CN112759162A - Method and system for recycling waste acid - Google Patents
Method and system for recycling waste acid Download PDFInfo
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- CN112759162A CN112759162A CN202011619381.3A CN202011619381A CN112759162A CN 112759162 A CN112759162 A CN 112759162A CN 202011619381 A CN202011619381 A CN 202011619381A CN 112759162 A CN112759162 A CN 112759162A
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Abstract
The invention belongs to the field of waste acid treatment, and particularly relates to a waste acid recycling treatment method and system, which comprise the following steps: sulfurizing to remove arsenic and heavy metal, purifying with acid-resistant nanofiltration membrane, acid-purifying with fluidized bed, electrodialysis, hot air blowing to remove fluorine and chlorine, negative pressure evaporation and concentration, and treating with mixed acid of fluorine and chlorine; the specific treatment method for removing arsenic and heavy metals by vulcanization comprises the following steps: the waste acid is collected and enters an adjusting tank for water quality and water quantity adjustment, the wastewater after adjustment enters a weight removal reactor, and simultaneously generated H is blown in2S gas, the hydrogen sulfide gas reacts with the arsenic heavy metal in the contaminated acid in the heavy metal removal reactor to generate precipitate, the precipitate is pumped into an FBL filter by a pump for solid-liquid separation, the bottom flow of the filter is subjected to filter pressing separation by a plate-and-frame filter press, and the sulfide slag is safely disposed. The weak solution obtained by treating the waste acid is reused for supplementing fresh water to a production system, and the obtained sulfuric acid is reused for the production system, so that the valuable waste acid is fully recovered, zero discharge of waste acid and waste water is realized, and the method has positive significance for environmental protection.
Description
Technical Field
The invention belongs to the field of waste acid treatment, and particularly relates to a waste acid recycling method and system.
Background
The production process of non-ferrous metal smelting is easy to generate waste acid, the waste acid amount discharged in the production process of recycling flue gas to prepare acid is larger and larger, the pollution to the environment is increasingly serious, the harm of the pollution of the waste acid to the environment and human is known more and more, and the pollution treatment problem of the waste acid is urgently solved because the influence of the waste acid to the environment is larger.
At present, various domestic nonferrous smelting enterprises are mainly treated by methods such as a chemical precipitation method, an electric flocculation method, a biological agent method and the like, wherein most of polluted acid generated by the smelting enterprises adopts a treatment process of 'sulfuration sedimentation and lime neutralization', and a large amount of neutralized slag is generated by the process;
meanwhile, because of the influence of the heavy metal removal efficiency in the vulcanization process, the neutralization slag still contains heavy metals such as lead, arsenic, cadmium and the like, has certain leaching toxicity and cannot be comprehensively utilized;
and a large amount of production wastewater which cannot meet the process recycling requirement is generated after the waste acid is treated and is directly discharged to a park industrial wastewater treatment plant, so that the requirements of environmental protection on zero discharge and resource of the production wastewater cannot be met, and great environmental hazard is caused;
the pressure filter can be used in the processing procedure of dirty sour, and most traditional pressure filters all are intermittent type processing, can't carry out filter-pressing work when unloading the filter cake, just need stop the entering of sewage when unloading the filter cake, work efficiency is limited, in addition, some traditional pressure filters can go on through the manual work at the process of clearance filter cake, operating personnel can unpack a plurality of filter plates that sticiss together apart, manual filter residue with between the filter plate is clear away again, and is not only inefficient, still greatly increased intensity of labour.
Therefore, a waste acid recycling method and a waste acid recycling system are provided to solve the problems.
Disclosure of Invention
The invention aims to provide a method and a system for recycling polluted acid, which can effectively improve the resource utilization rate, aiming at the problems that a large amount of neutralized slag is generated by the traditional polluted acid treatment method and liquid after polluted acid treatment cannot be recycled.
In order to achieve the purpose, the invention adopts the following technical scheme: a method and a system for recycling waste acid comprise the following steps: sulfurizing to remove arsenic and heavy metal, purifying with acid-resistant nanofiltration membrane, acid-purifying with fluidized bed, electrodialysis, hot air blowing to remove fluorine and chlorine, negative pressure evaporation and concentration, and treating with mixed acid of fluorine and chlorine;
the specific treatment method for removing arsenic and heavy metals by vulcanization comprises the following steps: the waste acid is collected and enters a regulating tank for regulating the water quality and the water quantity, the regulated waste water enters a weight removal reactor, generated H2S gas is blown in at the same time, hydrogen sulfide gas reacts with arsenic heavy metal in the waste acid in the weight removal reactor to generate precipitate, the precipitate is pumped into an FBL filter by a pump for solid-liquid separation, the bottom flow of the filter is subjected to filter pressing separation by a plate-and-frame filter press, and the sulfide slag is safely treated;
tail gas generated by the reactor is sent to a harm removal tower for treatment, and the gas reaches the standard and is discharged;
the absorption liquid of the harm removing tower is mainly sodium hydroxide solution, sodium sulfide solution is generated after hydrogen sulfide gas is absorbed, a batch of absorption liquid is sent to a gas generator for treatment at intervals, and resource utilization of the absorption liquid is realized;
sulfuric acid and sodium hydrosulfide or sodium sulfide react in a gas generator to produce hydrogen sulfide gas and sodium sulfate solution, the hydrogen sulfide gas is sent to a heavy reaction tank to take part in the reaction, the sodium sulfate solution in the gas generator is periodically discharged to be evaporated and crystallized, crystals are sent to a rotary kiln, and reducing agent carbon powder is added at the same time, so that a sodium sulfide product generated by the reaction is recycled as a medicament.
