CN105948084B - A kind of method that magnesium sulfate monohydrate is produced using copper tailing as raw material - Google Patents
A kind of method that magnesium sulfate monohydrate is produced using copper tailing as raw material Download PDFInfo
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- CN105948084B CN105948084B CN201610325212.6A CN201610325212A CN105948084B CN 105948084 B CN105948084 B CN 105948084B CN 201610325212 A CN201610325212 A CN 201610325212A CN 105948084 B CN105948084 B CN 105948084B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
Abstract
A kind of method that magnesium sulfate monohydrate is produced using copper tailing as raw material, is belonged to Making Use of Tailings and utilizes technical field.Copper tailing is mixed with the concentrated sulfuric acid, heated, products therefrom is soaked, separation of solid and liquid obtains immersion liquid containing magnesium and leached mud；H is added into immersion liquid containing magnesium2O2, add magnesium hydroxide adjust pH value to 3.3 ~ 3.5, be filtrated to get rich magnesium filtrate；Anhydrous magnesium sulfate is added into rich magnesium filtrate, stirring, stands, separate out crystal；Crystalline mother solution and aqueous magnesium sulfate are obtained through separation of solid and liquid, aqueous sulfuric acid magnesium crystal is dried and obtains magnesium sulfate monohydrate；Crystalline mother solution is returned in rich magnesium filtrate, promotes rich magnesium filtrate crystallization；Silicon, magnesium and iron are included in copper tailing, the wherein mass percent in copper tailing shared by magnesium is more than 17 %.A kind of method using copper tailing as raw material production magnesium sulfate monohydrate of the present invention can effectively improve the purity and yield of magnesium sulfate monohydrate, remove ferro element class impurity and simultaneously recycled, production cost is low, efficiency high, pollution-free.
Description
Technical field
The present invention relates to a kind of method that magnesium sulfate monohydrate is produced using copper tailing as raw material, belong to Making Use of Tailings and utilize skill
Art field.
Background technology
Copper tailing, also known as copper tailings, by ore through crushing, it is selected after the remaining fine powder grains of sand form.China is primary
Copper ore resource antipode lack, but copper tailing secondary resource amount is quite big.According to statistics, national copper tailing discharge is big between 2007
About 2,400,000,000, and year quantum of output is in increased trend year by year.The composition of copper tailing wherein copper content 0.3%, silver for 30 grams/it is per ton,
Zinc accounts for 0.35%, lead 0.6%, mineralogical composition mainly have calcite, plagioclase, diopside, hornblend, actinolite, garnet,
Chalcopyrite, quartz, chlorite, magnetic ore, magnetic iron ore etc., belong to aluminosilicate salt form mine tailing.
Applicant has found that existing copper tailing is dealt with improperly under study for action, can bring larger harm：Currently used tail
Ore deposit processing method is to establish Tailings Dam, and caused mine tailing is carried out into accumulation storage, and this processing mode easily produces many problems,
Land resource is not only occupied, also, after mine tailing is corroded by the external world, heavy metal element therein can be migrated to air and water and soil
In, serious environmental pollution is caused, in addition, Tailings Dam has the potential hazard of dam break.Goaf filling and as Building wood
Material etc. is also a kind of effective way for directly utilizing mine tailing.But this Land use systems waste substantial amounts of valuable element in mine tailing.
From the thinking of Developing Mining Recycling Economy, the higher value application of copper tailing is extremely urgent.Liu Sanjun etc. is to from copper tailing
Recovery barite is studied, and obtains the barite that barium sulfate grade is 91.68%.Technology of Anqing is from cupric 0.119%, iron content
Copper and iron resource have been reclaimed in 11% mine tailing.Mu Xiaohui is raw material using floatation desulphurization-weak magnetic separation iron-anti-using certain nominal group process
The sorting process of silicon drops in flotation, has obtained the iron ore concentrate of Iron grade 66.82% and the iron concentrate of sulfur grade 36.42%.Du Shuhua is opened
Having sent out valuable metal copper, sulphur, gold, silver, iron in copper tailing, the preferential separating technology joint new method of gradient, acquisition copper obtain successively
Copper, sulphur, iron concentrate grade are respectively 17.62%, 41.75% and 63.28%, and the rate of recovery is respectively 49.80%, 78.94% and
21.18%, wherein copper concentrate contains golden 24.49g/t, gold recovery 40.82%；Argentiferous 260.10g/t, the rate of recovery 22.77%, sulphur
Concentrate argentiferous 30g/t, silver raising recovery rate 21.92%, the accumulative rate of recovery 44.69% of silver.Applicant has found under study for action, prior art
Following defect in although be present：It is generally relatively low firstly for the recovery purity of metallic element, the rate of recovery in copper tailing, it is secondly, right
Element magnesium in copper tailing does not have preferable recovery method, such as using existing magnesium sulfate monohydrate extracting method recovery copper tailing
In magnesium, the purity of gained magnesium is low, the rate of recovery is low and the impurity containing more other elements.
