CN1029111C - Comprehensive utilization of Boron-Magnesium mine - Google Patents
Comprehensive utilization of Boron-Magnesium mine Download PDFInfo
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- CN1029111C CN1029111C CN 90110198 CN90110198A CN1029111C CN 1029111 C CN1029111 C CN 1029111C CN 90110198 CN90110198 CN 90110198 CN 90110198 A CN90110198 A CN 90110198A CN 1029111 C CN1029111 C CN 1029111C
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- boron
- magnesium
- ore deposit
- mother liquor
- calcium
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Abstract
The present invention relates to an improved technology for processing boron-magnesium ore by a sulfuric acid method. In the technology, boron-magnesium ore is oxidized to remove iron after being added in sulfuric acid to be treated by acidolysis, and then different precipitating agents are added step by step is added; thus, light magnesium carbonate and calcium sulfate dihydrate can be prepared respectively, and a mother solution can be returned to the acidolysis working procedure to be circularly used. Accordingly, the purposes of improving the yield of boron and the comprehensive utilization of boron-magnesium ore can be reached. The present invention can be used for processing boron-magnesium ore of which the grade is less than 20%, and enables the yield of boron to reach more than 80%.
Description
The invention belongs to the working method in boron magnesium ore deposit.
Sulfuric acid process processing boron magnesium ore deposit is an old commercial run, and it is to decompose boron magnesium ore deposit with sulfuric acid, through operations such as acidolysis, filter cleaner, evaporation, crystallisation by cooling, separation, finally obtains the boric acid product.Sulfuric acid process be fit to the processing grade more than 30%, magnesium boron ratio is 0.7～1.8(MgO/Bo) boron magnesium ore deposit, processes such ore deposit, the boron yield is generally about 50～65%.The boron magnesium ore deposit grade of China is lower, most of ore is below 20%, the magnesium boron of ore is more higher than also, be generally about 2.5～3.5, with old sulfuric acid process processing, mother liquor after the Crystallization Separation does not have and returns hydrolysis procedure and recycle, and makes to contain the boron that accounts for boron total amount 35～60% in the mother liquor and lose, and therefore makes the boron yield only reach 30～40%; Simultaneously, old sulfuric acid process only can obtain single boric acid product, and ore can not fully utilize, and many useful compositions such as magnesium, calcium, iron etc. all can not extract, and cause the waste of resource.Low according to China's boron magnesium ore deposit grade, magnesium boron is than high situation, and the technology in sulfuric acid process processing boron magnesium ore deposit must be improved.
About producing the impurities removal in the boric acid technological process, proposing among the Chinese patent CN87103625A to adopt hydrogen peroxide is oxygenant, the method of lime slurry or lye pH adjustment, its objective is by deironing to reach decolouring that with refining boric acid, its raw material is exactly thick boric acid, produce Magnesium Carbonate Light 41-45, many methods are also arranged, and Chinese patent CN86102539A adopts the method for the ammonia treatment magnesium-containing mineral of bicarbonate of ammonia and recovery, and the magnesium-containing mineral of this patent introduction mainly refers to magnesia or magnesite.The principle of the acid system system of employing terra alba and method also have been extensively to adopt in the industrial production.But, utilize boron magnesium ore deposit to carry out comprehensive process production the said products and yet there are no report.According to China's boron resource.The grade situation, it will be a new technology approach that the comprehensive process comprehensive utilization is carried out in boron magnesium ore deposit.
The objective of the invention is shortcoming, absorb comprehensive boric acid at old sulfuric acid process processing boron magnesium ore deposit existence.Magnesium Carbonate Light 41-45, the production principle of terra alba and technology propose the processing method in a comprehensive process boron magnesium ore deposit, reach to improve the boron yield, also can make boron magnesium ore deposit obtain the purpose of comprehensive utilization simultaneously.
The present invention decomposes the mining sulfuric acid of boron magnesium, and the separation of deironing post crystallization obtains boric acid, and the mother liquor substep adds different precipitation agents again, obtain magnesium salts, calcium salt product respectively, mother liquor returns hydrolysis procedure and recycles, and the boron in the mother liquor is fully extracted, and makes the boron yield reach 80～90%.