In the method and the system for recycling the polluted acid, the purification process of the acid-resistant nanofiltration membrane comprises the following steps: and (3) pretreating the polluted acid by sequentially passing the filtrate subjected to filter pressing separation through a multi-medium filter, an activated carbon filter, a microfiltration membrane and the like, pumping the pretreated purified acid into an acid-resistant nanofiltration membrane through a high-pressure pump, purifying the sulfuric acid by a permeation membrane, and intercepting metal ions by the membrane. And the purified acid generated by the nanofiltration membrane enters an electrodialysis for further treatment, and the waste acid generated by the nanofiltration membrane enters a resin mixed bed for further purification, impurity removal and recovery of sulfuric acid in the resin mixed bed.
In the above method and system for treating waste acid as resource, the purification process of the acid purification bed is as follows: dirty acid after nanofiltration treatment contains more metal ions and salt, the dirty acid is sent to an acid purification bed, acid recovery resin is carried in the bed layer, the acid recovery resin is existing resin, the surface of the resin has strong charges and can adsorb strong acid, and when acid-containing solution flows through the resin layer, the strong acid is adsorbed by the resin. The resin is regenerated by using clean water, water is reversely fed, and high-acid low-salt solution is extruded and then sent to an electrodialysis device for continuous treatment. Finally, a small amount of low-acid high-salt solution is left without recovery value and is sent to neutralization treatment.
In the polluted acid recycling treatment method and system, the electrodialysis process is as follows: conveying the solution subjected to nanofiltration treatment to an electrodialysis stock solution tank, conveying the electrodialysis stock solution to an electrodialysis device I for treatment by using a pump, controlling electrodialysis conditions, producing a concentrated solution I and a dilute solution I after treatment, discharging about 10% of the concentrated solution I, treating the concentrated solution I by using a hot waste gas evaporation concentration system, further treating the dilute solution by using an electrodialysis device II, separating the dilute solution II and the concentrated solution II after membrane treatment by using the electrodialysis device II, wherein the dilute solution II is discharged to 1-2% and then subjected to hot air blowing concentration fluorine and chlorine removal treatment, and the concentrated solution enters the electrodialysis stock solution tank II to enter the next round of electrodialysis circulation treatment.
In the method and the system for recycling the waste acid, the treatment process of blowing off, concentrating and removing fluorine and chlorine by hot air is as follows: after electrodialysis, dilute sulfuric acid in the dilute liquid II enters the top of the stripping tower through a pump, and is in countercurrent contact with hot air or hot waste gas (hot gas adopts an acid making dry absorption process) from the bottom of the tower to transfer materials and heat, and most of water, hydrochloric acid and hydrofluoric acid in the sulfuric acid enter a gas phase to further concentrate, separate and purify the sulfuric acid;
the sulfuric acid which reaches the design index and comes out from the bottom of the stripping tower enters a crystallization kettle for crystallization, the crystallization liquid is filtered to recover salt, the filtrate is sent into a settling tank for further solid-liquid separation, and the finished sulfuric acid solution enters a sulfuric acid storage tank for storage and can be returned to a production system for recycling. The tail gas from the top of the stripping tower contains a certain amount of moisture, hydrochloric acid and hydrofluoric acid, and is sent to a secondary absorption tower for harm removal treatment, the first-stage absorption is carried out to obtain a fluorine-chlorine mixed acid, and the mixed acid is sent to a neutralization salt treatment system;
and (3) absorbing residual hydrogen chloride and hydrogen fluoride in the tail gas by using sodium hydroxide alkali liquor at the tail gas final stage, and discharging the gas after reaching the standard.
In the method and the system for recycling the waste acid, the waste acid subjected to hot air stripping is subjected to negative pressure evaporation concentration treatment by the following steps: the concentration of the waste acid after hot air stripping and concentration is about 40 percent, the amount is large, the difficulty is brought to the whole recycling, and the single-effect negative pressure evaporation process is adopted for the waste acid. The 35% -40% dilute sulphuric acid solution passes through a preheating device and then enters an evaporation device, the solution is concentrated to 60%, water vapor generated by evaporation is condensed into distilled water with the acid content less than 0.6% through a condenser, and the distilled water can be repeatedly used or directly discharged after micro-treatment.
In the above waste acid recycling method and system, the treatment method of the mixed acid of fluorine and chlorine is as follows: the mixed acid of fluorine and chlorine obtained in the front end procedure enters a reactor, calcium hydroxide is added for reaction, the addition of the calcium hydroxide is controlled by controlling the pH value of the reactor, and fluorine in the mixed acid reacts with calcium to generate calcium fluoride precipitate;
and (3) after the reaction is finished, carrying out filter pressing on the reaction solution by using a filter press, wherein filter residues are calcium fluoride, evaporating and crystallizing filter liquor of the filter press to obtain calcium chloride crystals, and separating mixed acid of fluorine and chlorine to obtain qualified calcium fluoride and calcium chloride products for sale.
