CN104817096B - A kind of decalcification technique of the old halogen in high calcium salt pan - Google Patents
A kind of decalcification technique of the old halogen in high calcium salt pan Download PDFInfo
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Abstract
A kind of decalcification technique of the old halogen in high calcium salt pan, comprises the following steps：（1）Molten nitre；（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2‑Mol ratio is 1:1~1.2, which converts halogen, is well mixed, and the reaction time is 1~24h, obtains slurry；（3）Filtering；（4）Wash, dry；（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate.The present invention makes full use of salt lake itself or the sodium sulphate resource near it to be reacted with the calcium source in the old halogen of high calcium, to reach the purpose for making old halogen decalcification, its technological process is simple, cost is low, it can directly implement in resource location, can realize that halogen, and energy by-product gypsum product are converted in the circulation of the magnesium chloride bittern containing high concentration after the old halogen decalcification of high calcium, sulfur acid sodium sulfate decahydrate mineral are digested, mitigate salt lake local environment problem.
Description
Technical field
The present invention relates to a kind of decalcification technique of the old halogen in salt pan, and in particular to a kind of chloride type salt lake bittern high calcium salt pan
The decalcification technique of old halogen.
Background technology
China is the numerous country in a salt lake, and thousands of size salt lakes are a mass of in hinterland, main distribution
In Qinghai-Tibet Platean and Xinjiang region, larger has Cha Er Han and Lop Nur, respectively chloride type and sulfate type salt lake.Only examine
All kinds of salt gross reserves have been verified just up to more than 600 hundred million tons in your sweat salt lake, and whole salt lake extraction value exceedes tens of trillion yuans.
In current chloride type salt lake development process, in order to accelerate sodium chloride phase evaporation progress, shorten salt pan and shine
The ore deposit time, salt lake production efficiency is improved, adjusting former halogen by the way of the old halogen in salt pan and former halogen convert halogen mostly constitutes.But for green grass or young crops
Sea salt lake partial oxidation thing type bittern, calcium content is higher, and due to the circulative accumulation of calcium, its concentration also can be raised constantly, if pressed
Halogen technology is converted according to tradition, the old halogen of high calcium is not handled, this may bring certain influence to extracting potassium chloride in bittern, also have
Calcium salt may be made to bring potassium ores influence floatation process into, product quality is reduced, and high calcium carnallite preparing potassium chloride is simultaneously
It is the huge technical barrier that many enterprise's productions in Qinghai Salt Lake area face, it is therefore necessary to which the old halogen of high calcium is chemically treated.
Research on deliming technique at present, uses ion-exchange and precipitation method technique etc., such as mostly
CN203741143U, which discloses a kind of resin adsorption device, is used for the method for calcium ions and magnesium ions deep purifying, and CN103641264A is disclosed
A kind of sewage treatment area, secondary effluent is passed through be filled with mixture iron exchange resin reactor synchronously go deliming, barium,
The method of the polyvalent cations such as iron and negatively charged small molecule dissolved organic matter, both the above utilizes ion exchange principle,
Calcium ions and magnesium ions are synchronously replaced to reach the purpose of removal, but are only applicable to the low concentration that calcium ions and magnesium ions concentration is less than 100mg/L
The deep purifying of calcium-magnesium-containing water quality, and the exchanger resin adsorption capacity for adapting to specific ion is limited, one if excessive concentration
Aspect can increase adsorbent amount, and then increase production cost, while absorption regeneration effect also can be by extreme influence, into packet
Different degrees of destruction can be also caused to ion exchange resin chemical property, mechanical performance into complicated aqueous salt brine.
