CN102745726B - Method for producing magnesium sulfate heptahydrate by using desulfurization wastewater - Google Patents
Method for producing magnesium sulfate heptahydrate by using desulfurization wastewater Download PDFInfo
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Abstract
The present invention discloses a method for producing magnesium sulfate heptahydrate by using desulfurization wastewater. The method comprises the following steps: (1) pulping, (2) carrying out desulfurization, (3) discharging the pulp, (4) filtering, (5) carrying out concentration, and (6) carrying out crystallization. With the method of the present invention, high value byproducts can be synchronously produced during a flue gas desulfurization process by using a magnesium oxide method. In addition, with the method of the present invention, a stable running characteristic is provided, and quality of the produced magnesium sulfate heptahydrate after desulfurization reaches standards.
Description
Technical field
The present invention relates to utilize desulfurization waste liquor to produce the method for magnesium sulfate, especially utilize desulfurization waste liquor to produce the method for magnesium sulfate heptahydrate.
Background technology
Since 2005, in flue gas sulphur process, magnesium oxide method desulfurization technology obtains the extensive approval of iron and steel and electricity power enterprise, the advantage of this and magnesium oxide method desulfurization technology is inseparable, and everybody generally believes the features such as magnesium oxide method has desulfuration efficiency high (can reach more than 90%), initial cost is few, operation maintenance cost is low.In the area that has magnesium ore resources, it is a kind of competitive desulfurization technology.Current most enterprise adopts magnesium oxide to carry out flue gas desulfurization, and the treatment process of magnesium sulfate that desulfurization produces, magnesium sulfite waste liquid is mainly divided into method of reproduction, abandons three kinds of method, absorption methods etc.And adopt the enterprise of the method for abandoning in the majority, and the processing mode one of this desulfurization waste liquor is to cause a large amount of water resource waste, the 2nd, and environment is around produced and pollute, the 3rd, solid matter forms secondary pollution.
China in recent years on magnesium oxide desulfurizer, generally adopt a kind of double decomposition technique to reclaim magnesium compound and sulphur, it is recycled in sweetening process, as CN1775681A describes, its method is: first, to desulfurization waste liquor forced aeration, make magnesium sulfite, then enter roast in fluidizing furnace and resolve into sulfurous gas and magnesium oxide, sulphur is sold and is used as Industrial products, and magnesium oxide enters desulphurization system and recycles.But this technique has been inherited the part shortcoming of calcium oxide desulfurizer significantly, as a large amount of consumption magnesium oxide, byproduct remains sulfuric acid and the magnesium oxide product of low value, and magnesium oxide is as just a kind of carrier of desulfurization.A prior problem is that the magnesium sulfate particle that double decomposition process generates is relatively difficult to separate with magnesium hydroxide, and actually operating is very difficult.
Also have part technique to adopt after desulfurization to carry out recovery by the technique of forced oxidation, two effects or triple effect evaporation crystallization and make magnesium sulfate or other magnesium compound, as CN1544331A describes, its method is: by desulfurization waste liquor forced oxidation, add in magnesium oxide slurry and waste liquid in sulfuric acid, then make magnesium compound by evaporative crystallization.But such technique need to add magnesium oxide slurry neutralisation of sulphuric acid magnesium and sulfuric acid mixture liquid by rear end; the existing technique of result that the each composition of N-process reacts cannot be done accurate control; cause produced byproduct cannot guarantee that purity and content are consistent all the time, large-scale production is restricted.And evaporative crystallization technique itself consumes ample resources, cost is higher.Very easily in pipeline, form particulate matter from running condition evaporation and crystal process in addition and stop up, complicated operation, operation expense is higher.Forced oxidation process need operates by aerating system in addition, can not guarantee that effective ingredient in slurry transforms magnesium sulfate and the magnesium sulfite mixed solution of generation 90% above concentration under the impact of the factors such as aeration time, oxygen supply are how many, temperature height.From actual items effect, after operation for some time, still recurrence is processed desulfurizing byproduct by the method for abandoning mostly at present.
