CN113774213A - Recycling method and system of stainless steel mixed acid pickling sludge - Google Patents
Recycling method and system of stainless steel mixed acid pickling sludge Download PDFInfo
- Publication number
- CN113774213A CN113774213A CN202110936827.3A CN202110936827A CN113774213A CN 113774213 A CN113774213 A CN 113774213A CN 202110936827 A CN202110936827 A CN 202110936827A CN 113774213 A CN113774213 A CN 113774213A
- Authority
- CN
- China
- Prior art keywords
- sludge
- mixed acid
- stainless steel
- slurry
- roasting furnace
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1213—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a recycling method and a recycling system for stainless steel mixed acid pickling sludge; preparing alkaline solution by mixing the condensate or water or the mixture of the condensate and the water with ammonia water, and adding stainless steel mixed acid pickling sludge into the alkaline solution to perform high-speed dispersion pulping; the pH value of the obtained slurry reaches 6-9; discharging the sludge into a vibration filter containing a 40-60 mesh filter screen to remove large-particle sludge solids after the neutralization process is finishedDischarging the residual sludge body into a sludge tank with stirring; conveying the sludge slurry in the sludge tank to a mixed acid regeneration spray roasting furnace, and spraying the sludge slurry into the furnace by using a spray gun; the sludge slurry is subjected to chemical reaction in a roasting furnace to generate solid metal oxide, HF gas and HNO3A gas; the obtained solid metal oxide falls into the bottom of the roasting furnace and is discharged and recovered; the obtained gas enters an absorption tower from the top of the roasting furnace through a pre-concentrator to form regenerated acid; and (4) introducing redundant waste gas into a cooling tower, collecting generated condensate, and neutralizing the condensate by ammonia water.
Description
Technical Field
The invention relates to a recycling method and a recycling system for stainless steel mixed acid pickling sludge.
Background
In the metallurgical industry, the mixed solution of nitric acid and hydrofluoric acid is adopted to carry out acid pickling on stainless steel, and a large amount of MeF-containing waste pickling liquid can be generated3The sludge of (2). It generates the reaction equation as follows:
Me+4HNO3＝Me(NO3)3+NO+2H2O
Me(NO3)3+3HF＝MeF3↓+3HNO3
Me2O3+6HNO3＝2Me(NO3)3+3H2O
MeO+4HNO3＝Me(NO3)3+2H2O+NO2
Me3O4+10HNO3＝3Me(NO3)3+5H2O+NO2
Me(NO3)3+3HF＝MeF3↓+3HNO3
the pickling waste liquid sludge contains water, waste acid and various heavy metals (such as nickel, chromium, titanium, molybdenum and the like), is extremely harmful, and belongs to extremely harmful waste in the metallurgical industry. The waste acid contains the heavy metal ions or precipitates (containing MeF)3Sludge), the water content of the sludge is directly reduced to about 60-70% by a simple filter pressing system during the acid washing line treatment, and an acid sludge cake with low water content is formed. Enterprises with smelting systems at the front ends generally transport the collected materials to the smelting systems of the metallurgical enterprises to be used as raw materials to be mixed with iron ore and other raw materials, but the sludge still contains a large amount of F-、NO3 -During the heating process of the smelting system, a great amount of HF and HNO are generated3Causing severe corrosion to smelting equipment. In addition, enterprises send the sludge of the pickling line out for treatment, but the treatment cost is high; enterprises discharge the direct sewage to a wastewater treatment station for treatment, and heavy metal ions or sludge in the acid liquor is precipitated by adding lime or alkali liquor, but a larger amount of sludge is generated, so that the enterprises are subjected to greater treatment trouble.
Disclosure of Invention
In order to thoroughly eliminate the harm of waste acid sludge to the environment and reduce the treatment cost and the operation cost of enterprises, the invention provides the method and the system for recycling the stainless steel mixed acid pickling sludge, and the aims of thoroughly harmless and recycling the stainless steel enterprise mixed acid pickling sludge are fulfilled.