CN103864249A discloses a kind of technique for adding calcium ions and magnesium ions in sodium carbonate removing salt lake bittern, is also that calcium and magnesium is synchronously heavy
Form sediment；But process above all presence can not realize separating calcium and magnesium and the defect effectively utilized.CN103508472A discloses a kind of profit
It is substantially according to phase diagram theory, due to calcium and magnesium chemically with the method for evaporation-principle refrigeration enriching lithium deliming from the water of oil field
Matter is extremely similar, and the calcium sulfate saturation phase region of low temperature phasor is located exactly at by evaporating obtained concentration chloride-calcium type oil field water,
Therefore the purpose of freezing deliming can be realized by the method for freezing；CN103523801A discloses a kind of chloride type with containing potassium
Lower bittern combined extracting potassium, boron, the method for lithium, also with saltcake to eliminating calcium except the mother liquor progress deliming before potassium is analysed after boron
Influence to subsequently putting forward lithium technique, but the calcium sulfate of precipitation can be crystallized in sodium chloride salt pan with the co-precipitation of NaCl salt, due to
Sodium chloride amount of precipitation is big, and industrial value is low to cause harvesting cost higher, and is difficult to the calcium sulfate of precipitation with product form point
From reclaiming and use.Therefore, above-mentioned technique all has certain limitation applied to the bittern of specific composition, and not to removing
Calcium with product form reclaim get up, cause a certain degree of wasting of resources.
And gypsum（CaSO4·2H2O）It is a kind of purposes extremely wide industrial materials and construction material again, available for cement
Retarder, gypsum building products, modelling, medical food additive, gas washing in SA production, filler, paint filler etc., can be with
It is the product such as calcium sulfate crystal whiskers to continue deep processing, can also be widely used in as new function material plastics, rubber, binding agent,
It is a kind of minimum environmental protection material of toxicity in the product manufacturings such as friction material, coating, paint, heat-barrier material and light building material
Material, if the effectiveness of operation of salt lake production will also be greatly increased by being comprehensively utilized to the calcium of the old halogen of salt pan high calcium.Although China
It is a natural gypsum resource-rich country, but because its purposes is wide, the features such as consumption is big has also derived many by-product gypsums
Chemical industry, and wherein as the mirabilite gypsum of industrial production byproduct（Na2SO4·CaSO4）, drenched mostly using glauberite
The method leaching Na of leaching2SO4After form so-called mirabilite gypsum, alternative natural gypsum incorporation cement is used as retarder etc..But it is fresh
Have been reported that the technique using the old halogen by-product gypsum in salt pan.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art there is provided a kind of technological process is simpler, raw
Produce cost relatively low, the decalcification technique of the old halogen in high calcium salt pan of environmental protection, removing calcium retains magnesium, while can by-product gypsum
（CaSO4·2H2O）Product.
The present invention solve its technical problem use technical scheme be, a kind of decalcification technique of the old halogen in high calcium salt pan, including
Following steps：
（1）Molten nitre：By saltcake and water or the undersaturated light bittern of sodium chloride-containing according to 1:（0.5~10）（It is preferred that 1：0.6~
1.7）Mass ratio under normal temperature condition mixed dissolution, obtain saltcake mother liquor；
The undersaturated light bittern Brine salinity≤25wt% of sodium chloride-containing；
The purity of the saltcake（The content of sal glauberi）>=80wt%；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:（1~
1.2）Convert halogen to be well mixed, the reaction time is 1~24h（It is preferred that 8~12h）, obtain slurry；
（3）Filtering：By step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:（2~5）Through starching 10~60 again
Minute（It is preferred that 25~35 minutes）Stirring washing, is then dried, 105~120 DEG C of drying temperature, 1~4h of drying time obtains stone
Cream（CaSO4·2H2O）Product, then wash and starch water return to step（1）Instead of the undersaturated light bittern dissolving awns of part water or sodium chloride
Nitre is recycled；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate.
The old halogen in high calcium salt pan of the present invention is the old halogen of calcic that chloride type salt lake is obtained after evaporation and concentration, its bittern
In composition, Ca2+≥4.0wt%。
The present invention makes full use of salt lake itself or the sodium sulphate resource near it to be reacted with the calcium source in the old halogen of high calcium,
To reach the purpose for making old halogen decalcification, its technological process is simple, and cost is low, can directly implement in resource location, Ji Nengshi
Halogen is converted in the circulation of the magnesium chloride bittern containing high concentration after the old halogen decalcification of existing high calcium, and can by-product gypsum product, digestion sulfur acid sodium awns
Nitre mineral, mitigate salt lake local environment problem.