Summary of the invention
In order to overcome the defect of prior art, present inventor has carried out further investigation repeatedly, thereby completes the present invention.The object of the present invention is to provide a kind of desulfurization waste liquor that utilizes to produce the method for magnesium sulfate heptahydrate, it is utilizing magnesium oxide method to carry out in flue gas desulfurization course, synchronous production high value byproduct.The present invention also aims to provide a kind of method of utilizing desulfurization waste liquor to produce magnesium sulfate heptahydrate, the magnesium sulfate heptahydrate requisite quality generating after its stable and desulfurization.
According to a specific embodiment of the present invention, a kind of method of utilizing desulfurization waste liquor to produce magnesium sulfate heptahydrate, it comprises the steps:
(1) slurrying step: the sweetening agent that comprises magnesium oxide and oxygenant is added water and makes hydrogeneous magnesian slurry, and described oxygenant is the oxygenant that tetravalence sulphur can be oxidized to sexavalence sulphur;
(2) desulfurized step: in desulfurizer, the flue gas that comprises sulfurous gas is contacted with hydrogeneous magnesian slurry, to remove the sulfurous gas in flue gas, and carry out oxidizing reaction;
(3) plasma discharge step: in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the slurry forming after desulfurization is discharged;
(4) filtration step: the slurries filtration that step (3) is discharged, obtains the not liquid containing solid impurity;
(5) enrichment step: step (4) gained liquid is sent into vaporizer, slurry is discharged after concentrated, vaporization temperature is that 100～125 ℃ and dump temperature are 100～125 ℃;
(6) crystallisation step: the slurry that step (5) is discharged carries out crystallisation by cooling, and temperature is 30～45 ℃, generates magnesium sulfate heptahydrate.
According to another embodiment of the present invention, a kind of method of utilizing desulfurization waste liquor to produce magnesium sulfate heptahydrate, it comprises the steps:
(1 ') slurrying step: the sweetening agent that comprises magnesium oxide and oxygenant is added water and makes hydrogeneous magnesian slurry, and described oxygenant is the oxygenant that tetravalence sulphur can be oxidized to sexavalence sulphur;
(2 ') desulfurized step: in desulfurizer, the flue gas that comprises sulfurous gas is contacted with hydrogeneous magnesian slurry, to remove the sulfurous gas in flue gas, and carry out oxidizing reaction;
(3 ') plasma discharge step: in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the slurry forming after desulfurization is discharged;
(4 ') enrichment step: the slurry that step (3 ') is discharged is sent into vaporizer, discharges slurry after concentrated, and vaporization temperature is that 100～125 ℃ and dump temperature are 100～125 ℃;
(5 ') crystallisation step: the slurry that step (4 ') is discharged carries out crystallisation by cooling, and temperature is 30～45 ℃, generates magnesium sulfate heptahydrate.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the magnesium sulfate content in the slurry forming after desulfurization is more than 90wt%, in the total mass of the magnesium sulfate in slurry and magnesium sulfite.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, vaporization temperature is that 110～120 ℃ and dump temperature are 110～120 ℃.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, described oxygenant comprises MnO
2, KMnO
4or the combination of the two.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
MgO 70～90 weight parts,
CaO 0.1～1 weight part,
SiO
23～10 weight parts,
Fe
2o
30.1～0.4 weight part,
Al
2o
30.1～0.5 weight part,
MnO
25～10 weight parts;
Wherein, the active oxidation Mg content in MgO is 50～75wt%.
According to method of the present invention, preferably, sweetening agent also comprises KMnO
43～8 weight parts, take sweetening agent gross weight as 100 weight parts.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
MgO 80～90 weight parts,
CaO 0.1～0.5 weight part,
SiO
23～8.5 weight parts,
Fe
2o
30.1～0.2 weight part,
Al
2o
30.1～0.2 weight part,
MnO
28.1～10 weight parts;
Wherein, the active oxidation Mg content in MgO is 62～75wt%.