The content of the invention
The technical problem to be solved in the present invention is：Overcome the deficiencies in the prior art, there is provided a kind of to be given birth to by raw material of copper tailing
The method for producing magnesium sulfate monohydrate, this method can effectively improve the purity and yield of magnesium sulfate monohydrate, remove ferro element class impurity simultaneously
Recycled, production cost is low, efficiency high, pollution-free.
The technical solution adopted for the present invention to solve the technical problems is：Magnesium sulfate monohydrate should be produced by raw material of copper tailing
Method, it is characterised in that comprise the following steps：
1）By copper tailing and the concentrated sulfuric acid in mass ratio 1 ~ 3:1 mixing, is heated to 100 ~ 250 DEG C, 1 ~ 3h of constant temperature；
2）By step 1）Products therefrom is soaked, and 60 ~ 80 DEG C of extraction temperature, 2 ~ 4h of extraction time, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；
3）Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, add magnesium hydroxide adjust solution ph to
3.3 ~ 3.5, filter off except insoluble matter, be filtrated to get rich magnesium filtrate；
4）At 5 ~ 25 DEG C of temperature, anhydrous magnesium sulfate is added into rich magnesium filtrate, stirring, standing promote rich magnesium filtrate precipitation to contain
Water magnesium sulfate crystal；
5）By step 4）Rich magnesium filtrate carries out separation of solid and liquid, crystalline mother solution and aqueous sulfuric acid magnesium crystal is obtained, by aqueous sulphur
Sour magnesium crystal, which is dried, obtains magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote rich magnesium filtrate crystallization；
Silicon, magnesium and iron are included in described copper tailing, the wherein mass percent in copper tailing shared by magnesium is more than 17 %.
Mass percent in described copper tailing used shared by magnesium is 20 ~ 30 %.
The mass percent concentration of the described concentrated sulfuric acid is 92% ~ 98%.
Step 1）Concrete operations be：According to copper tailing and the concentrated sulfuric acid in mass ratio 1:1, into copper tailing with 10ml/min
Speed add the concentrated sulfuric acid, be heated to 250 DEG C, heat time 3h.
Element manganese, step 3 are included in described copper tailing）With step 4）Between also include following operation：To step 3）It is rich
Potassium permanganate is added in magnesium filtrate bivalent manganese is oxidized to insoluble tetravalent manganese, filtered rich magnesium filtrate and remove insoluble tetravalence
Manganese.
Step 4）Described anhydrous magnesium sulfate addition is 1 ~ 2g.
Step 4）The concrete operations of described stirring are：Speed of agitator 10r/min, 1 ~ 2h of mixing time.
Step 5）The concrete operations of described drying are：By aqueous sulfuric acid magnesium crystal in 250 ~ 300 DEG C of dry 4 ~ 10h.
Step 5）The concrete operations of described drying are：By aqueous sulfuric acid magnesium crystal in 250 DEG C of dry 10h.
The % of mass percent 10 ~ 20 in described copper tailing shared by iron.
