B as precipitation agent, add in filtrate A, under 5 DEG C ~ 100 DEG C conditions, react 10 ~ 180 minutes, and filtered, filter residue C and liquor C, filter residue C is through washing, the dry high purity magnesium hydroxide product that obtains;
3), liquor C mixes with lime solid or slurry, under 5 DEG C ~ 100 DEG C conditions, reacts 10 ~ 180 minutes, obtains floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle;
4), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, slag is abandoned;
5), filtrate E is carried out to evaporation concentration, obtain calcium chloride crystal;
6), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide through calcining.
Described organic amine is dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, triethylamine, tripropyl amine, hexahydroaniline, quadrol, a kind of or several mixing arbitrarily in amino dodecane.
The add-on of described heavy magnesium organic amine, with the mol ratio of the magnesium ion in seawater and salt lake brine raw material be 1 ~ 3:1.
Described lime solid or the add-on of slurry be, taking the mol ratio of wherein available hydrogen calcium oxide and organic amine as 0.6 ~ 1:1.
The calcining temperature that described high purity magnesium hydroxide obtains high-purity magnesium oxide through calcining is 400 ~ 1000 DEG C, and calcination time is 10 ~ 90 minutes.
The present invention has following beneficial effect:
1) the simple reduced investment of technical process;
2) organic amine can utilize density different from the method separation of phase-splitting from solution, realizes recycle;
3) produce magnesium hydroxide with traditional extra large bittern and bittern water milk of lime process and compare, in the situation that ensureing yield equally, have advantages of that product purity is high;
4) produce magnesium hydroxide with extra large bittern and bittern water ammonia process and compare, can ensure that equally product purity is high, in the situation of the advantage that filtration washing is good, there is yield high and reduced ammonia still process process, the advantage that energy consumption is low.Also avoided the pollution of ammonia volatilization to environment simultaneously;
5) produce magnesium oxide with extra large bittern and bittern water sodium hydroxide method and compare, there is obvious cost advantage.
Brief description of the drawings:
Fig. 1 is process flow sheet of the present invention.
Embodiment:
Referring to Fig. 1, this embodiment by the following technical solutions:
1), will obtain filtrate A by the solid suspension impurity removing by filter wherein except the old halogen in salt lake after boron;
2), taking organic amine B as precipitation agent, add in filtrate A, under 5 DEG C ~ 100 DEG C conditions, react 10 ~ 180 minutes, and filtered, filter residue C and liquor C, filter residue C is through washing, the dry high purity magnesium hydroxide product that obtains;
3), liquor C mixes with lime solid or slurry, under 5 DEG C ~ 100 DEG C conditions, reacts 10 ~ 180 minutes, obtains floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle;
4), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, slag is abandoned;
5), filtrate E is carried out to evaporation concentration, obtain calcium chloride crystal;
6), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide through calcining.
Described organic amine is dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, triethylamine, tripropyl amine, hexahydroaniline, quadrol, a kind of or several mixing arbitrarily in amino dodecane.
The add-on of described heavy magnesium organic amine, with the mol ratio of the magnesium ion in seawater and salt lake brine raw material be 1 ~ 3:1.
Described lime solid or the add-on of slurry be, taking the mol ratio of wherein available hydrogen calcium oxide and organic amine as 0.6 ~ 1:1.
The calcining temperature that described high purity magnesium hydroxide obtains high-purity magnesium oxide through calcining is 400 ~ 1000 DEG C, and calcination time is 10 ~ 90 minutes.
The related chemical equation of this embodiment is as follows:
MgCl
2+2RN.OH→Mg(OH)
2+2RN.Cl
2RN.Cl+Ca(OH)
2→2RN.OH+CaCl
2
Mg(OH)
2→MgO+H
2O
Wherein RN.OH is organic amine.
Embodiment mono-:
The raw material that the present embodiment uses has 1). filtrate A portion (molar weight of getting magnesium in filtrate A is 1 mole); 2). organic amine B is dibutylamine portion (molar weight of getting dibutylamine is 2 moles); 5). lime portion (molar weight of available hydrogen calcium oxide is 1 mole)
1), taking organic amine B portion as precipitation agent, add in filtrate A, under 30 DEG C of conditions, react 60 minutes, and filtered, obtain filter residue C and liquor C, pure water countercurrent washing, wash water that filter residue C weighs 2 times of volumes through slag are incorporated to liquor C, and filter residue is in 200 DEG C of dry high purity magnesium hydroxide products that obtain.