According to method of the present invention, preferably, sweetening agent also comprises KMnO
45～8 weight parts, take sweetening agent gross weight as 100 weight parts.
Method according to the present invention described in above-mentioned two kinds of embodiments, preferably, described crystallisation step carries out in the adjustable crystallisation by cooling groove of temperature.
The method of the application of the invention, can realize utilize magnesium oxide method carry out flue gas desulfurization course in synchronous production high value byproduct.
In addition, by the preferred method of the present invention, the magnesium sulfate heptahydrate requisite quality generating after its stable and desulfurization.
Have, produce magnesium sulfate heptahydrate purity can reach more than 98% by the preferred method of the present invention, heavy metal content and other composition all reach national respective quality standard, and output and quality are all better than other processing method.
Embodiment
In the present invention, utilize sweetening agent to react the sulfurous gas in flue gas is removed with the sulfurous gas in flue gas, meanwhile, in the slurry forming after desulfurization, generate magnesium sulfate.
Because sweetening agent is generally Powdered, therefore, first the present invention carries out slurrying step: sweetening agent is added water and makes hydrogeneous magnesian slurry.Sweetening agent of the present invention comprises magnesium oxide and oxygenant, and oxygenant wherein can be oxidized to tetravalence sulphur sexavalence sulphur.In the present invention, magnesium oxide can react to form magnesium sulfite with the sulfurous gas in flue gas; When sulfurous gas reacts formation sulfurous acid with water, magnesium oxide can react to form with sulfurous acid magnesium sulfite; In the time that sulfurous gas, sulfurous acid are oxidized to sulphur trioxide, sulfuric acid, magnesium oxide can also form magnesium sulfate with sulphur trioxide, sulfuric acid reaction.In the present invention, oxygenant can be oxidized to tetravalence sulphur sexavalence sulphur.For example, be sulphur trioxide by the oxidizing sulfur dioxide in flue gas, the sulfurous acid in slurry is oxidized to sulfuric acid, and/or the magnesium sulfite in slurry is oxidized to magnesium sulfate.
In the present invention, described oxygenant is preferably strong oxidizer, can enhance productivity like this.For example, described oxygenant comprises MnO
2, KMnO
4or the combination of the two.
In the present invention, in order to improve the quality of magnesium sulfate, preferred sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
MgO 70～90 weight parts, CaO 0.1～1 weight part, SiO
23～10 weight parts, Fe
2o
30.1～0.4 weight part, Al
2o
30.1～0.5 weight part, MnO
25～10 weight parts; Wherein, the active oxidation Mg content in MgO is 50～75wt%; Optionally, also comprise KMnO
43～8 weight parts.
In the present invention, in order further to improve the quality of magnesium sulfate, preferred sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts::
MgO 80～90 weight parts, CaO 0.1～0.5 weight part, SiO
23～8.5 weight parts, Fe
2o
30.1～0.2 weight part, Al
2o
30.1～0.2 weight part, MnO
28.1～10 weight parts; Wherein, the active oxidation Mg content in MgO is 62～75wt%.Optionally, also comprise KMnO
45～8 weight parts.
In desulfurized step of the present invention, in desulfurizer, the flue gas that comprises sulfurous gas is contacted with hydrogeneous magnesian slurry, to remove the sulfurous gas in flue gas, and carry out oxidizing reaction.The mode of contact can be the mode of hydrogeneous magnesian slurry spray, or the flue gas that comprises sulfurous gas is passed into the mode in hydrogeneous magnesian slurry.Be preferably the mode of hydrogeneous magnesian slurry spray.The not special restriction of desulfurizer of the present invention, is preferably thionizer.In flue gas and hydrogeneous magnesian slurry contact process, under the magnesium hydroxide in the sulfurous gas in flue gas and hydrogeneous magnesian slurry and the synergy of oxygenant, react, thereby obtain the slurry that magnesium sulfate content is high.