In order to achieve the purpose, the technical scheme is as follows:
the recycling method of the stainless steel mixed acid pickling sludge comprises the following steps:
(1) mixing the condensate or water or the mixture of the condensate and the water collected by the cooling tower with ammonia water to prepare an alkaline solution, and then transferring the alkaline solution to a high-speed dispersion machine;
(2) adding stainless steel mixed acid pickling sludge into the obtained alkaline solution for acid-base neutralization, and simultaneously dispersing at a high speed for pulping, wherein the pH value of the obtained pulp reaches 6-9;
the sludge contains nitric acid and hydrofluoric acid which have high corrosivity, so that the equipment tolerance of the subsequent process is guaranteed, the sludge is added into ammonia water for neutralization, and the neutralization process comprises the following chemical reactions:
HNO3+NH4OH＝NH4NO3+H2O；
HF+NH4OH＝NH4F+H2O；
Me(NO3)2+2NH4OH＝Me(OH)2+2NH4NO3；
Me(NO3)3+2NH4OH＝Me(OH)3+2NH4NO3；
3) discharging the sludge into a vibration filter containing a 40-60 mesh filter screen to remove large-particle sludge solids, and discharging residual sludge slurry into a slurry tank with stirring;
4) conveying the sludge slurry in the sludge tank to a mixed acid regeneration spray roasting furnace, and spraying the sludge slurry into the furnace by using a spray gun; the sludge slurry is subjected to chemical reaction in a roasting furnace to generate solid metal oxide, HF gas and HNO3A gas;
the firing process involves the following chemical reactions:
MeF2(aqueous solution) + H2O (gas) ═ MeO (solid) +2HF (gas), fluoride decomposition;
Me(NO3)2+H2o (gas) ═ MeO (solid) +2HNO3(gas), nitrate hydrolysis;
2NH4NO3＝2N2(gas) +2O2(gas) +4H2O, decomposing ammonium nitrate;
2NH4F＝NH3(gas) + HF (gas), ammonium fluoride decomposes;
2HNO3(gas) ═ NO2(gas) + H2O (gas) + O2(gas), decomposition with nitric acid;
NO2＝NO+1/2O2；
4NH3+3O2＝2N2+6H2O；
Me(OH)2＝MeO+H2O；
2Me(OH)3＝Me2O3+3H2O；
5) the obtained solid metal oxide falls into the bottom of the roasting furnace and is discharged and recovered; the obtained acid gas enters an absorption tower from the top of the roasting furnace through a pre-concentrator to form regenerated acid; and (4) introducing redundant waste gas into a cooling tower, and collecting generated condensate.
According to the scheme, the concentration of the ammonia water in the step 1 is more than 20 wt%.
According to the scheme, the concentration of the slurry obtained in the step 2 is 20-30 wt%.
According to the scheme, the large-particle sludge solids in the step 3 are collected and returned to the step 2 for high-speed dispersion pulping.
According to the scheme, the spray gun in the step 4 is provided with an atomizing nozzle, and the spray pressure at the nozzle is 0.4-0.6 MPa; the spray gun and the atomizing nozzle are made of SiC or SUS316L materials.
According to the scheme, the temperature of the top of the mixed acid regeneration spray roasting furnace in the step 4 is higher than 320 ℃.
According to the scheme, the mixed acid pickling waste liquid generated by the stainless steel pickling line is treated simultaneously in the step 4, and is sprayed into the roasting furnace by adopting different spray heads with the sludge slurry body; the mixed acid pickling waste liquid is supernatant liquid obtained after sludge is removed through precipitation.
According to the scheme, the condensate collected in the step 5 returns to the step 1 to prepare the alkaline solution with the ammonia water.
The recycling system of stainless steel mixed acid pickling sludge comprises:
a neutralization agitation tank for preparing an alkaline solution, having an inlet for water and an alkaline agent to enter, and discharging the resulting alkaline solution through a neutralization pump;
the high-speed dispersion machine is used for carrying out neutralization reaction on the alkaline solution and the stainless steel mixed acid washing sludge, is provided with an inlet for washing the sludge and is communicated with the neutralization liquid pump, and the neutralized sludge is discharged through the control of the electromagnetic valve;
the vibration filter is used for filtering the obtained neutralized slurry and is communicated with the electromagnetic valve; separating sludge particles and sludge slurry by vibration filtration;
the mud tank is used for collecting the mud body and is provided with a stirring paddle;
the mixed acid regeneration spray roasting furnace is used for treating the collected sludge slurry, the sludge slurry is conveyed to the roasting furnace through a slurry conveying pump and is sprayed from the top of the furnace through a sludge spray gun; the bottom of the roasting furnace is provided with a scraper rake for discharging metal oxide byproducts, and the top of the furnace is provided with an exhaust port;
the gas discharged from the gas outlet is treated by a pre-concentrator and an absorption tower, the gas enters the absorption tower after being pre-concentrated, and the residual gas after absorption treatment is discharged from the top of the tower;
and the cooling tower is used for condensing the residual gas, collecting condensed water for recycling, and feeding the condensed water into the neutralization stirring tank through a water inlet.
