CN102060313B - Novel process for producing high-purify magnesium oxide from salt lake brine - Google Patents
Novel process for producing high-purify magnesium oxide from salt lake brine Download PDFInfo
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- CN102060313B CN102060313B CN2010105596751A CN201010559675A CN102060313B CN 102060313 B CN102060313 B CN 102060313B CN 2010105596751 A CN2010105596751 A CN 2010105596751A CN 201010559675 A CN201010559675 A CN 201010559675A CN 102060313 B CN102060313 B CN 102060313B
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Abstract
The invention discloses a novel process for producing high-purify magnesium oxide from salt lake brine, belongs to the technical field of comprehensive utilization of brine and aims to provide a process for coproducing high-purify magnesium oxide, sodium sulfate and sodium chloride by taking natural salt lake brine and sodium hydrogen carbonate as raw materials. The process comprises the following steps of: blending according to an equivalence ratio of magnesian ions to bicarbonate ions, being (1:2.02)-(1:2.05); separating after reaction to obtain intermediate products, i.e. basic magnesium carbonate and mother liquid I; washing the basic magnesium carbonate with deionized water; calcining the washed basic magnesium carbonate to obtain the high-purify magnesium oxide; evaporating and concentrating the mother liquid I, and then centrifugally separating to obtain the basic magnesium carbonate and mother liquid II; evaporating and concentrating the mother liquid II, and then centrifuging to obtain anhydrous sodium sulfate and mother liquid III; and cooling and crystallizing the mother liquid III to obtain sodium chloride and mother liquid IV. The process has the advantages of realization of comprehensive utilization of brine, simplicity of operation in a reaction process, easiness for industrialized mass production, high magnesium conversion ratio, good product quality, no three-waste emission in the reaction process and favorable environment and societal benefits.
Description
Technical field
The invention belongs to the technical field of salt lake brine comprehensive utilization, be specifically related to a kind of novel process of producing high-purity magnesium oxide with salt lake brine.
Background technology
1., the serum method utilize halogen (sea) water to have following several kinds at present: for the raw material production method of magnesium oxide; Comprise two kinds of Wingdale serum method and rhombspar serum methods; I.e. magnesium chloride in (halogen) water of sea and grey serum (it is formulated to add water behind Wingdale or the dolomite calcination) reaction generates Marinco H, generates Natural manganese dioxide through calcining again.This method raw materials cost is low, is external maximum method that adopts, and just generally adopts this method production high purity seawater magnesia like Japan and Britain.Main drawback is that the calcium in the product is high, boron is high.2., ammonia process, utilize ammonia or ammoniacal liquor and soluble magnesium reactant salt to generate Marinco H solution, make Natural manganese dioxide through calcining again.Be characterized in that the Marinco H percent crystallinity that generates is higher, sedimentation speed is fast, is easy to filter and washing; Technology and technology are superior to the serum method.Shortcoming is that raw materials cost is higher than the serum method, and boron content is high in the product.3., carborization, contain in the mg ion bittern in high density and to feed carbonic acid gas,, make its method that generates magnesiumcarbonate or magnesium basic carbonate under certain condition, purified, light-burned, processing is ripe and technology that heavily burn is processed highly-purity magnesite.Carborization is that intermediate product is a magnesium basic carbonate than a remarkable advantage of serum method; Its strainability is better than Marinco H, and shortcoming is: equipment is huge, and investment is big; Magnesium basic carbonate is formed fixing, in the product calcium contents higher (with rhombspar or, there is this problem in magnesite when being raw material).4., the magnesium salts direct pyrolysis method, mainly be the magnesium chloride strong solution directly in High Temperature Furnaces Heating Apparatus thermolysis generate Natural manganese dioxide and hydrogen chloride gas.Decomposition course is: magnesium chloride hexahydrate is heated to 117 ℃ and promptly begins dehydration; Be warming up to 230 ℃ and just generate basic magnesium chloride; Temperature is during greater than 527 ℃, and the basic magnesium chloride hydrolysis generates Natural manganese dioxide and aqueous hydrogen chloride gas, and the Natural manganese dioxide of generation makes high purity magnesium oxide through the washing purifying again.Because this method has generated hydrogen chloride gas, at high temperature equipment corrosion is very serious, so very high to the equipment and materials requirement, existing several at home at present families prepare to go into operation.5., the soda ash method, utilize yellow soda ash and solubility magnesium salts to generate magnesium basic carbonate, can make Natural manganese dioxide through calcining again.This method technology is simply ripe, but because raw materials cost is high, and product market competitiveness is not strong, this method seldom adopts.Above the whole bag of tricks all exists the defective of aspects such as product purity, mother liquor processing, transformation efficiency, processing unit, raw materials cost to some extent.
