CN103304090B - Device and method for recycling waste sulfate in sulfate acid-making system - Google Patents
Device and method for recycling waste sulfate in sulfate acid-making system Download PDFInfo
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- CN103304090B CN103304090B CN201310224922.6A CN201310224922A CN103304090B CN 103304090 B CN103304090 B CN 103304090B CN 201310224922 A CN201310224922 A CN 201310224922A CN 103304090 B CN103304090 B CN 103304090B
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Abstract
The invention discloses a device and method for recycling waste sulfate in a sulfate acid-making system. The device is characterized in that a waste sulfate storage tank is additionally arranged in a pyrite acid-making system or a smoke-smelting acid-making system, after being input into a first filter through a sulfate pump, the waste sulfate in the waste sulfate storage tank is filtered, the electroosmosis is performed on the filtered waste sulfate through an electroosmosis film, and then the waste sulfate enters to a sulfuration reactor to react, after the sulfuration, the waste sulfate is input to the second filter so as to be filtered, and then input into an evaporator to evaporate to obtain the concentrated sulfate. The utilization rated of the sulfur resource, water resource, and the non-ferrous metal resource are improved without influencing the sulfate product quality of the acid-making system, the waste water discharge of the acid-making system is reduced, the economic benefit, environment benefit and social benefit of the pyrite acid-making system or a smoke-smelting acid-making system are greatly improved.
Description
Technical field
The present invention relates to device and recovery method thereof that a kind of Waste Sulfuric Acid reclaims, especially in high polluted low concentration sulfuric acid acid making system to the retrieving arrangement of Waste Sulfuric Acid and a recovery method thereof, be applicable to sulphur resource, nonferrous metal resource, water resources recycle device and the method for the Waste Sulfuric Acid that weak acid scrubbing refining plant in sulfurous iron ore, non-ferrous metal metallurgy flue gas acid preparing system discharges.
Background technology
Pyrite-based sulfuric acid production, non-ferrous metal metallurgy flue gas acid preparing are that sulfocompound is converted into broad-spectrum sulfuric acid process.Yet the sulfur dioxide gas of dust-laden, arsenic compound, fluorochemical adopts weak acid scrubbing wet processing to purify more, a large amount of lower concentration H that contain in device, have been produced
2sO
4and the pollutent waste water such as As, Pb, Hg, Cd, Zn, Cu, Fe, if directly discharge not only can be wasted the resources such as valuable sulphur, non-ferrous metal, water, also can bring serious environmental pollution.Therefore, acid waste water claims the comprehensive treating process of dilute sulphuric acid to recycle here, becomes the key of sulfuric acid industry, the full green industry of nonferrous metallurgy.
According to the processing intent of sulfuric acid acid making system dilute sulphuric acid, divide, be divided into the partially recycled type that utilizes of qualified discharge type, recycling type entirely and part qualified discharge.After dilute sulphuric acid is processed, reach state sewage emission standard discharge production battery limit (BL) and be qualified discharge type; And meet sulfuric acid product national standard after dilute sulphuric acid is processed, require to add to dry desorption system with process water and be called recycling type.Qualified discharge type dilute sulphuric acid treatment process has multiple, mainly contains: neutralisation, sulfuration method, ion exchange method, the magnesium salts precipitator method, biological treatment etc.But single method, can not meet the requirement of present environmental protection, often cost too high, be difficult to industrialization.The method of being used widely is neutralisation-iron salt method, neutralization-sulfuration method; To generally adopt lime neutralization containing the lower waste water of arsenic concentration.The reaction principle that sulfuration method is removed As, heavy metal ion is: 2M
n++ nS
2-=M
2sn ↓.From the dissolubility data of metallic sulfide, the solubility product of sulfide is much smaller, this means that sulfuration method can obtain higher clearance, and can under higher acidic conditions, also can reach very high purification rate; And neutralisation need to add the alkaline matter of higher amount in dilute sulphuric acid, make the OH in solution
-concentration reaches higher level, just can reach desirable clearance.Qualified discharge from dilute sulphuric acid requires, and reaches the sewage drainage standard of increasingly stringent, must be by the SO in dilute sulphuric acid
4 2-, As
x-, F
-and heavy metal ion almost all precipitation remove, like this, need to consume a large amount of alkaline matters.Generally, in order to reduce alkali consuming cost, use milk of lime or carbide slag more.In order to reach higher metal ion emission standard, the technique that adopts neutralization-sulfuration-neutralization more.No matter, all there are a series of serious problems in employing neutralization-iron salt method, neutralization-sulfuration method, as, equipment is huge, flow process is long, investment is higher; All need to consume a large amount of unslaked lime or white lime, need set up huge milk of lime production equipment, sewage precipitation device; A large amount of gypsum that reaction forms, due to market problem, usually need larger stacking place, and owing to containing a certain amount of As, F and toxic heavy metal ion, gypsum has formed new pollution.And be worth higher heavy metal and be not used, can not realize changing waste into resources.