Compared with the prior art, the invention has the beneficial effects that:
(1) the sludge is roasted after pulping, so that complete recycling and harmless treatment of the stainless steel mixed acid sludge can be realized, high-value metals such as nickel, chromium, titanium, molybdenum and the like in the acid sludge can be recovered, and the treatment cost of a metallurgical enterprise is reduced.
(2) The method for pretreating the acid-washing sludge by adopting the alkaline solution can effectively improve the material application applicability of pulping and screening equipment, prolong the service life of the equipment and realize simple and reliable process operation.
(3) The method for performing synergistic treatment by directly spraying the filtered sludge slurry into the mixed acid regeneration roasting furnace can complete roasting regeneration of sludge and waste acid at the same time, and maximally improve the applicability of a unit.
(4) The condensate generated in the mixed acid regeneration system is used as the pulping raw material, so that the full cyclic utilization of water is realized, and the waste of water resources is reduced.
Drawings
FIG. 1: the invention discloses a schematic diagram of a stainless steel mixed acid waste liquid sludge recycling system.
Wherein, 1, a neutralization stirring tank; 2. a neutralization liquid pump; 3. a high-speed disperser; 4. an electromagnetic valve; 5. a vibration filter; 6. a mud tank; 7. a slurry delivery pump; 8. a sludge spray gun; 9. regenerating a spray roasting furnace by using mixed acid; 10. scraping and harrowing; 11. rotating the valve; 12. a waste acid spray gun; 13. concentrating a waste acid filter; 14. a roasting furnace pump; 15. a pre-concentration pump; 16. a preconcentrator; 17. an absorption tower; 18. and (5) cooling the tower.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Example 1:
the embodiment provides a recycling method and a corresponding system for stainless steel mixed acid pickling sludge, and the specific process is as follows:
firstly, water (or condensate collected by a cooling tower 18) and ammonia water solution are delivered into a neutralization stirring tank 1 according to a certain proportion, taking the example of treating 400 kg of acid-washing sludge per day in a stainless steel factory in a certain area, the thickness of the acid-washing sludge needs 0.8m3Water (g) and 60L of a 20% aqueous ammonia solution. Then, the prepared alkaline solution is delivered to a high-speed dispersion machine 3 containing the acid-washed sludge by a neutralization liquid pump 2, and the acid-washed sludge is prepared to be neutral or weakly alkaline under dispersion conditions. After the slurry is fully dispersed, the electromagnetic valve 4 is opened, and the neutralized slurry passes through a filter screen by gravity and is subjected to vibration filtration with 40-60 meshesIn the device 5, the filtered sludge slurry flows out from the lower port of the vibrating filter screen and is sent to a sludge tank 6, and large solid particles of the sludge which is not filtered are collected by the upper port of the vibrating filter screen and return to the high-speed dispersion machine 3 for re-dispersion and pulping. The sludge slurry in the sludge tank is stably conveyed to a sludge spray gun 8 through a slurry conveying pump 7, the sludge spray gun and one waste acid spray gun share a lower gun mouth, the acid gun needs to be lifted when the sludge is sprayed, and meanwhile, the treatment capacity of the sludge spray gun is consistent with that of the acid gun, so that the integral treatment capacity of the roasting furnace is ensured to be unchanged. The neutralization stirring tank 1, the high-speed dispersion machine 3, the vibration filter 5 and the mud tank 6 are made of stainless steel, and the parts of the high-speed dispersion machine, which are in contact with the mixed acid waste liquid and mud, can be made of acid-resistant materials, such as stainless steel lined glass fiber reinforced plastics, stainless steel lined PPH and the like, are mainly dispersible tablets, and can be used as consumables and can be replaced at regular time.