In the method and the system for recycling the waste acid, the filter press comprises a vertically arranged slag discharging cylinder, the upper end port and the lower end port of the slag discharging cylinder are both arranged in an open mode and are fixedly connected with horizontally arranged liquid material boxes, a plurality of vertically and closely arranged hollow filter plates are arranged in the slag discharging cylinder, a plurality of extrusion springs are fixedly connected between the two hollow filter plates positioned on two sides and the inner side wall of the slag discharging cylinder, the side walls on two sides of each hollow filter plate are inwards sunken to form a filter tank, the upper end and the lower end of each hollow filter plate are communicated with the liquid material boxes through guide pipes, each hollow filter plate is provided with a feed pipe in a penetrating mode, two ends of each feed pipe are communicated with the filter tank, a slag removing mechanism is arranged in each hollow filter plate, and a reciprocating mechanism.
In the method and the system for recycling the waste acid, the plurality of feeding pipes are arranged close to the upper end of the hollow filter plate, and the bottoms of the hollow filter plates are not in contact with the upper side wall of the liquid material box at the lower end.
In the method and the system for recycling the waste acid, the slag removal mechanism comprises a fixed bag fixedly connected to the side wall of the upper end of the hollow filter plate, electrorheological fluid is contained in the fixed bag, magnetic plates are fixedly connected to the opposite side walls of the two liquid material boxes, a rotating fan is fixedly installed in each hollow filter plate, and a conductive block coupled with the electrorheological fluid is fixedly embedded in each blade of the rotating fan; in the method and the system for recycling the waste acid, the plurality of rotating fans are all positioned at the upper end of the feeding pipe, and the side wall of the hollow filter plate, which is far away from one side of the fixed bag, is provided with a clamping groove matched with the fixed bag; in the above method and system for recycling waste acid, the reciprocating mechanism comprises a reciprocating rod which penetrates through two liquid material boxes, two plugs are fixedly connected to the reciprocating rod, two racks are horizontally arranged at one end of the reciprocating rod through a vertical rod and are fixedly connected with the connecting rod, two incomplete gears are meshed between the racks, multiple sections of teeth are arranged on the incomplete gears, two limit blocks are fixedly connected to one ends of the reciprocating rod away from the vertical rod, and the number of the sections of the teeth on the incomplete gears corresponds to the number of the hollow filter plates.
Compared with the prior art, the method and the system for recycling the waste acid have the advantages that:
1. according to the invention, by arranging the sulfuration arsenic removal and heavy metal treatment system, the waste acid contains sulfuric acid, heavy metal ions, arsenic and fluorine and chlorine, and the arsenic can react with hydrogen sulfide in the heavy metal removal reactor to generate precipitate to be removed; harmful tail gas can be purified and discharged by the harmful tower; after sodium hydroxide in the harm removal tower absorbs hydrogen sulfide gas which is not completely reacted, sodium sulfide solution can be generated and flows back to the gas generator for recycling.
2. The acid-resistant nanofiltration membrane is arranged for purification, so that heavy metal ions such as cadmium, mercury and the like in the polluted acid can be further removed, the multi-medium filter, the activated carbon filter and the microfiltration membrane play a role in physical filtration, the micro suspended matters in the polluted acid are mainly removed, and the turbidity of the polluted acid can be reduced to below 3; and the acid-resistant nanofiltration membrane can further remove heavy metal ions such as cadmium, mercury and the like in the polluted acid.
3. According to the invention, by arranging electrodialysis, the waste acid purified by the acid-resistant nanofiltration membrane contains a large amount of sulfuric acid, fluorine and chlorine and a small amount of heavy metal ions, the selective electrodialysis system can realize acid concentration and water desalination in the waste acid wastewater, and most of fluorine and chlorine ions enter concentrated acid, so that fluorine and chlorine in a dilute solution are low; and the concentrated solution generated by electrodialysis can enter the next round of electrodialysis circulation treatment.
4. According to the invention, the hot air blowing, concentrating and fluorine and chlorine removing process is set, the hot air blowing system adopts high-efficiency hot air concentration blowing, so that convection of dilute sulfuric acid materials and hot air is realized, most of water, hydrochloric acid and hydrofluoric acid with lower boiling points in sulfuric acid can be mixed into the hot air, and the sulfuric acid can flow down along the blowing and removing tower, so that sulfuric acid concentration and fluorine and chlorine removal in waste acid are realized; the tail gas containing moisture, hydrochloric acid and hydrofluoric acid from the top of the stripping tower is sent to an absorption tower to be absorbed by absorption liquid to form a fluorine-chlorine mixed acid which can be sent to a neutralized salt treatment system for recycling.
5. The invention sets a negative pressure evaporation concentration process, and the negative pressure evaporation concentration system adopts a single-effect negative pressure evaporation process for the waste acid. The 35% -40% dilute sulphuric acid solution passes through a preheating device and then enters an evaporation device, the solution is concentrated to 60%, water vapor generated by evaporation is condensed into distilled water with the acid content less than 0.6% through a condenser, and the distilled water can be repeatedly used or directly discharged after micro-treatment.