Present inventor is surprised to find, and between the magnesium sulfate content in slurry and pH, has close contacting.When the pH of slurry is during at certain specified range, the magnesium sulfate content in slurry is higher.In plasma discharge step of the present invention, in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the slurry forming after desulfurization is discharged.Now, the magnesium sulfate content in the slurry forming after desulfurization is more than 90wt%, take the total mass percentage ratio of magnesium sulfate and magnesium sulfite as 100wt%.Therefore, the control of pH value key very.If pH is lower than 6.5, in slurry, the content of magnesium sulfate is not high; If pH is higher than 7.5, the by product in slurry is more, also can affect the content of magnesium sulfate.Take the total mass percentage ratio of magnesium sulfate and magnesium sulfite as 100wt%, preferably, the magnesium sulfate content in the slurry forming after desulfurization is more than 92wt%, more preferably more than 95wt%, most preferably more than 98wt%.
In addition, the present invention optionally comprises the following steps: will be expelled in a container and carry out aeration at the reacted slurry of desulfurizer.Particularly, will after abundant reacted slurry discharge, leave in waste liquid pool aeration in waste liquid pool with flue gas in thionizer bottom.Owing to containing a large amount of oxygen in air, magnesium sulfite residual in slurry can be further converted to magnesium sulfate like this.
In the present invention, optionally comprise filtration step: by the slurries filtration forming after desulfurization, obtain the not liquid containing solid impurity.In order to make gained magnesium sulfate purity higher, preferably include filtration step.The device filtering is not particularly limited, and is preferably vacuum filter, and its filtration efficiency is high.The fineness of filtering is preferably more than and equals 20 microns.If reacted slurry does not carry out aeration, it is directly sent in vacuum filter and removes impurity, obtain the not liquid containing solid impurity.Carry out aeration if reacted slurry is delivered to waste liquid pool, the solution after aeration is sent in vacuum filter and removed impurity, obtain the not liquid containing solid impurity.
In the present invention, do not filter or filter after liquid need to concentrate.For example, these liquid are sent in vaporizer.In order to prepare magnesium sulfate heptahydrate, need to control the problem of vaporizer.For example, be 100～130 ℃ by vaporization temperature control, be preferably 110～120 ℃, more preferably 115～118 ℃; Be 100～130 ℃ by dump temperature control, be preferably 110～120 ℃, more preferably 115～118 ℃.The kind of vaporizer of the present invention is not particularly limited.In order to improve concentrated effect, preferably use triple-effect evaporator.The use step of triple-effect evaporator can, with reference to CN101549210A, be incorporated herein by reference in its entirety.Triple-effect evaporator is known in the art, is commonly used to condensing crystal.The present invention adopts triple-effect evaporator to be used for concentrating slurry, and avoids crystallization in this process as far as possible.
In the present invention, the slurry after concentrated is carried out to crystallisation by cooling, temperature is 30～45 ℃, generates magnesium sulfate heptahydrate.For example, the slurry after concentrated is directly sent into and in cooling tank, carried out crystallisation by cooling.Cooling tank is preferably the cooling tank of temperature-adjustable.In cooling tank, temperature is preferably constant in 30～45 ℃.In the present invention, the slurry after concentrating carries out crystallisation by cooling and has formed wet magnesium sulfate heptahydrate and mother liquor, and wet magnesium sulfate heptahydrate send drying machine dry, and mother liquor returns in aeration tank and recycles.Like this, method of the present invention will not have discharge of wastewater, more environmental protection.
In the present invention, optionally also comprise dry packing step.The wet magnesium sulfate heptahydrate of above-mentioned steps is dried.Drying temperature can 50～100 ℃, in order to control quality product, are preferably 80～90 ℃.The dry equipment involving vibrations vulcanization bed drying machine adopting.Finished product is after drying sent into the packing shop moulding of directly packing by conveying belt.