The purification process that dilute sulphuric acid is recycled mainly contains sulfuration-concentration technology.So-called recycling is exactly that the diluted acid that acid-scrubbing cleaning is discharged turns back to dry desorption system through purifying, and makes full use of sulphur and the water resources of discharge diluted acid.But need As, F, metal ion to be controlled at certain level here, make it can not cause the As of product acid, the content overproof of F metal ion.This will face two problems, the one,, peracidity condition remove As, F, metal ion, the 2nd,, control the water-content (or acid concentration) that returns to diluted acid, maintain the water balance of dry desorption system, make the output of variant production acid meet market demands.Generally, will make the content of each metal ion species reach sewage drainage standard very difficult in high-concentration sulfuric acid, but reach the requirement of Returning utilization or possible, this point has obtained the proof of industrial experiment.But the water yield that the diluted acid that will make to return is taken back does not affect the water balance of dry desorption system.
If sulfidation vulcanizing agent adopts salts substances, as the most frequently used, be Na cheap and easy to get
2s can form metabisulfite solution in diluted acid, and this material solubleness at 40 ℃ of temperature is the highest, but declines to some extent with the temperature solubleness that further raises, and likely in evaporative process, on heat transfer wall, crystallization forms solid Na
2sO
410H
2o, worsens operation of equipment condition.Adopt H
2s can avoid concentration process to form the possibility of vitriol.So, at the on-the-spot hydrogen sulfide H that occurs of acid making system
2s becomes good selection.
Hydrogen sulfide belongs to Poisons, boiling point-60 ℃.Generally in industry, can only prepare gaseous hydrogen sulfide, inconvenience is deposited and is used.Hydrogen sulfide production method mainly contains at present: sulfurous gas and hydrocarbon polymer gas and solid phase catalyzing preparation method; Sulphur and hydrogen direct reaction preparation method; Sulphur and hydrocarbon polymer replacement method; Sulphur and hydrocarbon polymer and water vapor catalysis synthesis process; Metallic sulfide vitriol oil acidization; Under low temperature, phosphoric acid and Sodium sulfhydrate are directly prepared liquid hydrogen sulfide method etc.The known general reaction conditions of method sulphur hydrogen reduction method all carries out at higher temperature, as: temperature is 400 ℃ ~ 600 ℃, and air speed is 300 h
-1~ 1000 h
-1, aluminum oxide is catalyzer, and this technique need possess hydrogen generating device, and investment is large, poor stability.Sulphur reacts with Sweet natural gas and generates hydrogen sulfide, and this method hydrogen sulfide per ton consumes Sweet natural gas 380 Nm
3~ 390Nm
3, whole production equipment flow process is long, equipment is more, investment is higher.Vitriol oil acidifying sulfide (being mainly Fe, Cu sulfides ore deposit) method, except consuming a large amount of sulfuric acid, also can produce a large amount of slags containing high concentrated acid, brings new pollution.Phosphoric acid sulfide low-temp reaction rule needs liquid nitrogen cryogenics refrigeration system, invests higher, poor stability.Therefore, find the key that new hydrogen sulfide production technology becomes dilute acid recycle use device.
Summary of the invention
For the problems referred to above, the present invention is not affecting under the prerequisite of sulfurous iron ore, metallurgical gas sulphuric acid system sulfuric acid product quality, improve the utilization ratio of sulphur resource, water resources, nonferrous metal resource, reduce the wastewater discharge of acid making system, and the devices and methods therefor that in a kind of sulfuric acid acid making system, Waste Sulfuric Acid is recycled is provided.