Applicant is described as follows for preparation method of the present invention：
Applicant has found that iron is that content is more in copper tailing, and the element of more difficult removing, and applicant exists under study for action
Step 3）In ferro element can effectively be recycled, thus define and silicon, magnesium and iron included in copper tailing.Applicant limits
The mass percent in copper tailing shared by magnesium is determined and has been more than 17 %, its effect is：When the content of magnesium in copper tailing is less than 17 %,
The cost recovery of magnesium sulfate monohydrate is too high, economically for be not quite reasonable, and content of magnesium is too low, one prepared
Water magnesium sulfate purity can decrease, and cause the reduction of its added value.Mass percent in preferable copper tailing shared by magnesium for 20 ~
30 %, the content are that a proper value of magnesium sulfate monohydrate is produced from copper tailing, and the content of magnesium is general not in copper tailing
Can be more than 30%.After the copper tailing of the % containing magnesium 20 ~ 30 is using the method extraction of the present invention, the yield of gained magnesium sulfate monohydrate is larger,
With higher economic benefit.Silicon, magnesium, iron exist in the form of its oxide in copper tailing, step 2）It is main in gained leached mud
It is silica to want composition, and construction material is used as after can reclaiming.
Applicant is in step 1）In the concentrated sulfuric acid used mass percent concentration be 92% ~ 98%.What the known concentrated sulfuric acid referred to
It is the sulfuric acid that mass percent concentration is more than 70%.But applicant has found under study for action, when being reacted with copper tailing：When the concentrated sulfuric acid is small
When 92%, can cause the leaching rate of magnesium reduces, so as to cause the rate of recovery of magnesium the harmful effect such as to decline；When the concentrated sulfuric acid is more than 98%
When, concentrated sulfuric acid raw material is difficult to obtain.Therefore, mass percent concentration is used to be reacted for 92% ~ 98% concentrated sulfuric acid with copper tailing, energy
Enough realized in terms of technology, economy and environmental benefit optimizes.
Applicant is in step 1）Middle copper tailing and the concentrated sulfuric acid in mass ratio 1 ~ 3:1 addition, the scope are according in copper tailing
The combined factors such as the content of magnesium and sulfuric acid concentration determine, when content of magnesium is in low value in the range of it, copper tailing and the concentrated sulfuric acid
Mass ratio can be high, on the contrary, content of magnesium in the range of it at a high value when, the mass ratio of copper tailing and the concentrated sulfuric acid can be with low
Some, because：（1）In the reasonable scope, the magnesium in copper tailing both can have at utmost been leached, the concentrated sulfuric acid will not be caused again
Waste.（2）Concentrated sulfuric acid amount is excessive, easily leaches other impurity compositions in copper tailing, and can increase follow-up leachate
Clean difficulty, influences the quality of magnesium sulfate monohydrate.
Applicant is in step 1）In " concentrated sulfuric acid is added with 10ml/min speed into copper tailing, is heated to 100 ~ 250
DEG C, 1 ~ 3h " of constant temperature.It is due to that temperature is to influence an important parameter of chemical reaction, the slaking reaction is the endothermic reaction,
Heating is advantageous to reaction and carried out to positive direction, the magnesium in copper tailing is at utmost converted into magnesium sulfate, but the too high appearance of temperature
The volatilization of sulfuric acid is easily caused, reduces the concentration that sulfuric acid participates in reaction indirectly, the conversion ratio of magnesium can be reduced, and temperature is too high to increase
Add energy consumption.On the contrary, the too low speed that can reduce reaction of temperature, causes the production cycle elongated.
Applicant is in step 2）Middle 60 ~ 80 DEG C of extraction temperature of design, 2 ~ 4h's of extraction time.Extraction temperature reaction speed is normal
Number has exponent relation with temperature, properly increases extraction temperature and is advantageous to raising leaching velocity and leaching rate, molten due to magnesium sulfate
Xie Du can be raised in the range of 30-80 DEG C as temperature raises, and continue to raise temperature, and the solubility of magnesium sulfate can reduce, because
This scope is suitable temperature range.Leaching rate improves as extraction time extends, but peak value, the long meeting of extraction time
Reduce the disposal ability and increase production cost of equipment.
Applicant is in step 3）Middle design adds magnesium hydroxide and adjusts solution ph to 3.3-3.5, is adjusted in the system
PH value can ensure that iron farthest precipitates removing to 3.3-3.5, and it is not thorough that excessive or too small pH value can cause iron to remove
Or magnesium precipitate, the loss of magnesium is caused, can avoid introducing other impurity using magnesium hydroxide regulation pH.