The present invention mixes boron magnesium ore deposit and water or the mother liquor of calcium that returns and is made into slip, control liquid-solid ratio 2.0～4.0,50 ℃ of stirrings add 0.50～1.10 95% sulfuric acid of ore deposit amount down, kept 90～100 ℃ of temperature of reaction 1～2 hour, reaction is cooled to later 0.05%～1.5% 26% the hydrogen peroxide that room temperature adds the ore deposit amount, 5～25% the precipitation agent lime carbonate that adds ore deposit amount then, slag and iron are removed in heating fully reaction after-filtration washing, filtrate and washing evaporation to 32～34 degree Beaume, under 35～65 ℃, remove by filter calcium sulfate, adjust pH to 2～3 then are in 25 ℃ of following Crystallization Separation boric acid.Mother liquor after the Crystallization Separation is called the boron mother liquor, 0.5～1.5 ammoniacal liquor and the bicarbonate of ammonia mixed solution that add theoretical amount (in MgO), ammoniacal liquor in the mixed solution is 1.10～1.95 with bicarbonate of ammonia titre ratio, reacted 0.5～2 hour down at 50～85 ℃, filtration washing makes Magnesium Carbonate Light 41-45, and the mother liquor of this moment is called mother liquid of magnesium.With mother liquid of magnesium and theoretical amount (with SO
= 4Meter) milk of lime reacted 1～2 hour down at 90～100 ℃, was reaction end when the pH value is 6～8, and the ammonia that produces in the reaction absorbs through water and can be recycled.Reaction finishes back sulfuric acid adjust pH to 2～4, and filtration washing makes terra alba, and the mother liquor of this moment is called mother liquor of calcium.Mother liquor of calcium partly returns the batching hydrolysis procedure and recycles, and sends to the Crystallization Separation preparing boric acid again after the remainder evaporation.
Because the present invention has taked the mother liquor after the boric acid crystallization is extracted step by step the measure of magnesium, calcium, has realized the recycle of mother liquor, and the boron yield can be brought up to more than 80%.Simultaneously, again the useful component magnesium in the ore deposit, calcium are extracted and is used, realized the comprehensive utilization in boron magnesium ore deposit.Adopt the improved sulfuric acid process of the present invention, can make sulfuric acid process processing China boron magnesium ore deposit reach requirement in the industrialization.
Example 1
Grade is 26.77%, magnesium boron is than boron magnesium ore deposit 100 grams that are 1.65, mix with 350 milliliters of last round-robin mother liquor of calcium, under agitation add 50 milliliters in 95% sulfuric acid, reacted one hour down at 95 ℃, be cooled to and add 10 gram lime carbonate again after room temperature adds 1.0 milliliters hydrogen peroxide, heating fully reaction filtration washing removes slag and iron, and filtrate and wash water steam together to 32 degree Beaume, filters down in 55 ℃, with sulfuric acid adjust pH to 2～3, crystallisation by cooling makes boric acid 39.3 grams, and the rate of decomposition of boron is 92.75%, the boron yield is 84.65%, and mother liquor is referred to as the boron mother liquor.
Boron mother liquor (containing wash water) is heated to 75 ℃ for 335 milliliters, mixes with the ammonia precipitation process agent that contains 85 gram bicarbonate of ammonia and 19 milliliters 25%, under constantly stirring, reacted one hour, dry behind the filtration washing, make 71.3 gram Magnesium Carbonate Light 41-45s, mother liquor is referred to as mother liquid of magnesium (containing wash water).
Mother liquid of magnesium is heated to 80～90 ℃ for 1048 milliliters, mixes with the milk of lime that contains 60 gram calcium oxide, and reaction is one hour under boiling, transfers pH to 2～4 with sulfuric acid, and the filtration washing oven dry makes 129 gram terra albas, and mother liquor is referred to as mother liquor of calcium.The mother liquor of calcium part is returned hydrolysis procedure by the liquid curing ratio of batching and is recycled, and remainder returns the boric acid Crystallization Procedure.
Example 2
Grade is 15.1%, magnesium boron is than being 2.85 boron magnesium ore deposit, 100 grams, mixes with 400 milliliters mother liquor of calcium, adds sour 61 milliliters of 95% sulfuric acid under constantly stirring, reacted one hour down at 95 ℃, be cooled to and add 18 gram lime carbonate again after room temperature adds 1.2 milliliter 26% hydrogen peroxide, heating is the washing of reaction after-filtration fully, removes slag and iron, filtrate and wash water steam to 32 degree Beaume, filter down in 55 ℃, filtrate makes boric acid 29.3 grams with sulfuric acid adjust pH 2～3, crystallisation by cooling.The boron rate of decomposition is 98.01%, and the boron yield is 91.34%.
Boron mother liquor treating processes makes Magnesium Carbonate Light 41-45 117 grams with example 1.
Boron mother liquor treating processes makes terra alba 196.5 grams with example 1.
Mother liquor of calcium is handled with example 1.