In order to address the above problem, the technical solution used in the present invention is as follows:
The device that in sulfuric acid acid making system, Waste Sulfuric Acid reclaims, comprises pyrite-based sulfuric acid production system and metallurgical gas sulphuric acid system; It is characterized in that: in pyrite-based sulfuric acid production system or metallurgical gas sulphuric acid system, have additional Waste Sulfuric Acid storage tank, the first sulfuric acid pump, the first strainer, electrodialysis membrane stack, vulcanization reaction device, the second sulfuric acid pump, the second strainer and vaporizer; Wherein, the Waste Sulfuric Acid of described Waste Sulfuric Acid storage tank is inputted after the first strainer filtration by the first sulfuric acid pump, through electrodialysis membrane stack, carry out electrodialysis again, and enter vulcanization reaction device and react, vulcanization reaction is inputted the second strainer by the second sulfuric acid pump and is filtered, then enter vaporizer and evaporate, form thus Waste Sulfuric Acid retrieving arrangement in sulfuric acid acid making system.
In the technical scheme of above-mentioned retrieving arrangement, further additional technical feature is as follows:
The first strainer and the second strainer are one or more the series connection in plate filter, dynamic membrane filtering device and Ge Er film filter.
The compartment of electrodialysis membrane stack is three Room membrane stacks, and it is cationic membrane, anionic membrane, Bipolar Membrane, cationic membrane, anionic membrane, Bipolar Membrane that the ion-exchange membrane of three Room membrane stacks puts in order; Or
Four Room membrane stacks, it is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane, cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that the ion-exchange membrane of four Room membrane stacks puts in order;
A recovery method for the retrieving arrangement of Waste Sulfuric Acid in above-mentioned sulfuric acid acid making system, is characterized in that: described method is to follow these steps to carry out:
(1) dilute sulphuric acid in sulfuric acid storage tank is input in the first strainer and is filtered by the first sulfuric acid pump, make the dustiness in dilute sulphuric acid be less than 10mg L
-1;
(2) dilute sulphuric acid after filtering is incorporated in three Room membrane stacks in electrodialysis membrane stack, the compartment forming between two films of three Room membrane stacks is respectively to having sulfide or the sulfohydrate aqueous solution, pending dilute sulphuric acid and hydroxide aqueous solution, the current/voltage of adjusting electrodialysis membrane stack generates hydrogen sulfide dilution heat of sulfuric acid in the respective compartment of electrodialysis membrane stack; Or
Dilute sulphuric acid after filtering is incorporated in four Room membrane stacks in electrodialysis membrane stack, the compartment forming between four Room membrane stack two films is respectively to having sulfide or the sulfohydrate aqueous solution, pending dilute sulphuric acid, dilution heat of sulfuric acid and hydroxide aqueous solution, the current/voltage of adjusting electrodialysis membrane stack generates hydrogen sulfide dilution heat of sulfuric acid in the respective compartment of electrodialysis membrane stack;
(3) the hydrogen sulfide dilution heat of sulfuric acid of above-mentioned steps (2) is incorporated in vulcanization reaction device, carries out revulcanization reaction, the metal ion in dilute sulphuric acid is fully precipitated, obtain the dilute sulphuric acid of containing metal sulfide;
(4) dilute sulphuric acid of containing metal sulfide is input in the second strainer and is filtered by the second sulfuric acid pump, and collect the metallic sulfide precipitating in dilute sulphuric acid, make its solid content be less than 10mg L
-1;
(5) dilute sulphuric acid that removes metallic sulfide is introduced in vaporizer and evaporated, make its concentration reach 30% ~ 60%, obtain the sulfuric acid after concentrating.
In the technical scheme of above-mentioned recovery method, further additional technical feature is as follows:
In three Room membrane stacks in electrodialysis membrane stack, the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending dilute sulphuric acid is 0.5% ~ 25%; The concentration of aqueous solution that passes into sulfide or sulfohydrate is 0.5% ~ 30%; Or
In four Room membrane stacks in electrodialysis membrane stack, the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending dilute sulphuric acid is 0.5% ~ 25%; The concentration that passes into dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that passes into the aqueous solution of sulfide or sulfohydrate is 0.5% ~ 45%.