Step 3）Effect be by adding H into filtrate containing magnesium2O2, by it is ferrous oxidising be ferric iron, add hydrogen-oxygen
Change magnesium and adjust solution ph to 3.3 ~ 3.5, iron is with Fe (OH)3The filtered removal of precipitation form.When containing manganese element in copper tailing
When, applicant is designed in step 3）With step 4）Between also include following operation：To step 3）Permanganic acid is added in rich magnesium filtrate
Bivalent manganese is oxidized to insoluble tetravalent manganese by potassium, is filtered rich magnesium filtrate and is removed insoluble tetravalent manganese, is gone using above method
Except harmful effect of the manganese element to magnesium sulfate monohydrate purity.Step 3）Middle H2O2Water and oxygen can be converted into after being excessively added, will not
In the solution, the addition of potassium permanganate can be determined residual by manganese content in the copper tailing of measure.
Step 4）It is middle that the higher aqueous sulfuric acid magnesium crystal of purity is obtained by the way of crystallization.Due to obtained rich magnesium net liquid
Close to saturation, it is all that 1 ~ 2g of addition can promote its crystallization to add anhydrous magnesium sulfate, and applicant adds 1 ~ 2g anhydrous magnesium sulfates
Reason：Be due to that anhydrous magnesium sulfate has the characteristic that easily absorbs water, become aqueous magnesium sulfate after adding, so have two it is good
Place：（1）Water a small amount of in filtrate can be absorbed, the effect for improving magnesium sulfate concentration is served indirectly, avoids the heating of filtrate
Operation is concentrated, energy consumption is reduced, has saved cost.（2）The aqueous magnesium sulfate of formation serves the effect of crystal seed, adds sulfuric acid
The rate of recovery of magnesium.
Step 5）It is middle that crystalline mother solution is added into step 4 again）Rich magnesium filtrate in, promote rich magnesium filtrate crystallization；Wherein tie
Brilliant mother liquor can be recycled and reused for step 4）Devitrification step, even if containing other elements impurity in crystalline mother solution, still can lead to
The mode for crossing crystallization obtains the aqueous magnesium sulfate of high-purity.Precious metal gold, silver are not contained in copper tailing used in the present invention, can
A small amount of copper can be contained, in step 3）Can go out copper strips when precipitating iron removaling a part, while in step 4）Crystallization
Either the concentration of temperature or copper does not all reach the standard of precipitation during precipitation, and copper sulphate separates out and generally requires evaporation crystallisation by cooling
Method, the purity of magnesium sulfate monohydrate will not be had an impact.
Compared with prior art, possessed by a kind of method using copper tailing as raw material production magnesium sulfate monohydrate of the invention
Beneficial effect is：
1st, the purity and receipts of magnesium sulfate monohydrate can be effectively improved by being somebody's turn to do the method using copper tailing as raw material production magnesium sulfate monohydrate
Rate, remove ferro element class impurity and recycled, production cost is low, efficiency high, pollution-free.
2nd, should be that the method method of raw material production magnesium sulfate monohydrate can effectively remove manganese element class impurity and go forward side by side using copper tailing
Row recycles, and further improves the purity of magnesium sulfate monohydrate,
3rd, the method abundant raw material of magnesium sulfate monohydrate should be produced using copper tailing as raw material, no acid mist produces, technique, equipment letter
Single, reaction condition is easily controllable, and obtained filter residue can be as the raw material of construction material, and iron, the manganese of recovery are recycling, crystallization
Mother liquor can recycle.
Brief description of the drawings
Fig. 1 is the process chart that magnesium sulfate monohydrate is produced by raw material of copper tailing.
Embodiment
Embodiment 1 ~ 5 is a kind of specific embodiment party of method that magnesium sulfate monohydrate is produced using copper tailing as raw material of the present invention
Formula, wherein embodiment 1 are most preferred embodiment.Step 1 in embodiment）Firing equipment used is Muffle furnace, step 2）With step 5）
Solid-liquid separating equipment used is with vacuum filtration machine.