6. The method comprises the steps of treating by setting a mixed acid of fluorine and chlorine, introducing the mixed acid of fluorine and chlorine obtained in the front end procedure into a reactor, reacting with calcium under the condition of pH value to generate calcium fluoride which is an insoluble substance and calcium chloride which is an easily soluble substance, performing filter pressing by a filter press to obtain a calcium fluoride solid, and performing evaporation crystallization on the calcium chloride dissolved in the solution to obtain calcium chloride crystals, thereby realizing waste recycling.
7. According to the invention, the plurality of hollow filter plates which are tightly attached are arranged, materials enter the filter tanks on the plurality of hollow filter plates through the feeding pipes, liquid in the materials can enter the hollow filter plates through the through holes on the hollow filter plates, and filter pressing residues can be remained in the filter tanks, so that the filter pressing of the materials is realized.
8. According to the invention, by arranging the two liquid material boxes and the slag discharging barrel, filtrate can flow into the two liquid material boxes through the guide pipes at the upper end and the lower end of the hollow filter plate, when the two hollow filter plates are separated under the driving of the reciprocating mechanism and the slag discharging mechanism, filter pressing residues in the filter tank can fall to the bottom of the slag discharging barrel, so that the filter pressing of other hollow filter plates is not influenced in the slag discharging process, and the efficiency is higher.
9. The invention has the advantages that through the arrangement of the deslagging mechanism, under the normal condition, the rotating fan is driven to rotate in the process that liquid in the hollow filter plates flows to the liquid material box through the guide pipe, the conductive blocks in the rotating fan blades can cut magnetic induction lines between the two magnet plates to generate induced current, so that the electrorheological fluid in the fixed bag is solidified, the hollow filter plates can be tightly attached, when the reciprocating mechanism blocks the pipe openings at the upper end and the lower end of the two adjacent hollow filter plates, the liquid in the two blocked hollow filter plates can be in a non-flowing state, the rotating fan can stop rotating at the moment, the electrorheological fluid after power failure can be recovered to be in a liquid state, the two hollow filter plates can overcome the elasticity of the extrusion spring to be easily separated, and filter residues in the filter tank can fall into the deslagging cylinder.
10. According to the invention, the reciprocating mechanism is arranged, the incomplete gear is connected with a power device such as a motor, the incomplete gear can drive the two racks to intermittently reciprocate back and forth when rotating, the vertical rod drives the two reciprocating rods to move in the liquid material box, the two plug heads on the reciprocating rods can sequentially plug the pipe openings on the two adjacent hollow filter plates, the discharge of filter residues is realized, the working efficiency is high, and the time and the labor are saved.
Drawings
FIG. 1 is a general flow chart of a waste acid recycling method provided by the invention;
FIG. 2 is a flow chart of a system for treating arsenic sulfide and heavy metals in the method for recycling contaminated acid provided by the invention;
FIG. 3 is a flow chart of purification of an acid-resistant nanofiltration membrane in the method for recycling contaminated acid provided by the invention;
FIG. 4 is a flow chart of a process of hot air blowing, concentration and fluorine and chlorine removal in the polluted acid recycling treatment method provided by the invention;
FIG. 5 is a flow chart of the mixed acid treatment of fluorine and chlorine in the method for recycling contaminated acid provided by the invention;
FIG. 6 is a schematic structural diagram of a waste acid recycling system provided by the present invention;
fig. 7 is an enlarged schematic view of a structure at a in fig. 6.
In the figure, a slag discharging barrel 1, a liquid material box 2, a hollow filter plate 3, an extrusion spring 4, a filter tank 5, a guide pipe 6, a feed pipe 7, a fixed bag 8, a magnet plate 9, a rotating fan 10, a reciprocating rod 11, a plug 12, a vertical rod 13, a rack 14, a connecting rod 15, an incomplete gear 16 and a limiting block 17.
Detailed Description
The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Examples
As shown in fig. 1-5, a method for recycling waste acid includes the following steps: sulfurizing to remove arsenic and heavy metal, purifying with acid-resistant nanofiltration membrane, acid-purifying with fluidized bed, electrodialysis, hot air blowing to remove fluorine and chlorine, negative pressure evaporation and concentration, and treating with mixed acid of fluorine and chlorine;
the specific treatment method for removing arsenic and heavy metals by vulcanization comprises the following steps: the waste acid is collected and enters an adjusting tank for water quality and water quantity adjustment, and the wastewater enters a weight removal reaction after adjustmentDevice for simultaneously blowing in the generated H2S gas, in the heavy metal removal reactor, hydrogen sulfide gas reacts with arsenic heavy metal in the waste acid to generate precipitate, the precipitate is pumped into an FBL filter by a pump for solid-liquid separation, the bottom flow of the filter is subjected to filter pressing separation by a plate-and-frame filter press, and the sulfide slag is safely disposed;
tail gas generated by the reactor is sent to a harm removal tower for treatment, and the gas reaches the standard and is discharged;
the absorption liquid of the harm removing tower is mainly sodium hydroxide solution, sodium sulfide solution is generated after hydrogen sulfide gas is absorbed, a batch of absorption liquid is sent to a gas generator for treatment at intervals, and resource utilization of the absorption liquid is realized;
sulfuric acid and sodium hydrosulfide or sodium sulfide react in a gas generator to produce hydrogen sulfide gas and sodium sulfate solution, the hydrogen sulfide gas is sent to a heavy reaction tank to take part in the reaction, the sodium sulfate solution in the gas generator is periodically discharged to be evaporated and crystallized, crystals are sent to a rotary kiln, and reducing agent carbon powder is added at the same time, so that a sodium sulfide product generated by the reaction is recycled as a medicament.