2), liquor C and lime are a mixes, and under 30 DEG C of conditions, react 60 minutes, obtain floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle.
3), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, filter residue is washed rear slag and is abandoned.
4), filtrate E is carried out to evaporation concentration, obtain calcium chloride crystal.
5), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide for 30 minutes through 800 DEG C of calcinings.
The weight of the magnesium hydroxide obtaining through above-mentioned steps is 53.9 grams, and purity is 99%, and direct yield is 92%, and calcining gained magnesium oxide is 37.1 grams, and purity is 99%.
The demonstration of gained magnesium hydroxide scanning electron microscope, magnesium hydroxide in the form of sheets, concentrate, between 0.7 ~ 15um by size-grade distribution.Specific surface area is 70m
2/ g.
Embodiment bis-:
The raw material that the present embodiment uses has 1). filtrate A portion (molar weight of getting magnesium in filtrate A is 1 mole); 2). organic amine C is dibutylamine and dihexylamine portion (molar weight of getting dibutylamine is 1 mole, and the molar weight of getting dihexylamine is 1 mole); 3). lime portion (molar weight of available hydrogen calcium oxide is 1.5 moles)
1), taking organic amine B portion as precipitation agent, add in filtrate A, under 50 DEG C of conditions, react 90 minutes, and filtered, obtain filter residue C and liquor C, pure water countercurrent washing, wash water that filter residue C weighs 2 times of volumes through slag are incorporated to liquor C, and filter residue is in 200 DEG C of dry high purity magnesium hydroxide products that obtain.
2), liquor C and lime are a mixes, and under 50 DEG C of conditions, react 90 minutes, obtain floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle.
3), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, filter residue is washed rear slag and is abandoned.
4), filtrate E is carried out to evaporation concentration, obtain calcium chloride crystal.
5), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide for 30 minutes through 800 DEG C of calcinings.
The weight of the magnesium hydroxide obtaining through above-mentioned steps is 54.5 grams, and purity is 99%, and direct yield is 93%, and calcining gained magnesium oxide is 37.5 grams, and purity is 99.1%.
Embodiment tri-:
The raw material that the present embodiment uses has 1). filtrate A portion (molar weight of getting magnesium in filtrate A is 1 mole); 2). organic amine B is dipropyl amine, dibutylamine and dihexylamine portion (molar weight of getting dipropyl amine is 1 mole, and the molar weight of getting dibutylamine is 1 mole, and the molar weight of getting dihexylamine is 1 mole); 3). lime portion (molar weight of available hydrogen calcium oxide is 2 moles)
1), taking organic amine B portion as precipitation agent, add in filtrate A, under 70 DEG C of conditions, react 60 minutes, and filtered, obtain filter residue C and liquor C, pure water countercurrent washing, wash water that filter residue C weighs 2 times of volumes through slag are incorporated to liquor C, and filter residue is in 200 DEG C of dry high purity magnesium hydroxide products that obtain.
2), filtrate D and lime are a mixes, and under 70 DEG C of conditions, react 60 minutes, obtain floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle.
3), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, filter residue is washed rear slag and is abandoned.
4), filtrate F is carried out to evaporation concentration, obtain calcium chloride crystal.
5), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide for 30 minutes through 800 DEG C of calcinings.
The weight of the magnesium hydroxide obtaining through above-mentioned steps is 54.8 grams, and purity is 99%, and direct yield is 93.6%, and calcining gained magnesium oxide is 37.8 grams, and purity is 99%.
Embodiment tetra-:
The raw material that the present embodiment uses has 1). filtrate A portion (molar weight of getting magnesium in filtrate A is 1 mole); 2). organic amine B is diamylamine portion (molar weight of getting diamylamine is 2 moles); 5). lime portion (molar weight of available hydrogen calcium oxide is 1 mole)
1), taking organic amine B portion as precipitation agent, add in filtrate A, under 50 DEG C of conditions, react 10 minutes, and filtered, obtain filter residue C and liquor C, pure water countercurrent washing, wash water that filter residue C weighs 2 times of volumes through slag are incorporated to liquor C, and filter residue is in 200 DEG C of dry high purity magnesium hydroxide products that obtain.