Embodiment 1
The composition of following mass percent is included in copper tailing used in the present embodiment：The % of magnesium 30, silicon 30%, iron 12%, manganese
0.74%。
1）Slaking reaction：500g copper tailings are added in reactor, then add 98% with 10ml/min speed
The concentrated sulfuric acid, control copper tailing and the concentrated sulfuric acid in mass ratio 1：1 mixing, is heated to 250 DEG C, constant temperature 3h；
2）Water logging：By step 1）Products therefrom is soaked, and 80 DEG C of extraction temperature, extraction time 2h, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；Leached mud is used as construction material；
3）Removal of impurities：Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, by it is ferrous oxidising be ferric iron,
Add magnesium hydroxide and adjust solution ph to 3.5, iron is with Fe (OH)3Form form insoluble matter, filter off except insoluble matter, filtering
Obtain rich magnesium filtrate；To step 3）Potassium permanganate is added in rich magnesium filtrate bivalent manganese is oxidized to insoluble tetravalent manganese, filtered
Rich magnesium filtrate removes insoluble tetravalent manganese；
4）Crystallization：At 20 DEG C of temperature, 1g anhydrous magnesium sulfates, speed of agitator 10r/min, during stirring are added into rich magnesium filtrate
Between 2h, stand and promote rich magnesium filtrate to separate out aqueous sulfuric acid magnesium crystal；
5）Dry：By step 4）Rich magnesium filtrate carries out separation of solid and liquid, obtains crystalline mother solution and aqueous sulfuric acid magnesium crystal, will contain
Water magnesium sulfate crystal is in 250 DEG C of dry 10h, acquisition magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote
Enter rich magnesium filtrate crystallization.
Embodiment 2
The composition of following mass percent is included in copper tailing used in the present embodiment：The % of magnesium 25, silicon 35%, iron 13%, manganese
0.70%。
1）Slaking reaction：500g copper tailings are added in reactor, then add 95% with 10ml/min speed
The concentrated sulfuric acid, control copper tailing and the concentrated sulfuric acid in mass ratio 2:1 mixing, is heated to 200 DEG C, constant temperature 2h；
2）Water logging：By step 1）Products therefrom is soaked, and 70 DEG C of extraction temperature, extraction time 3h, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；Leached mud is used as construction material；
3）Removal of impurities：Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, by it is ferrous oxidising be ferric iron,
Add magnesium hydroxide and adjust solution ph to 3.5, iron is with Fe (OH)3Form form insoluble matter, filter off except insoluble matter, filtering
Obtain rich magnesium filtrate；To step 3）Potassium permanganate is added in rich magnesium filtrate bivalent manganese is oxidized to insoluble tetravalent manganese, filtered
Rich magnesium filtrate removes insoluble tetravalent manganese；
4）Crystallization：At 18 DEG C of temperature, 1.5g anhydrous magnesium sulfates, speed of agitator 10r/min, stirring are added into rich magnesium filtrate
Time 1.5h, stand the rich magnesium filtrate precipitation aqueous sulfuric acid magnesium crystal of promotion；
5）Dry：By step 4）Rich magnesium filtrate carries out separation of solid and liquid, obtains crystalline mother solution and aqueous sulfuric acid magnesium crystal, will contain
Water magnesium sulfate crystal is in 280 DEG C of dry 7h, acquisition magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote
Enter rich magnesium filtrate crystallization.
Embodiment 3
The composition of following mass percent is included in copper tailing used in the present embodiment：The % of magnesium 20, silicon 35%, iron 14%, manganese
0.65%。
1）Slaking reaction：500g copper tailings are added in reactor, then add 93% with 10ml/min speed
The concentrated sulfuric acid, control copper tailing and the concentrated sulfuric acid in mass ratio 3:1 mixing, is heated to 150 DEG C, constant temperature 2.5h；
2）Water logging：By step 1）Products therefrom is soaked, and 60 DEG C of extraction temperature, extraction time 4h, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；Leached mud is used as construction material；
3）Removal of impurities：Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, by it is ferrous oxidising be ferric iron,
Add magnesium hydroxide and adjust solution ph to 3.4, iron is with Fe (OH)3Form form insoluble matter, filter off except insoluble matter, filtering
Obtain rich magnesium filtrate；To step 3）Potassium permanganate is added in rich magnesium filtrate bivalent manganese is oxidized to insoluble tetravalent manganese, filtered
Rich magnesium filtrate removes insoluble tetravalent manganese；
4）Crystallization：Under the conditions of 15 DEG C of temperature, 2g anhydrous magnesium sulfates are added into rich magnesium filtrate, speed of agitator 10r/min, are stirred
Mix time 1h, stand the rich magnesium filtrate precipitation aqueous sulfuric acid magnesium crystal of promotion；
5）Dry：By step 4）Rich magnesium filtrate carries out separation of solid and liquid, obtains crystalline mother solution and aqueous sulfuric acid magnesium crystal, will contain
Water magnesium sulfate crystal is in 300 DEG C of dry 5h, acquisition magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote
Enter rich magnesium filtrate crystallization.