The waste acid contains sulfuric acid, heavy metal ions, arsenic and fluorine and chlorine, and the arsenic can react with hydrogen sulfide in the weight removal reactor to generate precipitate to be removed; harmful tail gas can be purified and discharged by the harmful tower; after sodium hydroxide in the harm removal tower absorbs hydrogen sulfide gas which is not completely reacted, sodium sulfide solution can be generated and flows back to the gas generator for recycling.
And (3) water quality conditions after sulfuration arsenic removal and heavy metal treatment:
effluent quality (unit: mg/L) of waste acid vulcanizing section
| Index (I) | Acid concentration | F- | Cl- | As | Pb |
| After |
5～10％ | 2000 | 4000 | ≤1 | ≤1 |
The purification process of the acid-resistant nanofiltration membrane comprises the following steps: and (3) pretreating the polluted acid by sequentially passing the filtrate subjected to filter pressing separation through a multi-medium filter, an activated carbon filter, a microfiltration membrane and the like, pumping the pretreated purified acid into an acid-resistant nanofiltration membrane through a high-pressure pump, purifying the sulfuric acid by a permeation membrane, and intercepting metal ions by the membrane. The heavy metal ions such as cadmium, mercury and the like in the polluted acid can be further removed, the multi-medium filter, the activated carbon filter and the microfiltration membrane play a role in physical filtration, the micro suspended matters in the polluted acid are mainly removed, and the turbidity of the polluted acid can be reduced to below 3; and the acid-resistant nanofiltration membrane can further remove heavy metal ions such as cadmium, mercury and the like in the polluted acid.
The electrodialysis process is as follows: conveying the solution subjected to nanofiltration treatment to an electrodialysis stock solution tank, conveying the electrodialysis stock solution to an electrodialysis device I for treatment by using a pump, controlling electrodialysis conditions, producing a concentrated solution I and a dilute solution I after treatment, discharging about 10% of the concentrated solution I, treating the concentrated solution I by using a hot waste gas evaporation concentration system, further treating the dilute solution by using an electrodialysis device II, separating the dilute solution II and the concentrated solution II after membrane treatment by using the electrodialysis device II, wherein the dilute solution II is discharged to 1-2% and then subjected to hot air blowing concentration fluorine and chlorine removal treatment, and the concentrated solution enters the electrodialysis stock solution tank II to enter the next round of electrodialysis circulation treatment.
Dirty acid after nanofiltration treatment contains more metal ions and salt, the dirty acid is sent to an acid purification bed, acid recovery resin is carried in the bed layer, the acid recovery resin is existing resin, the surface of the resin has strong charges and can adsorb strong acid, and when acid-containing solution flows through the resin layer, the strong acid is adsorbed by the resin. The resin is regenerated by using clean water, water is reversely fed, and high-acid low-salt solution is extruded and then sent to an electrodialysis device for continuous treatment. Finally, a small amount of low-acid high-salt solution is left without recovery value and is sent to neutralization treatment.
The waste acid purified by the acid-resistant nanofiltration membrane contains a large amount of sulfuric acid, fluorine and chlorine and a small amount of heavy metal ions, the selective electrodialysis system can realize acid concentration and water desalination in waste acid and waste water, and most of fluorine and chlorine ions enter concentrated acid, so that fluorine and chlorine in a dilute solution are low; and the concentrated solution generated by electrodialysis can enter the next round of electrodialysis circulation treatment.
The hot air blowing concentration fluorine and chlorine removal process comprises the following steps: after electrodialysis, dilute sulfuric acid in the dilute liquid II enters the top of the stripping tower through a pump and is in countercurrent contact with hot air or hot waste gas from the bottom of the tower to transfer materials and heat, and most of water, hydrochloric acid and hydrofluoric acid in the sulfuric acid enter a gas phase to further concentrate, separate and purify the sulfuric acid;
the sulfuric acid which reaches the design index and comes out from the bottom of the stripping tower enters a crystallization kettle for crystallization, the crystallization liquid is filtered to recover salt, the filtrate is sent into a settling tank for further solid-liquid separation, the finished sulfuric acid solution enters a sulfuric acid storage tank for storage and can be returned to a production system for recycling, the tail gas coming out from the top of the stripping tower contains a certain amount of moisture, hydrochloric acid and hydrofluoric acid and is sent into a secondary absorption tower for hazard removal treatment, the mixed acid of fluorine and chlorine is obtained by primary absorption, and the mixed acid is sent to a neutralization salt treatment system;
and (3) absorbing residual hydrogen chloride and hydrogen fluoride in the tail gas by using sodium hydroxide alkali liquor at the tail gas final stage, and discharging the gas after reaching the standard.
