CN103304090A - 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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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 a kind of device and recovery method thereof of sulfur waste acid recovery, especially to retrieving arrangement and the recovery method thereof of sulfur waste acid, be applicable to sulphur resource, nonferrous metal resource, water resources recycle device and the method for the sulfur waste acid that the weak acid scrubbing refining plant is discharged in sulfurous iron ore, the non-ferrous metal metallurgy flue gas acid preparing system in a kind of high polluted low concentration sulfuric acid acid making system.
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 the weak acid scrubbing wet processing to purify more, has produced a large amount of lower concentration H that contain in the device
2SO
4And pollutent waste water such as As, Pb, Hg, Cd, Zn, Cu, Fe, if directly discharging not only can be wasted resources such as valuable sulphur, non-ferrous metal, water, also can bring serious environmental to pollute.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 industry greenization of nonferrous metallurgy.
Processing intent according to sulfuric acid acid making system dilute sulphuric acid is divided, and is divided into the partially recycled type that utilizes of qualified discharge type, recycling type entirely and part qualified discharge.Be the qualified discharge type with reaching state sewage emission standard discharge production battery limit (BL) after the dilute sulphuric acid processing; Require to add to dried desorption system with process water and be called the recycling type and satisfy the sulfuric acid product national standard after dilute sulphuric acid handled.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 has not satisfied present environmental protection requirement, often cost too high, be difficult to industrialization.The method of being used widely is neutralisation-iron salt method, neutralization-sulfuration method; Generally adopt the lime neutralization to containing the lower waste water of arsenic concentration.The reaction principle that the sulfuration method is removed As, heavy metal ion is: 2M
N++ nS
2-=M
2Sn ↓.By the dissolubility data of metallic sulfide as can be known, the solubility product of sulfide is much smaller, this means that the sulfuration method can obtain higher clearance, and can also can reach very high purification rate under higher acidic conditions; And neutralisation need add the alkaline matter of higher amount in dilute sulphuric acid, makes the OH in the solution
-Concentration reaches higher level, just can reach desirable clearance.Qualified discharge by dilute sulphuric acid requires as can be known, reaches the sewage drainage standard of increasingly stringent, must be with the SO in the 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 the alkali consuming cost, use milk of lime or carbide slag more.In order to reach higher metal ion emission standard, the technologies that adopt 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, settlement of sewage device; A large amount of gypsum that reaction forms are because the market problem usually needs bigger stacking place, owing to contain 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.The so-called recycling is exactly the diluted acid process that acid-scrubbing cleaning is discharged to be purified turn back to dried desorption system, takes full advantage of sulphur and the water resources of discharging diluted acid.But need here As, F, metal ion are controlled in certain level, make it can not cause the As of product acid, the content overproof of F metal ion.This will face two problems, the one,, the peracidity condition remove As, F, metal ion, the 2nd,, the water-content (perhaps acid concentration) of diluted acid is returned in control, maintains the water balance of dried desorption system, makes the output of variant production acid satisfy market demands.Generally, it is very difficult to make the content of each metal ion species reach sewage drainage standard in high-concentration sulfuric acid, but the requirement that reaches Returning utilization still is possible, and this point has obtained the proof of industrial experiment.But the water yield that the diluted acid that returns is taken back does not influence the water balance of dried desorption system.
If the sulfidation vulcanizing agent adopts salts substances, as the most frequently used be Na cheap and easy to get
2S then can form metabisulfite solution in diluted acid, this material solubleness under 40 ℃ of temperature is the highest, but descends to some extent with the temperature solubleness that further raises, might be in evaporative process on heat transfer wall crystallization form solid Na
2SO
410H
2O worsens the 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 takes place of acid making system
2S becomes selection preferably.