Embodiment 4
The composition of following mass percent is included in copper tailing used in the present embodiment：The % of magnesium 30, silicon 30%, iron 18%, is free of
Manganese.
1）Slaking reaction：500g copper tailings are added in reactor, then add 92% with 15ml/min speed
The concentrated sulfuric acid, control copper tailing and the concentrated sulfuric acid in mass ratio 1.5:1 mixing, is heated to 100 DEG C, constant temperature 3h；
2）Water logging：By step 1）Products therefrom is soaked, and 60 DEG C of extraction temperature, extraction time 3h, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；Leached mud is used as construction material；
3）Removal of impurities：Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, by it is ferrous oxidising be ferric iron,
Add magnesium hydroxide and adjust solution ph to 3.4, iron is with Fe (OH)3Form form insoluble matter, filter off except insoluble matter, filtering
Obtain rich magnesium filtrate；
4）Crystallization：At 15 DEG C of temperature, 1g anhydrous magnesium sulfates, speed of agitator 10r/min, during stirring are added into rich magnesium filtrate
Between 1h, stand and promote rich magnesium filtrate to separate out aqueous sulfuric acid magnesium crystal；
5）Dry：By step 4）Rich magnesium filtrate carries out separation of solid and liquid, obtains crystalline mother solution and aqueous sulfuric acid magnesium crystal, will contain
Water magnesium sulfate crystal is in 250 DEG C of dry 4h, acquisition magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote
Enter rich magnesium filtrate crystallization.
Embodiment 5
The composition of following mass percent is included in copper tailing used in the present embodiment：Magnesium 20%, silicon 30%, iron 20%, manganese 1%.
1）Slaking reaction：500g copper tailings are added in reactor, then add 98% with 10ml/min speed
The concentrated sulfuric acid, control copper tailing and the concentrated sulfuric acid in mass ratio 1:1 mixing, is heated to 200 DEG C, constant temperature 1h；
2）Water logging：By step 1）Products therefrom is soaked, and 60 DEG C of extraction temperature, extraction time 2h, is obtained through separation of solid and liquid
Magnesium immersion liquid and leached mud must be contained；
3）Removal of impurities：Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, by it is ferrous oxidising be ferric iron,
Add magnesium hydroxide and adjust solution ph to 3.3, iron is with Fe (OH)3Form form insoluble matter, filter off except insoluble matter, filtering
Obtain rich magnesium filtrate；To step 3）Potassium permanganate is added in rich magnesium filtrate bivalent manganese is oxidized to insoluble tetravalent manganese, filtered
Rich magnesium filtrate removes insoluble tetravalent manganese；
4）Crystallization：At 17 DEG C of temperature, 1g anhydrous magnesium sulfates, speed of agitator 10r/min, during stirring are added into rich magnesium filtrate
Between 1.5h, stand and promote rich magnesium filtrate to separate out aqueous sulfuric acid magnesium crystal；
5）Dry：By step 4）Rich magnesium filtrate carries out separation of solid and liquid, obtains crystalline mother solution and aqueous sulfuric acid magnesium crystal, will contain
Water magnesium sulfate crystal is in 300 DEG C of dry 4h, acquisition magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote
Enter rich magnesium filtrate crystallization.
Performance test
Detect the purity and the rate of recovery of the gained magnesium sulfate monohydrate of embodiment 1 ~ 5, and typing table 1.
The purity and the rate of recovery of the gained magnesium sulfate monohydrate of 1 embodiment of table 1 ~ 5
。
The product of the reaction gained of embodiment 1 ~ 5 is step 2）Gained leached mud, step 3）Gained Fe (OH)3, step 3）Institute
Obtain insoluble tetravalent manganese, step 5）The composition of mass percent more than 98% is two in gained magnesium sulfate monohydrate, wherein leached mud
Silica, it can serve as construction material, wherein Fe (OH)3, insoluble tetravalent manganese can be with recycling, magnesium sulfate monohydrate is institute
Obtain product.And it can be seen that by table 1, the purity and yield of the gained magnesium sulfate monohydrate of embodiment 1 ~ 5 can reach high value.Shen
Ask someone to make discovery from observation, embodiment 1 ~ 5 generates without acid mist or irritative gas in operation, and arranges without waste liquid
Put, environmental protection and economy.