Example 3
Grade 12.77%, magnesium boron be than being that 3.29 boron magnesium ore deposit, 150 grams mix for 450 milliliters with mother liquor of calcium, under agitation adds 75 milliliters in 95% sulfuric acid, reacted 1.5 hours down at 95 ℃, be cooled to the hydrogen peroxide of 1.5 milliliter 26% of room temperature adding, add 25 gram lime carbonate again, heating fully reaction after-filtration is washed, remove slag and iron, filtrate and wash water steam to 34 degree Beaume, and in 55 ℃ of filtrations, filtrate is used sulfuric acid adjust pH to 2～3, crystallisation by cooling makes boric acid 28.5 grams.The boron rate of decomposition is 96.47%, and the boron yield is 84.15%.
The boron mother liquor is handled with example 1, makes 106 gram Magnesium Carbonate Light 41-45s.
Mother liquid of magnesium is handled with example 1, makes 165 gram terra albas.
Mother liquor of calcium is handled with example 1.
Claims (1)
1, the method for comprehensive utilization in a kind of boron magnesium ore deposit is that boron magnesium ore deposit is mixed with slip, stirs to add the vitriol oil down, carry out acidolysis reaction more than 2 hours at 90～100 ℃, add hydrogen peroxide and lime carbonate with impurity such as deironing, filter, washing, slagging-off, the filtrate evaporation, crystallisation by cooling preparing boric acid, the mixed solution system Magnesium Carbonate Light 41-45 of adding bicarbonate of ammonia and ammoniacal liquor, add lime slurry system terra alba, it is characterized in that:
(1) to be made into liquid-solid ratio be 2.0～4.0 boron magnesium mineral aggregate slurry for boron magnesium ore deposit and the mother liquor of calcium that loops back, and 95% sulfuric acid that adds ore deposit amount 0.5～1.10% under 50 ℃ of stirrings carried out acidolysis 1～2 hour,
(2) 0.5～1.5% hydrogen peroxide was measured in the adding ore deposit after acid hydrolysis solution was cooled to room temperature, added the precipitation of calcium carbonate agent of ore deposit amount 5～25% again, and heating is fully reacted after-filtration and removed slag and iron,
(3) filtrate is evaporated to 32～34 degree Beaume, filters down at 35～65 ℃, remove calcium sulfate, then adjust pH to 2～3 make boric acid in 25 ℃ of following Crystallization Separation,
(4) the boron mother liquor after the crystallization adds the ammoniacal liquor of theoretical amount (in MgO) and the mixed solution of carbonic acid oronain, and the ratio of the titre of mixed solution is 1.10～1.95, and 50～85 ℃ of reactions 0.5～2 hour, filtration washing made Magnesium Carbonate Light 41-45,
(5) mother liquid of magnesium that will make behind the Magnesium Carbonate Light 41-45 adds theoretical amount (with SO
4Meter) milk of lime, 90～100 ℃ of reactions 1～2 hour, control pH value be 6～8 o'clock be reaction end, use sulfuric acid adjust pH to 2～4 then, filtration washing makes terra alba,
(6) mother liquor of calcium is partly returned the batching hydrolysis procedure and recycle, remainder returns the boric acid Crystallization Procedure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110198 CN1029111C (en) | 1990-12-24 | 1990-12-24 | Comprehensive utilization of Boron-Magnesium mine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90110198 CN1029111C (en) | 1990-12-24 | 1990-12-24 | Comprehensive utilization of Boron-Magnesium mine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1062883A CN1062883A (en) | 1992-07-22 |
| CN1029111C true CN1029111C (en) | 1995-06-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90110198 Expired - Fee Related CN1029111C (en) | 1990-12-24 | 1990-12-24 | Comprehensive utilization of Boron-Magnesium mine |
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| Country | Link |
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| CN (1) | CN1029111C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039112C (en) * | 1995-03-03 | 1998-07-15 | 大连理工大学 | Comprehensive utilization method for decomposition of B-Mg-Fe ore with sulfuric acid |
| CN1108987C (en) * | 1999-12-23 | 2003-05-21 | 化学工业部天津化工研究设计院 | Production process of boric acid and magnesium carbonate from boromagnesite |
| CN100441506C (en) * | 2006-11-10 | 2008-12-10 | 沈阳化工学院 | Method of preparing high activity nano-magnesium oxide using boric acid waste liquid |
| CN103359757A (en) * | 2013-07-16 | 2013-10-23 | 沈阳化工大学 | Iron removal method for one-step method boric acid production process |
| CN105480987A (en) * | 2015-11-04 | 2016-04-13 | 沈阳化工大学 | Reinforced optimized preparation method for boric acid through one-step process |
| CN108101078B (en) * | 2018-01-31 | 2023-07-25 | 四川思达能环保科技有限公司 | Process system and method for producing magnesium sulfate heptahydrate by using boron-magnesium mud |
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1990
- 1990-12-24 CN CN 90110198 patent/CN1029111C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1062883A (en) | 1992-07-22 |
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