Sulfide or sulfohydrate are one or more the combinations in the soluble salt of sodium, potassium, lithium, caesium and ammonium ion.
Oxyhydroxide is a kind of in sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and weak ammonia.
Realize device and recovery method thereof that in the above-mentioned a kind of sulfuric acid acid making system of the present invention, Waste Sulfuric Acid reclaims, in existing sulfurous iron ore, metallurgical gas sulphuric acid system, by increasing Waste Sulfuric Acid retrieving arrangement and recovery method thereof, Waste Sulfuric Acid is processed, saved the input of a large amount of neutralization reaction alkali, ceramic vacuum drum type filteration device is sent in the isolated filter pulp of mine dust film filter or plate filter further dewaters, and send slag treatment process after making mine dust water content reach the requirement of <10%; The isolated filter pulp of metallic sulfide film filter is through the dehydration of sulfide ceramic vacuum drum strainer or plate filter, water content reached deliver to after <10% to reclaim system of processing and processes, and reclaims valuable metal.The present invention is by heavy metal ion, As in pyrite-based sulfuric acid production, non-ferrous metal metallurgy flue gas acid preparing
3-, F
-the outer acid discharge wastewater of acid-scrubbing cleaning flow process is through purifying back, further improved the utilization ratio of sulphur resource, water resources, nonferrous metal resource, reduce the wastewater discharge of acid making system, increased substantially economic benefit, environmental benefit and the social benefit of sulfurous iron ore, metallurgical gas sulphuric acid system.
Accompanying drawing explanation
Fig. 1 is the device of Waste Sulfuric Acid recovery in a kind of sulfuric acid acid making system and the structural principle schematic diagram of recovery method thereof.
In figure: 1: Waste Sulfuric Acid storage tank; 2: the first sulfuric acid pumps; 3: the first strainers; 4: electrodialysis membrane stack; 5: vulcanization reaction device; 6: the second sulfuric acid pumps; 7: the second strainers; 8: vaporizer.
Embodiment
Below the specific embodiment of the present invention is further illustrated.
Embodiment 1
As shown in Figure 1, implementing the device that in a kind of sulfuric acid acid making system provided by the present invention, Waste Sulfuric Acid reclaims is in existing sulfurous iron ore, metallurgical gas sulphuric acid system, by increasing Waste Sulfuric Acid retrieving arrangement provided by the present invention, Waste Sulfuric Acid is processed, and this retrieving arrangement comprises Waste Sulfuric Acid storage tank 1, the first sulfuric acid pump 2, the first strainer 3, electrodialysis membrane stack 4, vulcanization reaction device 5, the second sulfuric acid pump 6, the second strainer 7 and vaporizer 8; Wherein: the Waste Sulfuric Acid in described Waste Sulfuric Acid storage tank 1 is that the dilute sulphuric acid from weak acid scrubbing refining plant in sulfuric acid acid making system is incorporated in Waste Sulfuric Acid storage tank 1; And after filtering by first sulfuric acid pump 2 input the first strainers 3, through electrodialysis membrane stack 4, carry out electrodialysis again, and enter vulcanization reaction device 5 and react, vulcanization reaction filters by second sulfuric acid pump 6 input the second strainers 7, then enter vaporizer 8 and evaporate, form thus the retrieving arrangement of a kind of Waste Sulfuric Acid provided by the present invention.
In the retrieving arrangement of above-mentioned Waste Sulfuric Acid, the first strainer 3 adopting and the second strainer 7 are that one or more the series connection in plate filter, dynamic membrane filtering device and Ge Er film filter all can.
The compartment of the electrodialysis membrane stack 4 adopting is three Room membrane stacks or four Room membrane stacks, and wherein, it is cationic membrane, anionic membrane, Bipolar Membrane, cationic membrane, anionic membrane, Bipolar Membrane that the ion-exchange membrane that three Room membrane stacks adopt puts in order; It is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane, cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that the ion-exchange membrane that four Room membrane stacks adopt puts in order.