Hydrogen sulfide belongs to Poisons, boiling point-60 ℃.Generally can only prepare gaseous hydrogen sulfide in industry, inconvenience is deposited and is used.The 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(metathesis)reaction method; Sulphur and hydrocarbon polymer and water vapor catalysis synthesis process; Metallic sulfide vitriol oil acidization; Phosphoric acid and Sodium sulfhydrate directly prepare liquid hydrogen sulfide method etc. under the low temperature.The known general reaction conditions of method sulphur hydrogen reduction method all carries out under higher temperature, as: temperature is 400 ℃ ~ 600 ℃, and air speed is 300 h
-1~ 1000 h
-1, aluminum oxide is catalyzer, and this technology need possess the hydrogen generating apparatus, and investment is big, poor stability.Sulphur and Sweet natural gas reaction generate hydrogen sulfide, and this method hydrogen sulfide per ton consumes Sweet natural gas 380 Nm
3~ 390Nm
3, whole production device flow process is long, equipment is more, the investment is higher.Vitriol oil acidifying sulfide (mainly being Fe, Cu sulfides ore deposit) method except consuming a large amount of sulfuric acid, also can produce the slag that contains high concentrated acid in a large number, brings new pollution.Phosphoric acid sulfide low-temp reaction rule needs the liquid nitrogen cryogenics refrigeration system, invests higher, poor stability.Therefore, seek the key that new hydrogen sulfide production technology becomes the diluted acid recycle device.
Summary of the invention
At the problems referred to above, the present invention is under the prerequisite that does not influence sulfurous iron ore, metallurgical off-gas acid-making 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 the sulfur waste acid recovery utilizes in a kind of sulfuric acid acid making system is provided.
In order to address the above problem, the technical solution used in the present invention is as follows:
The device of sulfur waste acid recovery in a kind of sulfuric acid acid making system comprises pyrite-based sulfuric acid production system and metallurgical off-gas acid-making system; It is characterized in that: in pyrite-based sulfuric acid production system or metallurgical off-gas acid-making system, have additional sulfur waste acid storage tank, the first sulfuric acid pump, first strainer, electrodialysis membrane stack, vulcanization reaction device, the second sulfuric acid pump, second strainer and vaporizer; Wherein, after the sulfur waste acid of described sulfur waste acid storage tank is imported the filtration of first strainer by the first sulfuric acid pump, carry out electrodialysis through the electrodialysis membrane stack again, and enter the vulcanization reaction device and react, vulcanization reaction is imported second strainer by the second sulfuric acid pump and is filtered, enter vaporizer then and evaporate, constitute sulfur waste acid-restoring plant in the sulfuric acid acid making system thus.
In the technical scheme of above-mentioned retrieving arrangement, further additional technical feature is as follows:
First strainer and second strainer are one or more the series connection in plate filter, dynamic membrane filtering device and the 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
It is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane, cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that four Room membrane stacks, the ion-exchange membrane of four Room membrane stacks put in order;
The recovery method of the retrieving arrangement of sulfur waste acid in a kind of 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 the sulfuric acid storage tank is input in first strainer by the first sulfuric acid pump filters, make dustiness in the dilute sulphuric acid less than 10mg L
-1
(2) dilute sulphuric acid after will filtering is incorporated in the three Room membrane stacks in the electrodialysis membrane stack, the compartment that constitutes 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, adjust the current/voltage of electrodialysis membrane stack, in the respective compartment of electrodialysis membrane stack, generate the hydrogen sulfide dilution heat of sulfuric acid; Perhaps
Dilute sulphuric acid after filtering is incorporated in the four Room membrane stacks in the electrodialysis membrane stack, the compartment that constitutes between four Room membrane stacks, 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, in the respective compartment of electrodialysis membrane stack, generate the hydrogen sulfide dilution heat of sulfuric acid;
(3) the hydrogen sulfide dilution heat of sulfuric acid with above-mentioned steps (2) is incorporated in the vulcanization reaction device, carries out the revulcanization reaction, and the metal ion in the dilute sulphuric acid is fully precipitated, and obtains the dilute sulphuric acid of containing metal sulfide;
(4) dilute sulphuric acid of containing metal sulfide is input in second strainer by the second sulfuric acid pump filters, and collect the metallic sulfide that precipitates in the dilute sulphuric acid, make its solid content less than 10mg L
-1
(5) dilute sulphuric acid that will remove metallic sulfide is introduced in the vaporizer and is evaporated, and makes its concentration reach 30% ~ 60%, the sulfuric acid after obtaining to concentrate.