Sulfate type salt lake bittern is Na
+, Mg
2+//SO
4 2-, Cl
--H
2The O mutual system of quadruplex is an example with the Yuncheng, Shanxi salt lake, for many years; Follow summer always and support halogen, analyse nitre winter, is the technology of raw material production Sodium sulfate anhydrous.min(99) with the mirabilite hydrate; Because single extraction sodium sulfate; Making the magnesium salts enrichment not only influences the quality product of Sodium sulfate anhydrous.min(99), and causes wasting of magnesium resource.For making full use of salt lake resources, produce high value added product, utilize the Mg in the bittern
2+Produce high-purity magnesium oxide and mother liquor is fully utilized,, have important practical significance for changing salt lake resource exploitation mode for a long time.
Summary of the invention
The purpose of this invention is to provide a kind of technology of utilizing mineral salt lake bittern water and sodium hydrogencarbonate for raw material production high-purity magnesium oxide and co-producing sodium sulfate and sodium-chlor.
The present invention realizes through following technical scheme:
A kind of novel process of producing high-purity magnesium oxide with salt lake brine may further comprise the steps:
(1) bittern purifying: bittern is heated to 60-80 ℃, filters, must make with extra care bittern behind the elimination impurity with zeyssatite;
(2) be refining bittern that 1:2.02-1:2.05 slowly joins in the sodium hydrogen carbonate solution and reacts by the equivalence ratio of mg ion and bicarbonate ion; Being 30 rev/mins by rotating speed stirs; The reaction pyrolysis temperature is controlled at 50-80 ℃, reinforced 1 hour time, 2 hours reaction times; 50-80 ℃ of insulation ageing 2 hours, get intermediate product magnesium basic carbonate and mother liquor I after the spinning;
(3) magnesium basic carbonate is washed with Natural manganese dioxide quality 20-50 deionized water doubly at normal temperatures; Wash water is recycled; Magnesium basic carbonate after washed was calcined 2-4 hour down at 800-900 ℃, obtained high-purity magnesium oxide, and magnesian purity can reach more than 99%;
(4) after mother liquor I direct evaporation concentrated, spinning got magnesium basic carbonate and mother liquor II, and the transformation efficiency of magnesium reaches 98%;
(5) according to Na
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams is with mother liquor II evaporation concentration, and spinning gets SODIUM SULPHATE ANHYDROUS 99PCT and mother liquor III;
(6) mother liquor III crystallisation by cooling gets sodium-chlor and mother liquor IV, and the mother liquor IV is returned the recycle of mother liquor II.
The present invention compared with prior art has following advantage:
(1) the reaction process easy handling does not have particular requirement to equipment;
(2) be the raw material production high-purity magnesium oxide with bittern and sodium hydrogencarbonate, adopt limit coronite pyrolytic mode, the products obtained therefrom quality is high and stable, easy realization of large-scale production;
(3) transformation efficiency of magnesium can reach 98%;
(4) this technology is that a good in economic efficiency approach is found in the bittern comprehensive utilization;
(5) this technology good fortune is produced sodium sulfate and sodium-chlor, and mother liquid recycling does not have any pollution to environment.
Description of drawings
Fig. 1 is a kind of FB(flow block) of producing the novel process of high-purity magnesium oxide with salt lake brine of the present invention.