The hot air stripping system adopts high-efficiency hot air concentration stripping to realize convection of dilute sulfuric acid materials and hot air, most of water, hydrochloric acid and hydrofluoric acid with lower boiling points in the sulfuric acid can be mixed into the hot air, and the sulfuric acid can flow down along a stripping tower, so that sulfuric acid concentration and fluorine-chlorine removal in the waste acid are realized; the tail gas containing moisture, hydrochloric acid and hydrofluoric acid from the top of the stripping tower is sent to an absorption tower to be absorbed by absorption liquid to form a fluorine-chlorine mixed acid which can be sent to a neutralized salt treatment system for recycling.
The treatment method of the mixed acid treatment of fluorine and chlorine comprises the following steps: the mixed acid of fluorine and chlorine obtained in the front end procedure enters a reactor, calcium hydroxide is added for reaction, the addition of the calcium hydroxide is controlled by controlling the pH value of the reactor, and fluorine in the mixed acid reacts with calcium to generate calcium fluoride precipitate;
and (3) after the reaction is finished, carrying out filter pressing on the reaction solution by using a filter press, wherein filter residues are calcium fluoride, evaporating and crystallizing filter liquor of the filter press to obtain calcium chloride crystals, and separating mixed acid of fluorine and chlorine to obtain qualified calcium fluoride and calcium chloride products for sale.
The mixed acid of fluorine and chlorine obtained in the front end procedure is introduced into a reactor, and reacts with calcium under the condition of pH value to generate insoluble calcium fluoride and soluble calcium chloride, calcium fluoride solid can be obtained by filter pressing of a filter press, calcium chloride dissolved in the solution can be obtained by evaporation and crystallization to obtain calcium chloride crystals, and waste recycling is realized.
As shown in fig. 6-7, a dirty sour resourceful treatment system, the pressure filter includes the sediment section of thick bamboo 1 of vertical setting, and the equal uncovered setting of the upper and lower port of sediment section of thick bamboo 1 and equal fixed connection have the liquid magazine 2 of level setting, and the filtrating can flow to two liquid magazines 2 in through pipe 6 of the upper and lower extreme of hollow filter plate 3, when two hollow filter plates 3 wherein drive under reciprocating mechanism and slagging-off mechanism and separately, the filter-pressing sediment in the filter tank 5 then can drop the bottom of sediment section of thick bamboo 1, can not influence going on of the filter-pressing of other hollow filter plates 3 at the in-process of arranging the sediment, and efficiency is higher.
Arrange the hollow filter plate 3 that a plurality of equal vertical inseparable arrange in the sediment section of thick bamboo 1, be located two hollow filter plates 3 of both sides and arrange many extrusion springs 4 of fixedly connected with between the sediment section of thick bamboo 1 inside wall, 3 both sides lateral walls of hollow filter plate all inwards cave in and form filter-tank 5, the material enters into in the filter-tank 5 on a plurality of hollow filter plates 3 through inlet pipe 7, liquid in the material can enter into hollow filter plate 3 through the through-hole on the hollow filter plate 3 inside, and the filter-pressing sediment then can stay in filter-tank 5, thereby realize the filter-pressing of material.
Every hollow filter plate 3 go up the lower extreme and all communicate with liquid magazine 2 through pipe 6, all run through connection has inlet pipe 7 on every hollow filter plate 3, the both ends of inlet pipe 7 all communicate with rose tank 5, it is worth mentioning, many inlet pipes 7 all are close to 3 upper ends of hollow filter plate and set up, 3 upper end liquid of hollow filter plate are more clarified, avoid inlet pipe 7 to be blocked, rotate fan 10 and blocked by impurity, the 3 bottoms of polylith hollow filter plate with be located 2 side wall contactless settings on the lower extreme liquid magazine.
Be equipped with the slagging-off mechanism in the hollow filter plate 3, it is concrete, the slagging-off mechanism includes fixed bag 8 of fixed connection on the lateral wall of hollow filter plate 3 upper end, contains the electrorheological fluids in the fixed bag 8, all fixedly connected with magnet board 9 on the lateral wall that two liquid magazine 2 back on the back, all fixedly mounted has rotation fan 10 in every hollow filter plate 3.
All fixedly in the blade of every rotation fan 10 to inlay the conducting block who is connected with the electrorheological fluids coupling, it should be said that, a plurality of rotation fans 10 all are located the inlet pipe 7 upper end, offer the joint groove that matches the setting with fixed bag 8 on the lateral wall of hollow filter plate 3 keeping away from fixed bag 8 one side.
Under the normal condition, the in-process that the liquid in the hollow filter plate 3 passes through 6 flow direction liquid magazine 2 of pipe can drive the rotation fan 10 and rotate, the conducting block in the rotation fan 10 blade can cut the magnetic induction line between two magnet plates 9 and produce induced-current, make the electrorheological fluid in the fixed bag 8 solid state, can closely laminate between the hollow filter plate 3 of polylith, when 6 mouths of pipe of lower extreme are plugged up with two adjacent hollow filter plates 3 to reciprocating mechanism, the liquid in two hollow filter plates 3 that are plugged up just can be in the non-flow state, rotation fan 10 wherein can stall this moment, the electrorheological fluid of outage just can resume to liquid, two hollow filter plates 3 just can overcome extrusion spring 4's elasticity and part easily, the filter residue in the filter tank 5 just can drop in the sediment section of thick bamboo 1.