Embodiment 2
As shown in Figure 1, implement the recovery method of the device that in a kind of described sulfuric acid acid making system provided by the present invention, Waste Sulfuric Acid reclaims, the method follows these steps to carry out.
Step 1, the Waste Sulfuric Acid in Waste Sulfuric Acid storage tank 1 is input in the first strainer 3 and is filtered by the first sulfuric acid pump 2, make the dustiness in dilute sulphuric acid be less than 10mg L
-1.
Step 2, the dilute sulphuric acid after filtering is incorporated in three Room membrane stacks in electrodialysis membrane stack 4, the compartment forming between two films of three Room membrane stacks is respectively to having sulfide or the sulfohydrate aqueous solution, pending Waste Sulfuric Acid and hydroxide aqueous solution, adjust the current/voltage of electrodialysis membrane stack 4, in the respective compartment of electrodialysis membrane stack 4, generate mixing of hydrogen sulfide solution and dilute sulphuric acid.
Or, dilute sulphuric acid after filtering is incorporated in four Room membrane stacks in electrodialysis membrane stack 4, the compartment forming between four Room membrane stack two films is respectively to having sulfide or the sulfohydrate aqueous solution, pending dilute sulphuric acid, dilution heat of sulfuric acid and hydroxide aqueous solution, adjust the current/voltage of electrodialysis membrane stack 4, in the respective compartment of electrodialysis membrane stack 4, generate mixing of hydrogen sulfide solution and dilute sulphuric acid.
Step 3, the hydrogen sulfide solution of above-mentioned steps (2) and dilution heat of sulfuric acid are incorporated in vulcanization reaction device 5, carry out revulcanization reaction, the metal ion in dilute sulphuric acid is fully precipitated, obtain the dilute sulphuric acid of containing metal sulfide.
Step 4, the dilute sulphuric acid of containing metal sulfide is input in the second strainer 7 and is filtered by the second sulfuric acid pump 6, and collect the metallic sulfide precipitating in dilute sulphuric acid, make its solid content be less than 10mg L
-1.
Step 5, the dilute sulphuric acid that removes metallic sulfide is introduced in vaporizer 8 and evaporated, make its concentration reach 30% ~ 60%, obtain the sulfuric acid after concentrated.
In the recovery method of above-mentioned Waste Sulfuric Acid retrieving arrangement, in three Room membrane stacks in electrodialysis membrane stack 4, the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending dilute sulphuric acid is 0.5% ~ 25%; The concentration of aqueous solution that passes into sulfide or sulfohydrate is 0.5% ~ 30%;
Or in four Room membrane stacks in electrodialysis membrane stack 4, the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending dilute sulphuric acid is 0.5% ~ 25%; The concentration that passes into dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that passes into the aqueous solution of sulfide or sulfohydrate is 0.5% ~ 45%.
Further, the sulfide adopting or sulfohydrate are one or more the combinations of selecting in the soluble salt of sodium, potassium, lithium, caesium and ammonium ion; The oxyhydroxide adopting is to select a kind of in sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and weak ammonia.
Below by specific embodiment, the specific embodiment of the present invention is further illustrated.
Embodiment 1
The recovery method of implementing the device that in a kind of sulfuric acid acid making system provided by the present invention, Waste Sulfuric Acid reclaims, the method follows these steps to carry out.
Step 1, the Waste Sulfuric Acid from weak acid scrubbing refining plant in sulfuric acid acid making system is incorporated in Waste Sulfuric Acid storage tank 1.
Step 2, the useless diluted acid in Waste Sulfuric Acid storage tank 1 is squeezed into strainer 3 with sulfuric acid pump 2, the elimination overwhelming majority (95%) mine dusts in strainer 3, make dustiness in diluted acid lower than 10mg L
-1.
Step 3, the Waste Sulfuric Acid after filtering is incorporated into electrodialysis membrane stack 4, at this, adds hydrogen sulfide, after the concentration of hydrogen sulfide in Waste Sulfuric Acid reaches requirement, leave electrodialysis membrane stack.