In the technical scheme of above-mentioned recovery method, further additional technical feature is as follows:
In the three Room membrane stacks in the electrodialysis membrane stack, the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending dilute sulphuric acid is 0.5% ~ 25%; The concentration of aqueous solution that feeds sulfide or sulfohydrate is 0.5% ~ 30%; Perhaps
In the four Room membrane stacks in the electrodialysis membrane stack, the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending dilute sulphuric acid is 0.5% ~ 25%; The concentration that feeds dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that feeds 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 the weak ammonia.
Realize device and the recovery method thereof of sulfur waste acid recovery in the above-mentioned a kind of sulfuric acid acid making system of the present invention, be in existing sulfurous iron ore, metallurgical off-gas acid-making system, by increasing sulfur waste acid-restoring plant and recovery method thereof, acid is handled to sulfur waste, saved the input of a large amount of neutralization reaction alkali, the ceramic vacuum drum type filteration device is sent in the isolated filter pulp of mine dust film filter or plate filter further dewaters, make the mine dust water content reach＜send the slag treatment process after 10% the requirement; The isolated filter pulp of metallic sulfide film filter is through the dehydration of sulfide ceramic vacuum drum strainer or plate filter, makes water content reach＜deliver to after 10% to reclaim system of processing to handle, and reclaims valuable metal.The present invention is with heavy metal ion, As in pyrite-based sulfuric acid production, the non-ferrous metal metallurgy flue gas acid preparing
3-, F
-The acid-scrubbing cleaning flow process effluxes acid waste water 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 off-gas acid-making system.
Description of drawings
Fig. 1 is the device of sulfur waste acid recovery in a kind of sulfuric acid acid making system and the structural principle synoptic diagram of recovery method thereof.
Among the figure: 1: the sulfur waste acid storage tank; 2: the first sulfuric acid pumps; 3: the first strainers; 4: the electrodialysis membrane stack; 5: the 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 made further instruction.
Embodiment 1
As shown in Figure 1, the device of implementing sulfur waste acid recovery in a kind of sulfuric acid acid making system provided by the present invention is in existing sulfurous iron ore, metallurgical off-gas acid-making system, by increasing sulfur waste acid-restoring plant provided by the present invention, acid is handled to sulfur waste, and this retrieving arrangement comprises sulfur waste acid storage tank 1, the first sulfuric acid pump 2, first strainer 3, electrodialysis membrane stack 4, vulcanization reaction device 5, the second sulfuric acid pump 6, second strainer 7 and vaporizer 8; Wherein: the sulfur waste acid in the described sulfur waste acid storage tank 1 is that the dilute sulphuric acid from weak acid scrubbing refining plant in the sulfuric acid acid making system is incorporated in the sulfur waste acid storage tank 1; And by after 3 filtrations of the first sulfuric acid pump, 2 inputs, first strainer, carry out electrodialysis through electrodialysis membrane stack 4 again, and enter vulcanization reaction device 5 and react, vulcanization reaction filters by the second sulfuric acid pump, 6 inputs, second strainer 7, enter vaporizer 8 then and evaporate, constitute the retrieving arrangement of a kind of sulfur waste acid provided by the present invention thus.
In the retrieving arrangement of above-mentioned sulfur waste acid, first strainer 3 that adopts and second strainer 7 are that one or more the series connection in plate filter, dynamic membrane filtering device and the Ge Er film filter all can.
The compartment of the electrodialysis membrane stack 4 that adopts 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 of sulfur waste acid recovery in a kind of described sulfuric acid acid making system provided by the present invention, this method follows these steps to carry out.
Step 1, the sulfur waste acid in the sulfur waste acid storage tank 1 is input in first strainer 3 by the first sulfuric acid pump 2 filters, make dustiness in the dilute sulphuric acid less than 10mg L
-1
Step 2, the dilute sulphuric acid after will filtering are incorporated in the three Room membrane stacks in the electrodialysis membrane stack 4, the compartment that constitutes between two films of three Room membrane stacks is respectively to having sulfide or the sulfohydrate aqueous solution, pending sulfur waste 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.