The sludge spray gun 8 can be arranged at the top or the waist of the mixed acid regeneration spray roasting furnace 9, the sludge spray gun 8 and the waste acid spray gun 12 are provided with the atomizing nozzles as the same as the spray guns, only the aperture sizes of the nozzles are different, the sludge spray gun 8 and the atomizing nozzles are made of SiC or SUS316L, and sludge slurry is sprayed into the roasting furnace 9 in a spraying state for independent treatment. In the mode, the preconcentrator 16 is in a water operation mode, the mixed acid pickling waste liquid diluted in the preconcentrator 16 is subjected to self circulation through the preconcentration pump 15, when sludge slurry is sprayed into the roasting furnace 9 through the sludge spray gun 8, the system is adjusted in a linkage manner, the temperature of the top of the roasting furnace 9 is rapidly increased to be higher than 320 ℃ to control the temperature of the top of the roasting furnace 9, meanwhile, the rotating speed of the scraper 10 at the bottom of the roasting furnace 9 is reduced to be lower than 1r/min, and the longer retention time of solid metal oxide and incompletely decomposed mixed acid waste liquid sludge is obtained by reducing the rotating speed of the scraper 10, so that fluoride in the mixed acid waste liquid sludge is completely decomposed.
The sludge slurry fully reacts in a roasting furnace 9 to generate solid metal oxide, HF gas and HNO3Gas, wherein the solid metal oxide falls to the bottom of the roasting furnace 9 under the action of gravity and centrifugal force, and is discharged to an oxide collecting system through a scraper 10 and a rotary valve 11 for storage; HF gas, HNO3Negative pressure suction of gas in waste gas fan of mixed acid regeneration systemUnder the action, the mixed acid enters an absorption tower 17 through a preconcentrator 16 and is absorbed by spray liquid to produce regenerated mixed acid; and discharging the residual gas after the absorption treatment from the tower top to a cooling tower 18, and collecting condensate for recycling in the neutralization stirring tank 1 to prepare an alkaline solution together with ammonia water. Unabsorbed flue gas containing nitrogen oxides and the like continuously enters subsequent flue gas oxidation equipment for continuous treatment, and is discharged after reaching the standard.
Example 2:
the embodiment provides a recycling method and a corresponding system for stainless steel mixed acid waste liquid sludge, the treated sludge and pickling waste acid normally sprayed into a roasting furnace are allocated together for operation treatment, and the specific process is as follows:
the condensate and ammonia water produced by the mixed acid regeneration unit are delivered into a neutralization stirring tank 1 according to a certain proportion, taking the example of treating 400 kg of acid-washing sludge per day in a stainless steel plant in a certain area, the treatment needs 0.8m3Water (g) and 60L of a 20% aqueous ammonia solution. The prepared alkaline solution is conveyed to a high-speed disperser 3 containing the acid-washed sludge by a neutralization liquid pump 2, and the acid-washed sludge is prepared to be neutral or weakly alkaline under dispersion conditions. After the slurry is fully dispersed, the electromagnetic valve 4 is opened, the slurry passes through the vibration filter 5 with a 40-60-mesh filter screen by gravity, wherein the filtered sludge slurry flows out from the lower port of the vibration filter screen and is conveyed into the slurry tank 6, and the large solid particles which are not filtered are collected by the upper port of the vibration filter screen and return to the high-speed disperser 3 for re-dispersing and pulping. The sludge slurry in the sludge tank is stably conveyed to a sludge spray gun 8 through a slurry conveying pump 7, the sludge spray gun and one waste acid spray gun share a lower gun mouth, the acid gun is lifted during sludge spraying, and meanwhile, the treatment capacity of the sludge spray gun is consistent with that of the acid gun, so that the integral treatment capacity of the roasting furnace is guaranteed to be unchanged. Wherein neutralization agitator tank 1, high-speed dispersion machine 3, vibration filter 5, mud jar 6 adopt stainless steel material can, and the high dispersion machine with mixed acid waste liquid mud contact site can all adopt acid-fast material, like stainless steel lining glass steel, stainless steel lining PPH etc. mainly is the dispersion tablet, this part can regard as the consumptive material, regularly change can.