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The basic parameter following table of embodiment 1～8.
Table 1, basic technology parameter
| Sequence number | Parameter | Unit | Numerical value |
| 1 | Desulfurizer inlet flue gas amount (work | m 3/h | 960000 |
| 2 | Desulfurizer inlet flue gas amount (mark condition | Nm 3/h | 619574 |
| 3 | Design coal-fired sulfur | ％ | 1 |
| 4 | Desulfurizer inlet flue gas temperature | ℃ | 150 |
| 6 | Design desulfurization degree | ％ | ≥98％ |
| 7 | Magnesium sulphur ratio | Mg/S | 1 |
embodiment 1
(1) modulation of sweetening agent:
According to following formula, each component is mixed, obtain sweetening agent.
(2) utilize desulfurization waste liquor to produce the technique of magnesium sulfate
1, slurrying:
The desulfurizer powder modulating is added water, and to form main component after slurrying, slaking be hydrogeneous magnesian slurry (being called for short hydrogeneous magnesian slurry), and stay in slurry tank for subsequent use.
2, desulfurization and oxidation:
Sulfurous gas in flue gas in thionizer with hydrogeneous magnesian slurry reaction, remove the SO in flue gas
2.
In thionizer, in hydrogeneous magnesian slurry, contain strong oxidizer MnO
2, make slurry in tower, at desulphurization reaction, moment generates 95wt% magnesium sulfate and 5wt% magnesium sulfite solution by desulfurization slurry occur, the above-mentioned per-cent all weight percent sum based on magnesium sulfate and magnesium sulfite is 100wt% meter.
3, plasma discharge material:
Thionizer inner bottom part, with the abundant reacted slurry of flue gas, in the time that pH value reaches 7.0, starts to discharge desulfurization slurry, leaves in waste liquid pool.
4, filter:
Solution after aeration is sent in vacuum filter and is removed impurity, obtains the not liquid containing solid impurity, and filtering fineness is more than or equal to 20 microns.
5, enrichment step:
The liquid of removing after impurity is sent into triple-effect evaporator, by vaporization temperature be controlled at 115 ℃ of left and right, dump temperature control is 115 ℃ of left and right.
6, crystallisation step:
The slurry of discharging directly enters in the cooling tank of temperature-adjustable and carries out crystallisation by cooling, in cooling tank, homo(io)thermism is 40 ℃ of left and right, reaction generates wet magnesium sulfate heptahydrate and mother liquor, and wet magnesium sulfate heptahydrate send drying machine dry, and mother liquor returns in aeration tank and recycles.
7, dry packing: evaporation, the wet magnesium sulfate heptahydrate that obtains after cooling are dried, and wherein, the dry equipment adopting is mainly vibration vulcanization bed drying machine, and drying temperature is 85 ℃ of left and right; Finished product is after drying sent into the packing shop moulding of directly packing by conveying belt.
The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 2
Except increase by 5 weight part KMO in sweetening agent
4, desulfurization slurry being generated outside the solution (the described per-cent all weight percent sum based on magnesium sulfate and magnesium sulfite is 100wt% meter) of 97wt% magnesium sulfate and 3wt% magnesium sulfite, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 3
Except magnesian weight part being changed into 80 weight parts in sweetening agent, desulfurization slurry is generated outside the solution (the described per-cent all weight percent sum based on magnesium sulfate and magnesium sulfite is 100wt% meter) of 90wt% magnesium sulfate and 10wt% magnesium sulfite, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 4
Start to discharge outside desulfurization slurry except when pH value reaches at 7.5 o'clock, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 5
Except vaporization temperature being controlled to 110 ℃ of left and right, dump temperature control is that 110 ℃ of left and right, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 6
Except by homo(io)thermism in cooling tank 35 ℃ of left and right, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 7
Except the content of activated magnesia is adjusted into 55wt%, other conditions are identical with embodiment 1.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
embodiment 8
(1) modulation of sweetening agent:
According to following formula, each component is mixed, obtain sweetening agent.