Perhaps, dilute sulphuric acid after filtering is incorporated in the four Room membrane stacks in the electrodialysis membrane stack 4, the compartment that constitutes between four Room membrane stacks, 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, hydrogen sulfide solution and the dilution heat of sulfuric acid of above-mentioned steps (2) is incorporated in the vulcanization reaction device 5, carries out the revulcanization reaction, the metal ion in the 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 second strainer 7 by the second sulfuric acid pump 6 filters, and collect the metallic sulfide that precipitates in the dilute sulphuric acid, make its solid content less than 10mg L
-1
Step 5, the dilute sulphuric acid that will remove metallic sulfide are introduced in the vaporizer 8 and are evaporated, and make its concentration reach 30% ~ 60%, the sulfuric acid after obtaining to concentrate.
In the recovery method of above-mentioned sulfur waste acid-restoring plant, in the three Room membrane stacks in the electrodialysis membrane stack 4, the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending dilute sulphuric acid is 0.5% ~ 25%; The concentration of aqueous solution that feeds sulfide or sulfohydrate is 0.5% ~ 30%;
Perhaps, in the four Room membrane stacks in the electrodialysis membrane stack 4, the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending dilute sulphuric acid is 0.5% ~ 25%; The concentration that feeds dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that feeds the aqueous solution of sulfide or sulfohydrate is 0.5% ~ 45%.
Further, the sulfide that adopts or sulfohydrate are one or more the combinations of selecting to the soluble salt of sodium, potassium, lithium, caesium and ammonium ion; The oxyhydroxide that adopts is to select a kind of to sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and the weak ammonia.
Below by specific embodiment the specific embodiment of the present invention is made further instruction.
Embodiment 1
Implement the recovery method of the device of sulfur waste acid recovery in a kind of sulfuric acid acid making system provided by the present invention, this method follows these steps to carry out.
Step 1, will be incorporated in the sulfur waste acid storage tank 1 from the sulfur waste acid of weak acid scrubbing refining plant in the sulfuric acid acid making system.
Step 2, the useless diluted acid in the sulfur waste acid storage tank 1 is squeezed into strainer 3 with sulfuric acid pump 2, the elimination overwhelming majority (95%) mine dust in strainer 3 makes the dustiness in the diluted acid be lower than 10mg L
-1
Step 3, the sulfur waste acid after will filtering are incorporated into electrodialysis membrane stack 4, add hydrogen sulfide at this, treat to leave the electrodialysis membrane stack after concentration of hydrogen sulfide in the sulfur waste acid reaches requirement.
Step 4, the dilute sulphuric acid that will contain a certain amount of hydrogen sulfide are incorporated into vulcanization reaction device 5, fully finish vulcanization reaction here, and metal ion is precipitated fully.
Step 5, the dilute sulphuric acid of containing metal sulfide is driven into strainer 7 with sulfuric acid pump 6, filters and collect metallic sulfide in the dilute sulphuric acid by strainer 7, make the dilute sulphuric acid solid content of filter outlet be lower than 10mg L
-1
Step 6, the dilute sulphuric acid that will remove metallic sulfide are introduced vaporizer 8, evaporate part moisture by vaporizer 8, make the concentration of outlet sulfuric acid reach 30% ~ 60%.
Dilute sulphuric acid after the purification is guided to the diluted acid vapo(u)rization system and is finished and concentrate and except F
-Process, the concentrated vitriol that reaches normality is introduced the sour circulation groove of the dried desorption system of sulfuric acid sulphuric acid plant.So far, contain mine dust, heavy metal ion, As
3-, F
-The acid-scrubbing cleaning flow process effluxes acid waste water and obtains reclaiming through purifying, and contained heavy metal, As, F also obtain reclaiming the input of having saved a large amount of neutralization reaction alkali simultaneously as valuable resource.