Be equipped with reciprocating mechanism jointly between two liquid magazine 2, it is specific, reciprocating mechanism is including running through two reciprocating rod 11 that liquid magazine 2 set up, two chock plugs 12 of equal fixedly connected with on two reciprocating rod 11, and the rack 14 that the level set up is all passed through montant 13 fixed connection to the one end of two reciprocating rod 11, and fixedly connected with connecting rod 15 between two racks 14, meshing is connected with incomplete gear 16 between two racks 14.
The incomplete gear 16 is provided with a plurality of sections of teeth, it should be noted that one end of each of the two reciprocating rods 11, which is far away from the vertical rod 13, is fixedly connected with a limiting block 17, and the number of the sections of the teeth on the incomplete gear 16 corresponds to the number of the hollow filter plates 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for recycling waste acid is characterized by comprising the following steps: sulfurizing to remove arsenic and heavy metal, purifying with acid-resistant nanofiltration membrane, electrodialysis, acid purification in fluidized bed, hot air blowing to remove fluorine and chlorine, negative pressure evaporation and concentration, and treating with mixed acid of fluorine and chlorine;
the specific treatment method for removing arsenic and heavy metals by vulcanization comprises the following steps: the waste acid is collected and enters an adjusting tank for water quality and water quantity adjustment, the wastewater after adjustment enters a weight removal reactor, and simultaneously generated H is blown in2S gas, in the heavy metal removal reactor, hydrogen sulfide gas reacts with arsenic heavy metal in the waste acid to generate precipitate, the precipitate is pumped into an FBL filter by a pump for solid-liquid separation, the bottom flow of the filter is subjected to filter pressing separation by a plate-and-frame filter press, and the sulfide slag is safely disposed;
tail gas generated by the reactor is sent to a harm removal tower for treatment, and the gas reaches the standard and is discharged;
the absorption liquid of the harm removing tower is mainly sodium hydroxide solution, sodium sulfide solution is generated after hydrogen sulfide gas is absorbed, a batch of absorption liquid is sent to a gas generator for treatment at intervals, and resource utilization of the absorption liquid is realized.
2. The method for recycling the polluted acid as claimed in claim 1, wherein the purification process of the acid-resistant nanofiltration membrane comprises the following steps: pretreating the polluted acid by sequentially passing the filtrate subjected to filter pressing separation through a multi-medium filter, an activated carbon filter, a microfiltration membrane and the like, pumping the pretreated purified acid into an acid-resistant nanofiltration membrane through a high-pressure pump, purifying the sulfuric acid by a permeation membrane, and intercepting metal ions by a membrane; purified acid directly enters electrodialysis for treatment after purification, and waste acid intercepted by a nanofiltration membrane enters an acid purification bed for further purification and impurity removal because the waste acid contains more metal ions and salt; the hydrogen sulfide gas is generated by two methods:
one method is that hydrogen gas prepared by methanol decomposition and sublimed sulfur steam are subjected to synthesis reaction in a synthesis tower to prepare hydrogen sulfide, the generated hydrogen sulfide gas is introduced into a rear-section vulcanization purification system to be used as a reactant, the generated carbon dioxide tail gas is directly discharged, and a gas generation system controls the gas generation amount by adding raw materials;
the method is characterized in that sulfuric acid and sodium hydrosulfide or sodium sulfide react in a gas generator to produce hydrogen sulfide gas and sodium sulfate solution, the hydrogen sulfide gas is sent to a heavy reaction tank to react, the sodium sulfate solution in the gas generator is periodically discharged to be evaporated and crystallized, crystals are sent to a rotary kiln, and reducing agent carbon powder is added at the same time, so that a sodium sulfide product generated by the reaction is recycled as a medicament.
3. The method for recycling waste acid according to claim 1, wherein the purification process of the acid purification bed comprises the following steps: dirty acid after nanofiltration treatment contains more metal ions and salt, and is sent to an acid purification bed, acid recovery resin is carried in the bed layer, the acid recovery resin is a type of existing resin, the surface of the type of resin has strong charges and can adsorb strong acid, and when acid-containing solution flows through the resin layer, the strong acid is adsorbed by the resin; the resin is regenerated by using clean water, water is reversely fed, and high-acid low-salt solution is extruded and then sent to an electrodialysis device for continuous treatment. Finally, a small amount of low-acid high-salt solution is left without recovery value and is sent to neutralization treatment.
4. The method for recycling waste acid according to claim 1, wherein the electrodialysis process comprises the following steps: and conveying the clean solution subjected to nanofiltration treatment to an electrodialysis stock solution tank, conveying the electrodialysis stock solution to an electrodialysis device I for treatment by using a pump, controlling the electrodialysis condition, producing a concentrated solution I and a dilute solution I after treatment, discharging about 10% of the concentrated solution I, conveying the discharged concentrated solution I into a hot waste gas evaporation concentration system for treatment, conveying the dilute solution into the electrodialysis device II for further treatment, separating the dilute solution II and the concentrated solution II after treatment by the electrodialysis device II, wherein the dilute solution II is directly reused in the production system after reaching 1-2% of the discharged dilute solution II, and conveying the concentrated solution into the electrodialysis stock solution tank II for next round of electrodialysis circulation treatment.