The sludge spray gun 8 can be arranged at the top or the waist of the mixed acid regeneration spray roasting furnace 9, the sludge spray gun 8 and the waste acid spray gun 12 are provided with the atomizing nozzles as the same, only the aperture sizes of the nozzles are different, and the sludge spray gun 8 and the atomizing nozzles are made of SiC or SUS 316L. Meanwhile, after the mixed acid pickling waste liquid is concentrated by the preconcentrator 16, the concentrated acid pickling waste liquid is sprayed into the roasting furnace 9 through the preconcentration pump 15, the roasting furnace pump 14, the concentrated waste acid filter 13 and the waste acid spray gun 12 in sequence, and the mixed acid regeneration spray roasting furnace 9 simultaneously carries out chemical reaction treatment on the mixed acid waste liquid sludge and the pickling waste acid. In the treatment mode, the temperature of the top of the roasting furnace 9 is increased to about 320 ℃ for control, meanwhile, the rotating speed of the scraper 10 at the bottom of the roasting furnace 9 is reduced to be below 1r/min, and the rotating speed of the scraper 10 is reduced to obtain the solid metal oxide and longer retention time of the incompletely decomposed mixed acid waste liquid sludge, so that the fluoride in the mixed acid waste liquid sludge is completely decomposed; meanwhile, the system automatically adjusts the acid inlet amount of the preconcentrator 16 and the spraying amount of the waste acid spray gun 12 at the top of the roasting furnace 9, the concentrated mixed acid pickling waste liquid and the sludge slurry sprayed by the sludge spray gun 9 are adjusted according to a certain proportion, under general conditions, the total spraying amount of the sludge slurry in the roasting furnace 9 and the mixed acid pickling waste liquid is not higher than the treatment amount when only the mixed acid pickling waste liquid is treated, and then the inlet amount of the mixed acid pickling waste liquid in the preconcentrator 16 and the spraying amount of the mixed acid pickling waste liquid at the top of the roasting furnace 9 are reduced according to a blending proportion, so that the sludge of the mixed acid pickling waste liquid can be fully reacted in the roasting furnace 9.
The mixed acid waste liquid sludge and the pickling waste acid are fully reacted in a roasting furnace 9 to generate solid metal oxide, HF gas and HNO3Gas, wherein the solid metal oxide falls to the bottom of the roasting furnace 9 under the action of gravity and centrifugal force, and is discharged to an oxide collecting system through a scraper 10 and a rotary valve 11 for storage; HF gas, HNO3Under the negative pressure suction effect of a waste gas fan of the mixed acid regeneration system, the gas enters an absorption tower 17 through a preconcentrator 16 and is absorbed by spraying liquid to produce regenerated mixed acid; and discharging the residual gas after the absorption treatment from the tower top to a cooling tower 18, and collecting the generated condensate for recycling in the neutralization stirring tank 1 for preparing the alkaline solution. Unabsorbed flue gas containing nitrogen oxides and the like continuously enters the post flue gas purification and oxidation equipment for continuous treatment, and is discharged after reaching the standard.
In the above embodiment, the roasting furnace 9 is composed of the upper part and the lower part, and the upper part and the lower part are uniformly provided with the burners for heating, so that the mixed acid waste liquid sludge can be subjected to full hydrolysis reaction in the roasting furnace 9; the scraper 10 is positioned at the lower part of the roasting furnace, so that solid metal oxides at the bottom of the roasting furnace 9 are prevented from being accumulated, and the reaction efficiency in the roasting furnace 9 is improved.
In conclusion, the stainless steel mixed acid waste liquid sludge harmless treatment method provided by the invention can greatly reduce the yield of acid sludge and reduce the treatment cost of metallurgical enterprises; on the other hand, the acidic sludge can be recycled, which is beneficial to the mixed acid regeneration system to improve F-NO3And the recovery rate is high, a large amount of high-value metal ions such as nickel, chromium, titanium, molybdenum and the like in the acid sludge are recovered, solid metal oxide with high added value is formed, the economic value is high, the corrosion of the solid metal oxide generated by the sludge to a front-end smelting system of an enterprise can be eliminated, and the stable operation of the preorder equipment is effectively protected.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims and any design similar or equivalent to the scope of the invention.
Claims (9)
1. The recycling method of the stainless steel mixed acid pickling sludge is characterized by comprising the following steps:
(1) mixing the condensate or water or the mixture of the condensate and the water collected by the cooling tower with ammonia water to prepare an alkaline solution, and then transferring the alkaline solution to a high-speed dispersion machine;
(2) adding stainless steel mixed acid pickling sludge into the obtained alkaline solution for acid-base neutralization, and simultaneously dispersing at a high speed for pulping, wherein the pH value of the obtained pulp reaches 6-9;
(3) discharging the sludge into a vibration filter containing a 40-60 mesh filter screen to remove large-particle sludge solids after the neutralization process is finished, and discharging residual sludge slurry into a slurry tank with stirring;
(4) conveying the sludge slurry in the sludge tank to a mixed acid regeneration spray roasting furnace, and spraying the sludge slurry into the furnace by using a spray gun; the sludge slurry is subjected to chemical reaction in a roasting furnace to generate solid metal oxide, HF gas and HNO3A gas;
(5) the obtained solid metal oxide falls into the bottom of the roasting furnace and is discharged and recovered; the obtained gas enters an absorption tower from the top of the roasting furnace through a pre-concentrator to form regenerated acid; and (4) introducing redundant waste gas into a cooling tower, collecting generated condensate, and neutralizing the condensate by ammonia water.