Present invention process has the beneficial effect that：
（1）Technological process is simple, and production cost is low, and energy consumption is low, environmental protection；
（2）Raw material is easy to get, and harvesting cost is low；
（3）By-produced gypsum purity is higher（≥98wt%）, can be high added value directly as building material or deep processing
New function material；
（4）Old halogen calcium removal efficiency is high（≥80wt%）；
（5）Zero-emission is realized, meets recycling economy requirement.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
The present embodiment is by taking the old halogen of China Qinghai chloride type salt lake high calcium as an example, in its old halogen composition, Ca2+:
5.98wt%, concrete operations comprise the following steps：
（1）Molten nitre：By saltcake and water according to 1:0.5 mass ratio is mixed, and stirring is complete to dissolving under normal temperature condition, obtains awns
Nitre mother liquor；Wherein saltcake purity 80%；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:1.2 convert
Halogen is well mixed, and the reaction time is 24h, obtains slurry；
（3）Filtering, by step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:2 through starching 20min stirring water again
Wash, then dry, 105 DEG C of drying temperature, drying time 4h obtains gypsum（CaSO4·2H2O）Product；Water is washed and starched again returns to step
Suddenly（1）Recycled instead of part aqueous solution saltcake；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate, and does not influence original salt pan to be classified.
In the present embodiment, old halogen calcium removal efficiency is 80%, gypsum in the present embodiment（CaSO4·2H2O）Product purity is
98.2%。
Embodiment 2
By taking the old halogen of China Qinghai chloride type salt lake high calcium as an example, its old halogen composition is：Ca2+:4.05wt%, specific bag
Include following steps：
（1）Molten nitre：By saltcake and the undersaturated light bittern of sodium chloride-containing（The undersaturated light Brine salinity of sodium chloride-containing
22wt%）According to 1:1 mass ratio is mixed, and stirring is complete to dissolving under normal temperature condition, obtains saltcake mother liquor；Wherein saltcake purity
85%；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:1 converts halogen
Well mixed, the reaction time is 8h, obtains slurry；
（3）Filtering：By step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:3 through starching 40min stirring water again
Wash, then dry, 110 DEG C of drying temperature, drying time 3h obtains gypsum CaSO4·2H2O products, then wash and starch water return to step（1）
Recycled instead of the undersaturated light bittern dissolving saltcake of part sodium chloride-containing；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate, and does not influence original salt pan to be classified.
In the present embodiment, old halogen calcium removal efficiency is 85%, gypsum（CaSO4·2H2O）Product purity 98.5%.
Embodiment 3
By taking the old halogen of China Qinghai chloride type salt lake high calcium as an example, in its old halogen composition：Ca2+:6.76wt%, including with
Lower step：
（1）Molten nitre：By saltcake and water according to 1:8 mass ratio mixing, stirring is complete to dissolving under normal temperature condition, obtains awns
Nitre mother liquor；Wherein saltcake purity 90%；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:1.1 convert
Halogen is well mixed, and the reaction time is 6h, obtains slurry；
（3）Filtering, by step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:4 through starching 60min stirring water again
Wash, then dry, 120 DEG C of drying temperature, drying time 2h obtains CaSO4·2H2O products, then wash and starch water return to step（1）Instead of
Part aqueous solution saltcake is recycled；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate, and does not influence original salt pan to be classified.
In the present embodiment, old halogen calcium removal efficiency is 88%, gypsum（CaSO4·2H2O）Product purity 98.0%.
Embodiment 4
By taking the old halogen of China Qinghai chloride type salt lake high calcium as an example, in its old halogen composition：Ca2+:7.50wt%, including with
Lower step：
（1）Molten nitre：By saltcake and the undersaturated light bittern of sodium chloride（Wherein, Brine salinity 20wt%）According to 1:10
Mass ratio is mixed, and stirring is complete to dissolving under normal temperature condition, obtains saltcake mother liquor；Wherein saltcake purity 80%；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:1.2 convert
Halogen is well mixed, and the reaction time is 12h, obtains slurry；
（3）Filtering：By step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:5 through starching 30min stirring water again
Wash, then dry, 115 DEG C of drying temperature, drying time 1h obtains gypsum CaSO4·2H2O products, then wash and starch water return to step（1）
Recycled instead of the undersaturated light bittern dissolving saltcake of part sodium chloride-containing；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate, and does not influence original salt pan to be classified.