The above described is only a preferred embodiment of the present invention, being not the limitation for making other forms to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (8)
- A kind of 1. method that magnesium sulfate monohydrate is produced using copper tailing as raw material, it is characterised in that comprise the following steps：1）By copper tailing and the concentrated sulfuric acid in mass ratio 1 ~ 3:1 mixing, is heated to 100 ~ 250 DEG C, 1 ~ 3h of constant temperature；2）By step 1）Products therefrom is soaked in water, and 60 ~ 80 DEG C of extraction temperature, 2 ~ 4h of extraction time, is contained through separation of solid and liquid Magnesium immersion liquid and leached mud；3）Under the conditions of 5 ~ 30 DEG C of temperature, H is added into immersion liquid containing magnesium2O2Stir evenly, addition magnesium hydroxide regulation solution ph to 3.3 ~ 3.5, filter off except insoluble matter, be filtrated to get rich magnesium filtrate；4）At 5 ~ 25 DEG C of temperature, anhydrous magnesium sulfate is added into rich magnesium filtrate, stirring, stands the aqueous sulphur of the rich magnesium filtrate precipitation of promotion Sour magnesium crystal；5）By step 4）Rich magnesium filtrate carries out separation of solid and liquid, crystalline mother solution and aqueous sulfuric acid magnesium crystal is obtained, by aqueous magnesium sulfate Crystal, which is dried, obtains magnesium sulfate monohydrate；Crystalline mother solution is added into step 4）Rich magnesium filtrate in, promote rich magnesium filtrate crystallization；Silicon, magnesium and iron are included in described copper tailing, the wherein mass percent in copper tailing shared by magnesium is more than 17 %；The mass percent concentration of the described concentrated sulfuric acid is 92% ~ 98%；Step 5）The concrete operations of described drying are：By aqueous sulfuric acid magnesium crystal in 250 ~ 300 DEG C of dry 4 ~ 10h.
- A kind of 2. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Institute Mass percent in the copper tailing used stated shared by magnesium is 20 ~ 30 %.
- A kind of 3. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Step Rapid 1）Concrete operations be：According to copper tailing and the concentrated sulfuric acid in mass ratio 1:1, added into copper tailing with 10ml/min speed The concentrated sulfuric acid, 250 DEG C are heated to, heat time 3h.
- A kind of 4. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Institute Element manganese, step 3 are included in the copper tailing stated）With step 4）Between also include following operation：To step 3）Add in rich magnesium filtrate Enter potassium permanganate and bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese.
- A kind of 5. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Step Rapid 4）Described anhydrous magnesium sulfate addition is 1 ~ 2g.
- A kind of 6. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Step Rapid 4）The concrete operations of described stirring are：Speed of agitator 10r/min, 1 ~ 2h of mixing time.
- A kind of 7. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Step Rapid 5）The concrete operations of described drying are：By aqueous sulfuric acid magnesium crystal in 250 DEG C of dry 10h.
- A kind of 8. method that magnesium sulfate monohydrate is produced using copper tailing as raw material according to claim 1, it is characterised in that：Institute The % of mass percent 10 ~ 20 in the copper tailing stated shared by iron.
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| CN110790290A (en) * | 2019-12-18 | 2020-02-14 | 河南省睿博环境工程技术有限公司 | Method for producing high-purity magnesium sulfate from magnesium-method desulfurization waste residues |
| CN111135773A (en) * | 2020-01-03 | 2020-05-12 | 河北佰斯特药业有限公司 | Method for removing iron and manganese in raw material medicine magnesium sulfate |
| CN115432789A (en) * | 2022-08-31 | 2022-12-06 | 中国矿业大学 | Method for preparing ferrous sulfate flocculating agent from copper smelting tailing slag |
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| CN104556158B (en) * | 2014-12-25 | 2017-09-26 | 昆明钢铁集团有限责任公司 | A kind of method for preparing calcium sulfate crystal whiskers and magnesium sulfate |
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