2. The method for recycling mixed acid pickling sludge of stainless steel according to claim 1, wherein the concentration of ammonia water in step 1 is 20 wt% or more.
3. The method for recycling the stainless steel mixed acid pickling sludge as claimed in claim 1, wherein the concentration of the slurry in the step 2 is 20-30 wt%.
4. The method for recycling stainless steel mixed acid pickling sludge as claimed in claim 1, wherein the large-particle sludge solids in step 3 are collected and returned to the high-speed dispersion pulping in step 2.
5. The recycling method of stainless steel mixed acid pickling sludge according to claim 1, wherein the spray gun in step 4 is provided with an atomizing nozzle, and the spray pressure at the nozzle is 0.4-0.6 MPa; the spray gun and the atomizing nozzle are made of SiC or SUS316L materials.
6. The method for recycling the stainless steel mixed acid pickling sludge as claimed in claim 1, wherein the temperature of the top of the mixed acid regeneration spray roasting furnace in the step 4 is higher than 320 ℃.
7. The method for recycling the stainless steel mixed acid pickling sludge as claimed in claim 1, wherein the mixed acid pickling waste liquid generated in the stainless steel pickling line is treated simultaneously in step 4 and sprayed into the roasting furnace by using different spray heads from the sludge slurry; the mixed acid pickling waste liquid is supernatant liquid obtained after sludge is removed through precipitation.
8. The method for recycling the stainless steel mixed acid pickling sludge as claimed in claim 1, wherein the condensate collected in the step 5 is returned to the step 1 to prepare the alkaline solution with the ammonia water.
9. The recycling system of stainless steel mixed acid pickling sludge is characterized by comprising the following components:
a neutralization agitation tank for preparing an alkaline solution, having an inlet for water and an alkaline agent to enter, and discharging the resulting alkaline solution through a neutralization pump;
the high-speed dispersion machine is used for carrying out neutralization reaction on the alkaline solution and the stainless steel mixed acid washing sludge, is provided with an inlet for washing the sludge and is communicated with the neutralization liquid pump, and the neutralized sludge is discharged through the control of the electromagnetic valve;
the vibration filter is used for filtering the obtained neutralized slurry and is communicated with the electromagnetic valve; separating sludge particles and sludge slurry by vibration filtration;
the mud tank is used for collecting the mud body and is provided with a stirring paddle;
the mixed acid regeneration spray roasting furnace is used for treating the collected sludge slurry, the sludge slurry is conveyed to the roasting furnace through a slurry conveying pump and is sprayed from the top of the furnace through a sludge spray gun; the bottom of the roasting furnace is provided with a scraper rake for discharging metal oxide byproducts, and the top of the furnace is provided with an exhaust port;
the gas discharged from the gas outlet is treated by a pre-concentrator and an absorption tower, the gas enters the absorption tower after being pre-concentrated, and the residual gas after absorption treatment is discharged from the top of the tower;
and the cooling tower is used for condensing the residual gas, collecting condensed water for recycling, and feeding the condensed water into the neutralization stirring tank through a water inlet.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110936827.3A CN113774213A (en) | 2021-08-16 | 2021-08-16 | Recycling method and system of stainless steel mixed acid pickling sludge |
| PCT/CN2021/125298 WO2023019719A1 (en) | 2021-08-16 | 2021-10-21 | Method and system for recycling stainless steel mixed acid pickling sludge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110936827.3A CN113774213A (en) | 2021-08-16 | 2021-08-16 | Recycling method and system of stainless steel mixed acid pickling sludge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113774213A true CN113774213A (en) | 2021-12-10 |