Below above-mentioned electrodialysis membrane stack (ED) is further described:
The electrodialysis membrane stack be a kind of selection perviousness of utilizing ionic membrane to ionogen charged ion in the water and a kind of equipment that neutral species separates under electric field action, reach intended purposes 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 constitutes compartment.Material is when the compartment, and the yin, yang ion is orientation movement round about under electric field action, through the selection of ionic membrane by with barrier effect, the cation permeation cationic membrane, negatively charged ion sees through anionic membrane.Compartment is divided into and removes two kinds of chamber and concentration compartmentss, removes ion in the chamber to the migration of lateral condensation chamber, and the ion of concentration compartments is because the selectivity of film and can't be to the chamber of removing migration, 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, be respectively sulfide compartment, pending sulfur waste 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 sulfur waste acid compartment and oxyhydroxide compartment.Wherein, the sulfide compartment is to remove the chamber, and pending dilute sulphuric acid compartment and oxyhydroxide compartment are the concentration compartmentss.Can make sulfidic materials be converted into hydrogen sulfide and hydroxide product by this electrodialysis membrane stack.If adopt sodium sulphite as the ionogen of sulfide compartment, then the concentration of sodium sulfide solution reduces gradually in this chamber, and concentration sodium hydroxide raises gradually in the oxyhydroxide compartment, and pending sulfur waste acid has increased 2 S component in the pending sulfur waste acid compartment.
The present invention relates to device and recoverying and utilizing method with the sulfur waste acid recovery utilization of sulfurous iron ore, the sulfuric acid washing scavenging process generation processed of non-ferrous metal metallurgy flue gas.Apparatus of the present invention are made up of strainer, electrodialysis membrane stack, vulcanization reaction device, strainer, vaporizer.The method that sulfur waste acid recovery of the present invention utilizes, sulfur waste acid acid-scrubbing cleaning device from the sulfuric acid acid making system is drawn, squeeze into wherein solid dust of strainer elimination with pump, particulate state suspended substances such as burning compound, obtain the bright dilute sulphuric acid of color, this dilute sulphuric acid is introduced the electrodialysis membrane stack to be mixed with hydrogen sulfide, hydrogen sulfide containing dilute sulphuric acid is introduced the vulcanization reaction device carry out the tight cure reaction, obtain containing metallic sulfide, the sulfuration dilute sulphuric acid that contains the sulfoarsenide suspended solid, to vulcanize dilute sulphuric acid pumps into strainer and removes wherein metallic sulfide, suspended solids such as arsenide, obtain the dilute sulphuric acid of bright cleaning, the sulfuric acid of cleaning is sent into evaporator evaporation part moisture, the concentration that obtains cleaning is 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 technology.The sulfide filter cake contains non-ferrous metal, rare metal even precious metal element, and filter cake is further processed recyclable valuable metal 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 under the prerequisite that does not influence 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 off-gas acid-making system.
Claims (7)
1. the retrieving arrangement of sulfur waste acid in the sulfuric acid acid making system comprises pyrite-based sulfuric acid production system and metallurgical off-gas acid-making system; It is characterized in that: in pyrite-based sulfuric acid production system or metallurgical off-gas acid-making system, have additional sulfur waste acid storage tank (1), the first sulfuric acid pump (2), first strainer (3), electrodialysis membrane stack (4), vulcanization reaction device (5), the second sulfuric acid pump (6), second strainer (7) and vaporizer (8); Wherein, after the sulfur waste acid of described sulfur waste acid storage tank (1) is filtered by the first sulfuric acid pump (2) input first strainer (3), carry out electrodialysis through electrodialysis membrane stack (4) again, and enter vulcanization reaction device (5) and react, vulcanization reaction filters by the second sulfuric acid pump (6) input second strainer (7), enter vaporizer (8) then and evaporate, constitute sulfur waste acid-restoring plant in the sulfuric acid acid making system.
2. the retrieving arrangement of sulfur waste acid in the sulfuric acid acid making system as claimed in claim 1 is characterized in that: first strainer (3) and second strainer (7) are one or more the series connection in plate filter, dynamic membrane filtering device and the Ge Ermo strainer.