Embodiment
Embodiment 1
With bittern with diatomite filtration after with sodium hydrogencarbonate; The equivalence ratio of mg ion and bicarbonate ion is that 1:2.02 (also can be 1:2.03 or 1:2.04 or 1:2.05) reacts; Bittern slowly joined under whipped state in 80 ℃ the saturated solution of sodium bicarbonate; Reaction is 2 hours under this temperature; And insulation ageing 2 hours; Behind the suction filtration intermediate product magnesium basic carbonate and mother liquor I, after will precipitate deionized water with 50 times of Natural manganese dioxide quality (also can be 20 times or 30 times or 40 times) and washing, 900 ℃ (they also can be 850 ℃ or 800 ℃) following calcine 4 hours (also can be 2 hours or 3 hours) the high-purity magnesium oxide product.
After mother liquor I direct evaporation concentrated, spinning got magnesium basic carbonate and mother liquor II.Through above-mentioned two-step reaction, can make the transformation efficiency of magnesium reach 98%.According to Na
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams to mother liquor II evaporation concentration after, spinning gets SODIUM SULPHATE ANHYDROUS 99PCT and mother liquor III.Mother liquor III crystallisation by cooling gets sodium-chlor and mother liquor IV, and the mother liquor IV is returned the recycle of mother liquor II.
Embodiment 2
Get Mg
2+Content is the bittern 1L of 40g/L and contains 228g NaHCO
3Saturated solution reaction, under 65 ℃ of heat-retaining conditions, slowly join bittern in the saturated solution of sodium bicarbonate; Under the stirring of 30 rev/mins of rotating speeds, to react 2 hours, the insulation ageing is after 2 hours; Carry out solid-liquid separation, get intermediate product magnesium basic carbonate 500g and mother liquor I.After with the 3.5L deionized water magnesium basic carbonate being washed, with filter cake 900 ℃ of calcinings 4 hours down, Natural manganese dioxide 57.7g, quality is 99.13%.
After mother liquor I 1.65L direct evaporation concentrated, spinning got magnesium basic carbonate 70g and mother liquor II 0.67L.After magnesium basic carbonate washs, calcined 4 hours down, get Natural manganese dioxide 7.8g, according to Na at 900 ℃
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams to mother liquor II evaporation concentration after, spinning gets SODIUM SULPHATE ANHYDROUS 99PCT 121.6g and mother liquor III 0.24L.Mother liquor III crystallisation by cooling gets sodium-chlor 32.5g and mother liquor IV 0.21L, and the mother liquor IV is returned the recycle of mother liquor II.
Embodiment 3
Get Mg
2+Content is the bittern 1L of 38g/L and contains 210g NaHCO
3Saturated solution reaction, under 70 ℃ of conditions of temperature, slowly join bittern in the saturated solution of sodium bicarbonate; Under the stirring of 35 rev/mins of rotating speeds, to react 2.5 hours, the insulation ageing is after 2 hours; Carry out solid-liquid separation, get intermediate product magnesium basic carbonate 480g and mother liquor I.After with the 3.0L deionized water magnesium basic carbonate being washed, with filter cake 850 ℃ of calcinings 3 hours down, Natural manganese dioxide 55.7g, quality is 99.05%.
After mother liquor I 1.55L direct evaporation concentrated, spinning got magnesium basic carbonate 68g and mother liquor II 0.62L.After magnesium basic carbonate washs, calcined 4 hours down, get Natural manganese dioxide 7.2g, according to Na at 900 ℃
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams to mother liquor II evaporation concentration after, spinning gets SODIUM SULPHATE ANHYDROUS 99PCT 120.8g and mother liquor III 0.23L.Mother liquor III crystallisation by cooling gets sodium-chlor 30.5g and mother liquor IV 0.20L, and the mother liquor IV is returned the recycle of mother liquor II.
Embodiment 4
Get Mg
2+Content is the bittern 1L of 42g/L and contains 240g NaHCO
3Saturated solution reaction, under 60 ℃ of heat-retaining conditions, slowly join bittern in the saturated solution of sodium bicarbonate; Under the stirring of 25 rev/mins of rotating speeds, to react 2.5 hours, the insulation ageing is after 3 hours; Carry out solid-liquid separation, get intermediate product magnesium basic carbonate 530g and mother liquor I.After with the 4.5L deionized water magnesium basic carbonate being washed, with filter cake 850 ℃ of calcinings 3.5 hours down, Natural manganese dioxide 60.5g, quality is 99.25%.