(2) utilize desulfurization waste liquor to produce the technique of magnesium sulfate
1, slurrying:
The desulfurizer powder modulating is added water, and to form main component after slurrying, slaking be hydrogeneous magnesian slurry (being called for short hydrogeneous magnesian slurry), and stay in slurry tank for subsequent use.
2, desulfurization and oxidation:
Sulfurous gas in flue gas in thionizer with main hydrogeneous magnesian slurry reaction, remove the SO in flue gas
2.
In thionizer, in hydrogeneous magnesian slurry, contain strong oxidizer (MnO
2) make slurry in tower, at desulphurization reaction, moment generates 90wt% magnesium sulfate and 10wt% magnesium sulfite solution by desulfurization slurry occur, the described per-cent all weight percent sum based on magnesium sulfate and magnesium sulfite is 100wt% meter.
3, plasma discharge material:
Thionizer inner bottom part, with the abundant reacted slurry of flue gas, in the time that pH value reaches 6.5, starts to discharge desulfurization slurry, leaves in waste liquid pool.
4, filter:
Solution after aeration is sent in vacuum filter and is removed impurity, obtains the not liquid containing solid impurity, and filtering fineness is more than or equal to 20 microns.
5, enrichment step:
The liquid of removing after impurity is sent into triple-effect evaporator, by vaporization temperature be controlled at 110 ℃ of left and right, dump temperature control is 110 ℃ of left and right.
6, crystallisation step:
The slurry of discharging directly enters in the cooling tank of temperature-adjustable and carries out crystallisation by cooling, in cooling tank, homo(io)thermism is 30 ℃ of left and right, reaction generates wet magnesium sulfate heptahydrate and mother liquor, and wet magnesium sulfate heptahydrate send drying machine dry, and mother liquor returns in aeration tank and recycles.
7, dry packing: evaporation, the wet magnesium sulfate heptahydrate or the aeration that obtain after cooling are dried, and wherein, the dry equipment adopting is mainly vibration vulcanization bed drying machine, and drying temperature is 85 ℃ of left and right; Finished product is after drying sent into the packing shop moulding of directly packing by conveying belt.The character of products therefrom is referring to table 2, and every experimental data is referring to table 3.
The character of table 2, products therefrom
| Main content is (with MgSO 4·7H 2O meter), wt% >= | 98.0 |
| Iron (in Fe) content, wt% >= | 0.005 |
| Muriate (in Cl) content, wt% >= | 0.30 |
| Water insoluble matter content, wt%≤ | 0.10 |
Table 3, every experimental data
| 1 | Current consumption | Degree | 730 |
| 2 | Water loss | t/h | 40/h |
| 3 | Steam consumption | t/h | 4 |
| 4 | Vapour temperature | ℃ | 250 |
| 5 | Desulfuration byproduct molecular formula | MgSO 4·7H 2O | |
| 6 | Transformation efficiency | ％ | 80 |
| 7 | Sweetening agent consumption | kg/h | 764 |
| 8 | Desulfurization product turnout | kg/h | 4584 |
Can find out by above case study on implementation, this has not only solved the problem of desulfurization waste liquor, solid slag secondary pollution the method for what the present invention proposed utilize flue gas desulphurization waste solution produces magnesium sulfate heptahydrate, and makes magnesium sulfate heptahydrate product.
In addition, technological process steam output of the present invention is little, production cost is low, non-wastewater discharge, transformation efficiency up to more than 80%, product purity can reach more than 98%.
The present invention is not limited to above-mentioned embodiment, and in the situation that not deviating from flesh and blood of the present invention, any distortion, improvement, the replacement that it may occur to persons skilled in the art that all fall into scope of the present invention.