In the present embodiment, old halogen calcium removal efficiency is 82%, gypsum（CaSO4·2H2O）Product purity 99.1%.
Claims (6)
1. a kind of decalcification technique of the old halogen in high calcium salt pan, it is characterised in that comprise the following steps：
（1）Molten nitre：By saltcake and water or the undersaturated light bittern of sodium chloride-containing according to 1:0.5~10 mass ratio is in normal temperature condition
Lower mixed dissolution, obtains saltcake mother liquor；
（2）Convert halogen：By step（1）Gained saltcake mother liquor presses Ca with the old halogen in high calcium salt pan2+:SO4 2-Mol ratio is 1:1~1.2 converts halogen
Well mixed, the reaction time is 1~24h, obtains slurry；
Step（2）In, the old halogen in high calcium salt pan is the old halogen of calcic that chloride type salt lake is obtained after evaporation and concentration, its bittern
In composition, Ca2+≥4.0wt%；
（3）Filtering：By step（2）Gained slurry filtration is separated, and obtains calcium-containing material and the old halogen of deliming；
（4）Wash, dry：By step（3）Gained calcium-containing material is with water according to mass ratio 1:2~5 stir through starching 10~60 minutes again
Washing is mixed, is then dried, 105~120 DEG C of drying temperature, 1~4h of drying time obtains gypsum product, then wash and starch water return step
Suddenly（1）Recycled instead of the undersaturated light bittern dissolving saltcake of part water or sodium chloride；
（5）By step（3）The old halogen of gained deliming, which returns to sodium chloride salt pan, to be continued to evaporate.
2. the decalcification technique of the old halogen in high calcium salt pan according to claim 1, it is characterised in that step（1）In, the saltcake
Mass ratio with the undersaturated light bittern of water or sodium chloride-containing is 1：0.6~1.7.
3. the decalcification technique of the old halogen in high calcium salt pan according to claim 1 or 2, it is characterised in that step（1）In, it is described
Content >=80wt% of sal glauberi in saltcake.
4. the decalcification technique of the old halogen in high calcium salt pan according to claim 1 or 2, it is characterised in that step（1）In, it is described
The undersaturated light bittern Brine salinity≤25wt% of sodium chloride-containing.
5. the decalcification technique of the old halogen in high calcium salt pan according to claim 1 or 2, it is characterised in that step（2）In, it is described
Reaction time is 8~12h.
6. the decalcification technique of the old halogen in high calcium salt pan according to claim 1 or 2, it is characterised in that step（4）In, it is described
The time for starching stirring washing again is 25~35 minutes.
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| CN109354052B (en) * | 2018-12-05 | 2020-11-10 | 中国科学院青海盐湖研究所 | Comprehensive utilization method of industrial tail liquid obtained by extracting potassium from salt lake brine |
| CN113929119B (en) * | 2021-12-02 | 2023-06-20 | 青海省地质矿产测试应用中心(青海省生态环境地质检验检测中心) | Lithium extraction method of chloride type low-grade deep brine |
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| US3846081A (en) * | 1972-03-08 | 1974-11-05 | Ppg Industries Inc | Process for separating sodium sulfate from brines |
| CN102120591A (en) * | 2010-01-12 | 2011-07-13 | 文军锋 | Method for removing CaCl2 and MgCl2 from finished salt |
| CN103523801B (en) * | 2013-09-29 | 2015-09-30 | 中国地质科学院郑州矿产综合利用研究所 | Method for combined extraction of potassium, boron and lithium from chloride type potassium-containing underground brine |
| CN103880042B (en) * | 2014-04-14 | 2015-12-02 | 唐山三友化工股份有限公司 | The method of saltcake refined brine and preventing scaring |
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