3. the retrieving arrangement of sulfur waste acid in the sulfuric acid acid making system as claimed in claim 1, it is characterized in that: 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
It is cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane, cationic membrane, anionic membrane, cationic membrane, Bipolar Membrane that four Room membrane stacks, the ion-exchange membrane of four Room membrane stacks put in order.
4. the recovery method of the retrieving arrangement of sulfur waste acid in the sulfuric acid acid making system as claimed in claim 1, it is characterized in that: described method is to follow these steps to carry out:
(1) the sulfur waste acid in the sulfur waste acid storage tank (1) is input in first strainer (3) by the first sulfuric acid pump (2) filters, make dustiness in the sulfur waste acid less than 10mg L
-1
(2) the sulfur waste acid after will filtering is incorporated in the three Room membrane stacks in the electrodialysis membrane stack (4), the compartment that constitutes 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, adjust the current/voltage of electrodialysis membrane stack (4), in the respective compartment of electrodialysis membrane stack (4), generate hydrogen sulfide solution and sulfur waste acid mixing solutions; Perhaps
Sulfur waste acid after filtering is incorporated in the four Room membrane stacks in the electrodialysis membrane stack (4), the compartment that constitutes between four Room membrane stacks, 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 hydrogen sulfide solution and mix with sulfur waste acid;
(3) hydrogen sulfide solution and the sulfur waste acid mixing solutions with above-mentioned steps (2) is incorporated in the vulcanization reaction device (5), carries out the revulcanization reaction, and the metal ion in the sulfur waste acid is fully precipitated, and obtains the dilute sulphuric acid of containing metal sulfide;
(4) dilute sulphuric acid of containing metal sulfide is input in second strainer (7) by the second sulfuric acid pump (6) filters, and collect the metallic sulfide that precipitates in the dilute sulphuric acid, make its solid content less than 10mg L
-1
(5) dilute sulphuric acid that will remove metallic sulfide is introduced in the vaporizer (8) and is evaporated, and makes its concentration reach 30% ~ 60%, the sulfuric acid after obtaining to concentrate.
5. the recovery method of sulfur waste acid-restoring plant in the sulfuric acid acid making system as claimed in claim 4 is characterized in that: in the three Room membrane stacks in the electrodialysis membrane stack (4), the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending sulfur waste acid is 0.5% ~ 25%; The concentration of aqueous solution that feeds sulfide or sulfohydrate is 0.5% ~ 30%; Perhaps
In the four Room membrane stacks in the electrodialysis membrane stack (4), the concentration that feeds hydroxide aqueous solution is 0.5% ~ 30%; The concentration that feeds pending sulfur waste acid is 0.5% ~ 25%; The concentration that feeds dilution heat of sulfuric acid is 0.5% ~ 25%; The concentration that feeds the aqueous solution of sulfide or sulfohydrate is 0.5% ~ 45%.
6. the recovery method of sulfur waste acid-restoring plant in the sulfuric acid acid making system as claimed in claim 4 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.
7. the recovery method of sulfur waste acid-restoring plant in the sulfuric acid acid making system as claimed in claim 4 is characterized in that: oxyhydroxide is one or more the combination in sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide and the weak ammonia.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553248A (en) * | 2013-10-23 | 2014-02-05 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN103864249A (en) * | 2014-03-28 | 2014-06-18 | 中国科学技术大学 | Method for extracting lithium hydroxide by salt lake brine |
| CN105036089A (en) * | 2015-07-14 | 2015-11-11 | 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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| 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553248A (en) * | 2013-10-23 | 2014-02-05 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN103553248B (en) * | 2013-10-23 | 2015-04-08 | 中南大学 | Heavy metal waste acid and wastewater resource recycling method and device |
| CN103864249A (en) * | 2014-03-28 | 2014-06-18 | 中国科学技术大学 | Method for extracting lithium hydroxide by salt lake brine |
| 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 |
| CN105036089A (en) * | 2015-07-14 | 2015-11-11 | 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 |
| 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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