2), liquor C and lime are a mixes, and under 50 DEG C of conditions, react 10 minutes, obtain floating on the organic amine B of liquid upper, and the slurry D of bottom.Separate organic amine B by phase-splitting, organic amine B enters next working cycle.
3), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, filter residue is washed rear slag and is abandoned.
4), filtrate F is carried out to evaporation concentration, obtain calcium chloride crystal.
5), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide for 30 minutes through 800 DEG C of calcinings.
The weight of the magnesium hydroxide obtaining through above-mentioned steps is 52.7 grams, and purity is 99%, and direct yield is 90%, and calcining gained magnesium oxide is 36.3 grams, and purity is 99%.
Claims (5)
1. to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material, it is characterized in that its preparation method is:
1), will obtain filtrate A by the solid suspension impurity removing by filter wherein except the old halogen in salt lake after boron;
2), taking organic amine B as precipitation agent, add in filtrate A, under 5 DEG C ~ 100 DEG C conditions, react 10 ~ 180 minutes, and filtered, filter residue C and liquor C, filter residue C is through washing, the dry high purity magnesium hydroxide product that obtains;
3), liquor C mixes with lime solid or slurry, under 5 DEG C ~ 100 DEG C conditions, reacts 10 ~ 180 minutes, obtains floating on the organic amine B of liquid upper, and the slurry D of bottom; Separate organic amine B by phase-splitting, organic amine B enters next working cycle;
4), by slurry D filter, washing, obtain filtrate E and filter residue E, filter residue E is impurity in a small amount of lime, slag is abandoned;
5), filtrate E is carried out to evaporation concentration, obtain calcium chloride crystal;
6), the high purity magnesium hydroxide obtaining is obtained to high-purity magnesium oxide through calcining.
2. according to claim 1 a kind of to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material, it is characterized in that described organic amine is dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, triethylamine, tripropyl amine, hexahydroaniline, quadrol, a kind of or several mixing arbitrarily in amino dodecane.
3. according to claim 1ly a kind ofly it is characterized in that the add-on of described heavy magnesium organic amine to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material, with the mol ratio of the magnesium ion in seawater and salt lake brine raw material be 1 ~ 3:1.
4. according to claim 1ly a kind ofly it is characterized in that to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material described lime solid or the add-on of slurry are, taking the mol ratio of wherein available hydrogen calcium oxide and organic amine as 0.6 ~ 1:1.
5. according to claim 1ly a kind ofly it is characterized in that to prepare the method for high-purity magnesium oxide except the old halogen in boron salt lake as raw material the calcining temperature that described high purity magnesium hydroxide obtains high-purity magnesium oxide through calcining is 400 ~ 1000 DEG C, calcination time is 10 ~ 90 minutes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229925A (en) * | 2007-10-11 | 2008-07-30 | 河北科技大学 | Method for preparing magnesium hydroxide with coproduction of calcium chloride |
| CN102275958A (en) * | 2011-07-29 | 2011-12-14 | 武汉工程大学 | Method for preparing magnesium hydroxide utilizing magnesium sulfate as raw material |
| CN102701476A (en) * | 2012-05-15 | 2012-10-03 | 山东大学 | Comprehensive utilization method of concentrated sea water or brackish water |
-
2012
- 2012-12-31 CN CN201210588257.4A patent/CN103896314A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101229925A (en) * | 2007-10-11 | 2008-07-30 | 河北科技大学 | Method for preparing magnesium hydroxide with coproduction of calcium chloride |
| CN102275958A (en) * | 2011-07-29 | 2011-12-14 | 武汉工程大学 | Method for preparing magnesium hydroxide utilizing magnesium sulfate as raw material |
| CN102701476A (en) * | 2012-05-15 | 2012-10-03 | 山东大学 | Comprehensive utilization method of concentrated sea water or brackish water |
Non-Patent Citations (3)
| Title |
|---|
| 于凯等: ""利用老卤制备高活性纳米氧化镁"", 《青岛科技大学学报(自然科学版)》 * |
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Application publication date: 20140702 |