Step 4, the dilute sulphuric acid that contains a certain amount of hydrogen sulfide is incorporated into vulcanization reaction device 5, fully completes vulcanization reaction here, metal ion is precipitated completely.
Step 5, the dilute sulphuric acid of containing metal sulfide is driven into strainer 7 with sulfuric acid pump 6, by strainer 7, filters and collect the metallic sulfide in dilute sulphuric acid, make the dilute sulphuric acid solid content of filter outlet lower than 10mg L
-1.
Step 6, the dilute sulphuric acid that removes metallic sulfide is introduced to vaporizer 8, by vaporizer 8, evaporate part moisture, make the concentration that exports sulfuric acid reach 30% ~ 60%.
Dilute sulphuric acid after purification is guided to diluted acid vapo(u)rization system and is completed concentrated and except F
-process, the concentrated vitriol that reaches normality is introduced the sour circulation groove of the dry desorption system of sulfuric acid sulphuric acid plant.So far, containing mine dust, heavy metal ion, As
3-, F
-the outer acid discharge wastewater of acid-scrubbing cleaning flow process is recycled through purifying, and contained heavy metal, As, F are also recycled as valuable resource, have saved the input of a large amount of neutralization reaction alkali simultaneously.
Below above-mentioned electrodialysis membrane stack (ED) is further described:
Electrodialysis membrane stack is that a kind of selection perviousness of ionic membrane of utilizing is carried out separated a kind of equipment under electric field action with neutral species to ionogen charged ion in water, reaches expection objects such as removing ionogen or concentrated ionogen.Electrodialytic major parts has anion-exchange membrane, cationic exchange membrane, dividing plate and electrode.The ionic membrane of dividing plate and both sides forms compartment.Material is when the compartment, and yin, yang ion is orientation movement round about under electric field action, through the selection of ionic membrane by with barrier effect, positively charged ion sees through cationic membrane, negatively charged ion sees through anionic membrane.Compartment is divided into and removes two kinds of Shi He concentration compartmentss, removes ion in chamber to the migration of lateral condensation chamber, and the ion of concentration compartments cannot be to the chamber of removing migration due to the selectivity of film, thereby will remove the ionogen of chamber and uncharged solute, separated from solvent.It is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that the present invention adopts the ion-exchange membrane of electrodialysis membrane stack to put in order, produce 4 compartments, respectively sulfide compartment, pending Waste Sulfuric Acid compartment, sulfuric acid compartment and oxyhydroxide compartment, or to adopt ion-exchange membrane to put in order be cationic membrane, anionic membrane, Bipolar Membrane, producing 3 compartments, is respectively sulfide compartment, pending Waste Sulfuric Acid compartment and oxyhydroxide compartment.Wherein, sulfide compartment is to remove chamber, and pending dilute sulphuric acid compartment and oxyhydroxide compartment are concentration compartmentss.By this electrodialysis membrane stack, can make sulfidic materials be converted into hydrogen sulfide and hydroxide product.If adopt sodium sulphite as the ionogen of sulfide compartment, in this chamber, the concentration of sodium sulfide solution reduces gradually, and in oxyhydroxide compartment, the concentration of sodium hydroxide raises gradually, and in pending Waste Sulfuric Acid compartment, pending Waste Sulfuric Acid has increased 2 S component.