Claims (7)
1. utilize desulfurization waste liquor to produce a method for magnesium sulfate heptahydrate, it comprises the steps:
(1) slurrying step: the sweetening agent that comprises magnesium oxide and oxygenant is added water and makes hydrogeneous magnesian slurry, and described oxygenant is the oxygenant that tetravalence sulphur can be oxidized to sexavalence sulphur;
(2) desulfurized step: in desulfurizer, the flue gas that comprises sulfurous gas is contacted with hydrogeneous magnesian slurry, to remove the sulfurous gas in flue gas, and carry out oxidizing reaction;
(3) plasma discharge step: in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the slurry forming after desulfurization is discharged;
(4) filtration step: the slurries filtration that step (3) is discharged, obtains the not liquid containing solid impurity;
(5) enrichment step: step (4) gained liquid is sent into vaporizer, slurry is discharged after concentrated, vaporization temperature is that 100～125 ℃ and dump temperature are 100～125 ℃;
(6) crystallisation step: the slurry that step (5) is discharged carries out crystallisation by cooling, and temperature is 30～45 ℃, generates magnesium sulfate heptahydrate,
Wherein,
In the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the magnesium sulfate content in the slurry forming after desulfurization more than 90wt%, in the total mass of the magnesium sulfate in slurry and magnesium sulfite,
Sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
Wherein, the active oxidation Mg content in MgO is 50～75wt%.
2. utilize desulfurization waste liquor to produce a method for magnesium sulfate heptahydrate, it comprises the steps:
(1 ') slurrying step: the sweetening agent that comprises magnesium oxide and oxygenant is added water and makes hydrogeneous magnesian slurry, and described oxygenant is the oxygenant that tetravalence sulphur can be oxidized to sexavalence sulphur;
(2 ') desulfurized step: in desulfurizer, the flue gas that comprises sulfurous gas is contacted with hydrogeneous magnesian slurry, to remove the sulfurous gas in flue gas, and carry out oxidizing reaction;
(3 ') plasma discharge step: in the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the slurry forming after desulfurization is discharged;
(4 ') enrichment step: the slurry that step (3 ') is discharged is sent into vaporizer, discharges slurry after concentrated, and vaporization temperature is that 100～125 ℃ and dump temperature are 100～125 ℃;
(5 ') crystallisation step: the slurry that step (4 ') is discharged carries out crystallisation by cooling, and temperature is 30～45 ℃, generates magnesium sulfate heptahydrate,
Wherein,
In the time that the pH of the slurry forming after desulfurization value reaches 6.5～7.5, the magnesium sulfate content in the slurry forming after desulfurization more than 90wt%, in the total mass of the magnesium sulfate in slurry and magnesium sulfite,
Sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
Wherein, the active oxidation Mg content in MgO is 50～75wt%.
3. method according to claim 1 and 2, vaporization temperature is that 110～120 ℃ and dump temperature are 110～120 ℃.
4. method according to claim 1 and 2, sweetening agent also comprises KMnO
43～8 weight parts, take sweetening agent gross weight as 100 weight parts.
5. method according to claim 1 and 2,
Sweetening agent comprises following component, take sweetening agent gross weight as 100 weight parts:
Wherein, the active oxidation Mg content in MgO is 62～75wt%.
6. method according to claim 5, sweetening agent also comprises KMnO
45～8 weight parts, take sweetening agent gross weight as 100 weight parts.
7. method according to claim 1 and 2, described crystallisation step carries out in the adjustable crystallisation by cooling groove of temperature.
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| CN102992362B (en) * | 2012-12-27 | 2014-04-16 | 青岛奥盖克化工股份有限公司 | Process for producing magnesium sulfate via air-cooling crystallization manner |
| CN103112908A (en) * | 2013-01-26 | 2013-05-22 | 刘晓钟 | Method for treating magnesium-sulfate-containing wastewater in hydrometallurgy |
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