After mother liquor I 1.72L direct evaporation concentrated, spinning got magnesium basic carbonate 78g and mother liquor II 0.68L.After magnesium basic carbonate washs, calcined 4 hours down, get Natural manganese dioxide 8.1g, according to Na at 900 ℃
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams to mother liquor II evaporation concentration after, spinning gets SODIUM SULPHATE ANHYDROUS 99PCT 122.8g and mother liquor III 0.26L.Mother liquor III crystallisation by cooling gets sodium-chlor 32.5g and mother liquor IV 0.23L, and the mother liquor IV is returned the recycle of mother liquor II.
Claims (1)
1. method of producing high-purity magnesium oxide with salt lake brine is characterized in that may further comprise the steps:
(1) bittern purifying: bittern is heated to 60-80 ℃, filters, must make with extra care bittern behind the elimination impurity with zeyssatite;
(2) be refining bittern that 1:2.02-1:2.05 slowly joins in the sodium hydrogen carbonate solution and reacts by the equivalence ratio of mg ion and bicarbonate ion; Being 30 rev/mins by rotating speed stirs; The reaction pyrolysis temperature is controlled at 50-80 ℃, reinforced 1 hour time, 2 hours reaction times; 50-80 ℃ of insulation ageing 2 hours, get intermediate product magnesium basic carbonate and mother liquor I after the spinning;
(3) magnesium basic carbonate is washed with Natural manganese dioxide quality 20-50 deionized water doubly at normal temperatures, wash water is recycled, and the magnesium basic carbonate after washing was calcined 2-4 hour down at 800-900 ℃, obtained high-purity magnesium oxide;
(4) after mother liquor I direct evaporation concentrated, spinning got magnesium basic carbonate and mother liquor II;
(5) according to Na
+//SO
4 2-, Cl
--H
2The O ternary phase diagrams is with mother liquor II evaporation concentration, and spinning gets SODIUM SULPHATE ANHYDROUS 99PCT and mother liquor III;
(6) mother liquor III crystallisation by cooling gets sodium-chlor and mother liquor IV, and the mother liquor IV is returned the recycle of mother liquor II.
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|---|---|---|---|
| CN2010105596751A CN102060313B (en) | 2010-11-26 | 2010-11-26 | Novel process for producing high-purify magnesium oxide from salt lake brine |
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| CN102060313B true CN102060313B (en) | 2012-07-25 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102320632A (en) * | 2011-08-26 | 2012-01-18 | 南风化工集团股份有限公司 | Method for preparing high-purity magnesium hydroxide and nanometer calcium carbonate as co-product from salt lake brine |
| CN105366694B (en) * | 2014-08-13 | 2016-10-05 | 南风化工集团股份有限公司 | The method that the deep pond of a kind of salt lake bittern stores |
| CN104261940B (en) * | 2014-09-24 | 2016-08-24 | 中国科学院青海盐湖研究所 | A kind of preparation method of potassic-magnesian fertilizer |
| CN104402025B (en) * | 2014-11-27 | 2016-04-13 | 中国科学院青海盐湖研究所 | A kind ofly utilize the rough method preparing high-purity magnesium oxide of magnesiumcarbonate |
| CN113800542A (en) * | 2020-06-16 | 2021-12-17 | 南风化工集团股份有限公司 | High-efficiency resource utilization technology for coking desulfurization ash |
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| EP1846328A1 (en) * | 2005-02-01 | 2007-10-24 | BHP Billiton Ssm Technology Pty Ltd. | Process for the production of magnesium oxide |
| CN100374373C (en) * | 2006-07-24 | 2008-03-12 | 和顺县银海镁业有限公司 | Prepn process of magnesia for silicon steel |
| CN101607720A (en) * | 2008-06-16 | 2009-12-23 | 中国科学院过程工程研究所 | With the bittern that contains magnesium chloride is the feedstock production method of magnesium oxide |
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