Device and recoverying and utilizing method that the Waste Sulfuric Acid that the present invention relates to produce with sulfurous iron ore, non-ferrous metal metallurgy flue gas sulfuric acid washing scavenging process processed is recycled.Apparatus of the present invention are comprised of strainer, electrodialysis membrane stack, vulcanization reaction device, strainer, vaporizer.The method that Waste Sulfuric Acid of the present invention is recycled, Waste Sulfuric Acid acid-scrubbing cleaning device from sulfuric acid acid making system is drawn, with pump, squeeze into wherein solid dust of strainer elimination, the particulate state suspended substances such as burning compound, obtain the bright dilute sulphuric acid of color, this dilute sulphuric acid is introduced to electrodialysis membrane stack to be mixed with hydrogen sulfide, hydrogen sulfide containing dilute sulphuric acid is introduced to vulcanization reaction device and carry out tight cure reaction, obtain containing metallic sulfide, sulfuration dilute sulphuric acid containing sulfoarsenide suspended solid, sulfuration dilute sulphuric acid is pumped into strainer and remove wherein metallic sulfide, the suspended solids such as arsenide, obtain bright clean dilute sulphuric acid, clean sulfuric acid is sent into evaporator evaporation part moisture, obtain clean concentration at 40% ~ 60% concentrated vitriol, concentrated vitriol is pumped into the drying tower sulfuric acid circulation groove of acid making system, as the moisturizing of acid making system technique.Sulfide filter cake contains even precious metal element of non-ferrous metal, rare metal, further processes recyclable valuable metal using filter cake as raw material, promotes the Atom economy of this environmental protecting device, increases the economic benefit of this environmental protecting device.The present invention is not affecting under the prerequisite of acid making system sulfuric acid product quality, improve sulphur resource, water resources, nonferrous metal resource utilization ratio, reduce the wastewater discharge of acid making system, increase substantially economic benefit, environmental benefit and the social benefit of sulfurous iron ore, metallurgical gas sulphuric acid system.
Claims (5)
1. the recovery method of the retrieving arrangement of Waste Sulfuric Acid in a sulfuric acid acid making system, it is characterized in that: in described sulfuric acid acid making system, the retrieving arrangement of Waste Sulfuric Acid comprises pyrite-based sulfuric acid production system and metallurgical gas sulphuric acid system, in pyrite-based sulfuric acid production system or metallurgical gas sulphuric acid system, have additional Waste Sulfuric Acid storage tank (1), the first sulfuric acid pump (2), the first strainer (3), electrodialysis membrane stack (4), vulcanization reaction device (5), the second sulfuric acid pump (6), the second strainer (7) and vaporizer (8); Wherein, after the Waste Sulfuric Acid of described Waste Sulfuric Acid storage tank (1) filters by the first sulfuric acid pump (2) input the first strainer (3), through electrodialysis membrane stack (4), carry out electrodialysis again, and enter vulcanization reaction device (5) and react, vulcanization reaction filters by the second sulfuric acid pump (6) input the second strainer (7), then enter vaporizer (8) and evaporate, form Waste Sulfuric Acid retrieving arrangement in sulfuric acid acid making system;
Described electrodialysis membrane stack (4) is three Room membrane stacks, and it is cationic membrane, anionic membrane, Bipolar Membrane, cationic membrane, anionic membrane, Bipolar Membrane that the ion-exchange membrane of three Room membrane stacks puts in order; Or
Four Room membrane stacks, it is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane, cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that the ion-exchange membrane of four Room membrane stacks puts in order;
Described recovery method is to follow these steps to carry out:
(1) Waste Sulfuric Acid in Waste Sulfuric Acid storage tank (1) is input in the first strainer (3) and is filtered by the first sulfuric acid pump (2), make the dustiness in Waste Sulfuric Acid be less than 10mg L
-1;
(2) Waste Sulfuric Acid after filtering is incorporated in three Room membrane stacks in electrodialysis membrane stack (4), the compartment forming between two films of three Room membrane stacks is respectively to having sulfide or the sulfohydrate aqueous solution, pending Waste Sulfuric Acid and hydroxide aqueous solution, adjust the current/voltage of electrodialysis membrane stack (4), in the respective compartment of electrodialysis membrane stack (4), generate the mixing solutions of hydrogen sulfide solution and Waste Sulfuric Acid; Or
Waste Sulfuric Acid after filtering is incorporated in four Room membrane stacks in electrodialysis membrane stack (4), the compartment forming between four Room membrane stack two films is respectively to having sulfide or the sulfohydrate aqueous solution, pending Waste Sulfuric Acid, dilution heat of sulfuric acid and hydroxide aqueous solution, adjust the current/voltage of electrodialysis membrane stack (4), in the respective compartment of electrodialysis membrane stack (4), generate the mixing solutions of hydrogen sulfide solution and Waste Sulfuric Acid;
(3) mixing solutions of the hydrogen sulfide solution of above-mentioned steps (2) and Waste Sulfuric Acid is incorporated in vulcanization reaction device (5), carries out revulcanization reaction, the metal ion in Waste Sulfuric Acid is fully precipitated, obtain the dilute sulphuric acid of containing metal sulfide;
(4) dilute sulphuric acid of containing metal sulfide is input in the second strainer (7) and is filtered by the second sulfuric acid pump (6), and collect the metallic sulfide precipitating in dilute sulphuric acid, make its solid content be less than 10mg L
-1;
(5) dilute sulphuric acid that removes metallic sulfide is introduced in vaporizer (8) and evaporated, make its concentration reach 30% ~ 60%, obtain the sulfuric acid after concentrating.