5. The method for recycling waste acid according to claim 1, wherein the treatment process of blowing off concentrated fluorine and chlorine by hot air comprises the following steps: after electrodialysis, dilute sulfuric acid in the dilute liquid II enters the top of the stripping tower through a pump and is in countercurrent contact with hot air or hot waste gas from the bottom of the tower to transfer materials and heat, and most of water, hydrochloric acid and hydrofluoric acid in the sulfuric acid enter a gas phase to further concentrate, separate and purify the sulfuric acid;
the sulfuric acid which reaches the design index and comes out of the bottom of the stripping tower enters a crystallization kettle for crystallization, the crystallization liquid is filtered to recover salt, the filtrate is sent into a settling tank for further solid-liquid separation, the finished sulfuric acid solution enters a sulfuric acid storage tank for storage and can be returned to a production system for recycling or enter the next step for continuous treatment, the tail gas coming out of the top of the stripping tower contains a certain amount of moisture, hydrochloric acid and hydrofluoric acid and is sent into a secondary absorption tower for pest removal treatment, the mixed acid of fluorine and chlorine is obtained by primary absorption, and the mixed acid is sent to a neutralization salt treatment system;
and (3) absorbing residual hydrogen chloride and hydrogen fluoride in the tail gas by using sodium hydroxide alkali liquor at the tail gas final stage, and discharging the gas after reaching the standard.
6. The method for recycling waste acid according to claim 1, wherein the negative pressure evaporation concentration treatment comprises the following steps: the concentration of the waste acid after hot air stripping and concentration is about 40 percent, the amount is large, the difficulty is brought to the whole recycling, and the waste acid is subjected to a single-effect negative pressure evaporation process; the 35% -40% dilute sulphuric acid solution passes through a preheating device and then enters an evaporation device, the solution is concentrated to 60%, water vapor generated by evaporation is condensed into distilled water with the acid content less than 0.6% through a condenser, and the distilled water can be repeatedly used or directly discharged after micro-treatment.
7. The method for recycling waste acid according to claim 1, wherein the method for recycling the mixed acid of fluorine and chlorine comprises: the mixed acid of fluorine and chlorine obtained in the front end procedure enters a reactor, calcium hydroxide is added for reaction, the addition of the calcium hydroxide is controlled by controlling the pH value of the reactor, and fluorine in the mixed acid reacts with calcium to generate calcium fluoride precipitate;
and (3) after the reaction is finished, carrying out filter pressing on the reaction solution by using a filter press, wherein filter residues are calcium fluoride, evaporating and crystallizing filter liquor of the filter press to obtain calcium chloride crystals, and separating mixed acid of fluorine and chlorine to obtain qualified calcium fluoride and calcium chloride products for sale.
8. A dirty acid recycling system for the dirty acid recycling method according to any one of claims 1 to 7, comprising: the filter press comprises a slag discharging barrel which is vertically arranged, wherein the upper end port and the lower end port of the slag discharging barrel are both provided with an opening and are fixedly connected with a liquid material box which is horizontally arranged, a plurality of vertical hollow filter plates which are closely arranged are arranged in the slag discharging barrel, two hollow filter plates are positioned on two sides, a plurality of extrusion springs are fixedly connected between the hollow filter plates and the inner side wall of the slag discharging barrel, the side walls of two sides of the hollow filter plates are both inwards sunken to form a filter tank, each hollow filter plate is communicated with the liquid material box through a guide pipe at the upper end and the lower end of the hollow filter plate, each hollow filter plate is provided with an inlet pipe in a penetrating mode, two ends of the inlet pipe are communicated with the filter tank.
9. The waste acid recycling treatment system according to claim 8, wherein the plurality of feed pipes are arranged close to the upper end of the hollow filter plate, and the bottoms of the plurality of hollow filter plates are arranged in a manner of not contacting with the upper side wall of the liquid material box at the lower end.
10. The waste acid recycling treatment system according to claim 9, wherein the deslagging mechanism comprises a fixed bag fixedly connected to a side wall of an upper end of the hollow filter plate, the fixed bag contains electrorheological fluid, two side walls of the two liquid material boxes, which are opposite to each other, are fixedly connected with a magnet plate, a rotating fan is fixedly installed in each hollow filter plate, and a conductive block coupled with the electrorheological fluid is fixedly embedded in a blade of each rotating fan; the rotating fans are all positioned at the upper end of the feeding pipe, and the side wall of the hollow filter plate, which is far away from one side of the fixed bag, is provided with a clamping groove matched with the fixed bag; reciprocating mechanism is including running through the reciprocating lever that two liquid magazine set up, two chock plug of equal fixedly connected with on the reciprocating lever, two the rack that montant fixed connection level set up is all passed through to the one end of reciprocating lever, two fixedly connected with connecting rod between the rack, two the meshing is connected with incomplete gear between the rack, be equipped with multistage tooth on the incomplete gear, two the reciprocating lever is kept away from the one end fixedly connected with stopper of montant, the number of sections of tooth corresponds the setting with the quantity of hollow filter plate on the incomplete gear.
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