2. the recovery method of the retrieving arrangement of Waste Sulfuric Acid in sulfuric acid acid making system as claimed in claim 1, is characterized in that: in three Room membrane stacks in electrodialysis membrane stack (4), the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending Waste Sulfuric Acid is 0.5% ~ 25%; The concentration of aqueous solution that passes into sulfide or sulfohydrate is 0.5% ~ 30%; Or
In four Room membrane stacks in electrodialysis membrane stack (4), the concentration that passes into hydroxide aqueous solution is 0.5% ~ 30%; The concentration that passes into pending Waste Sulfuric Acid is 0.5% ~ 25%; The concentration that passes into dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that passes into the aqueous solution of sulfide or sulfohydrate is 0.5% ~ 45%.
3. the recovery method of the retrieving arrangement of Waste Sulfuric Acid in sulfuric acid acid making system as claimed in claim 1, is characterized in that: sulfide or sulfohydrate are one or more the combinations in the soluble salt of sodium, potassium, lithium, caesium and ammonium ion.
4. the recovery method of the retrieving arrangement of Waste Sulfuric Acid in sulfuric acid acid making system as claimed in claim 1, is characterized in that: oxyhydroxide is one or more the combination in sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and weak ammonia.
5. the recovery method of the retrieving arrangement of Waste Sulfuric Acid in sulfuric acid acid making system as claimed in claim 1, is characterized in that: the first strainer (3) and the second strainer (7) are one or more the series connection in plate filter, dynamic membrane filtering device and Gore membrane filtration device.
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| CN103553248B (en) * | 2013-10-23 | 2015-04-08 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN103864249B (en) * | 2014-03-28 | 2015-06-24 | 中国科学技术大学 | Method for extracting lithium hydroxide by salt lake brine |
| CN105036089B (en) * | 2015-07-14 | 2017-02-01 | 太原理工大学 | Recovery device and recovery method for waste dilute sulfuric acid in sulfuric acid preparation system by using flue gas in nonferrous metal smelting |
| CN106045170A (en) * | 2016-07-20 | 2016-10-26 | 中国恩菲工程技术有限公司 | Treatment method of waste acid outwards discharged from smelting sulfuric acid production system |
| CN109052337A (en) * | 2018-08-27 | 2018-12-21 | 青岛惠城信德新材料研究院有限公司 | A kind of processing method of the Waste Sulfuric Acid of alkylation production process discharge |
| CN110844890A (en) * | 2019-11-18 | 2020-02-28 | 济源豫光有色冶金设计研究院有限公司 | Resource recycling method of waste sulfuric acid of storage battery |
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| CN101857203A (en) * | 2010-05-24 | 2010-10-13 | 东营方圆有色金属有限公司 | Process for comprehensively recycling heavy metal-polluted acid |
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| JPS52101690A (en) * | 1976-02-24 | 1977-08-25 | Asahi Glass Co Ltd | Separation of acid and metal from solution containing acid and its met al salts and recovery of them |
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| CN1052831A (en) * | 1989-12-27 | 1991-07-10 | 贵州省化工设计院 | The enclosed purification process by water-washing of gas washing in SA production |
| CN1201710A (en) * | 1997-01-23 | 1998-12-16 | 阿切尔丹尼尔斯密德兰公司 | Apparatus and process for electrodialysis of salts |
| CN1931729A (en) * | 2006-01-24 | 2007-03-21 | 兰州大学 | Process of treating and utilizing acid waste water containing heavy metal |
| CN101857203A (en) * | 2010-05-24 | 2010-10-13 | 东营方圆有色金属有限公司 | Process for comprehensively recycling heavy metal-polluted acid |
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