Family
ID=78837841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110936827.3A Pending CN113774213A (en) | 2021-08-16 | 2021-08-16 | Recycling method and system of stainless steel mixed acid pickling sludge |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113774213A (en) |
| WO (1) | WO2023019719A1 (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417141A (en) * | 2001-11-07 | 2003-05-14 | 安德里茨有限公司 | Method of treating acid metal-containing waste water |
| CN1843965A (en) * | 2006-04-28 | 2006-10-11 | 中冶南方工程技术有限公司 | Purification treatment process of waste liquor of hydrochloric acid |
| CN104250820A (en) * | 2013-06-27 | 2014-12-31 | 宝钢不锈钢有限公司 | Method and apparatus for regenerating all acid of stainless steel pickling waste liquid |
| CN104831298A (en) * | 2015-04-22 | 2015-08-12 | 鞍山创新废酸除硅再生工程有限公司 | Method and device for regeneration of stainless steel mixed acid pickling waste acid by spray roasting process |
| CN107601605A (en) * | 2017-10-20 | 2018-01-19 | 鞍山创新废酸除硅再生工程有限公司 | A kind of technique and system for improving stainless steel acid-washing waste liquid nitric acid regeneration yield |
| CN208082202U (en) * | 2018-03-14 | 2018-11-13 | 沈阳东北制药装备制造安装有限公司 | A kind of ammonia exhaust treatment system |
| CN109553152A (en) * | 2018-11-30 | 2019-04-02 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor regenerated acid technique |
| CN110330199A (en) * | 2019-07-29 | 2019-10-15 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor sludge harmless treatment method |
| CN111088412A (en) * | 2019-12-16 | 2020-05-01 | 霸州环瑞节能科技有限公司 | Acid pickling sludge resource utilization method |
| CN210528729U (en) * | 2019-07-29 | 2020-05-15 | 中冶南方工程技术有限公司 | Stainless steel acid-mixed waste liquid sludge harmless treatment system |
| CN111560522A (en) * | 2020-05-22 | 2020-08-21 | 四川君和环保股份有限公司 | Stainless steel pickling sludge treatment method |
| CN111704344A (en) * | 2020-06-05 | 2020-09-25 | 中冶南方工程技术有限公司 | Acid pickling process waste zero-emission recycling treatment device and process |
| CN112176356A (en) * | 2019-07-03 | 2021-01-05 | 宝钢新日铁汽车板有限公司 | Environment-friendly acid liquor purification method and system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4757813B2 (en) * | 2006-07-06 | 2011-08-24 | 日本冶金工業株式会社 | Raw material for reduction recycling of steel by-products and roasting reduction method thereof |
| CN103451422B (en) * | 2013-09-03 | 2015-03-11 | 天津城建大学 | Method for preparing iron oxide for iron making by using steel acid-washing wastewater sludge |
| CN207713438U (en) * | 2017-10-20 | 2018-08-10 | 鞍山创新废酸除硅再生工程有限公司 | A kind of system improving stainless steel acid-washing waste liquid nitric acid regeneration yield |
| CN111663044B (en) * | 2020-05-14 | 2023-12-29 | 中冶南方工程技术有限公司 | Acidic sludge and waste acid recycling device and process |
-
2021
- 2021-08-16 CN CN202110936827.3A patent/CN113774213A/en active Pending
- 2021-10-21 WO PCT/CN2021/125298 patent/WO2023019719A1/en unknown
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417141A (en) * | 2001-11-07 | 2003-05-14 | 安德里茨有限公司 | Method of treating acid metal-containing waste water |
| CN1843965A (en) * | 2006-04-28 | 2006-10-11 | 中冶南方工程技术有限公司 | Purification treatment process of waste liquor of hydrochloric acid |
| CN104250820A (en) * | 2013-06-27 | 2014-12-31 | 宝钢不锈钢有限公司 | Method and apparatus for regenerating all acid of stainless steel pickling waste liquid |
| CN104831298A (en) * | 2015-04-22 | 2015-08-12 | 鞍山创新废酸除硅再生工程有限公司 | Method and device for regeneration of stainless steel mixed acid pickling waste acid by spray roasting process |
| CN107601605A (en) * | 2017-10-20 | 2018-01-19 | 鞍山创新废酸除硅再生工程有限公司 | A kind of technique and system for improving stainless steel acid-washing waste liquid nitric acid regeneration yield |
| CN208082202U (en) * | 2018-03-14 | 2018-11-13 | 沈阳东北制药装备制造安装有限公司 | A kind of ammonia exhaust treatment system |
| CN109553152A (en) * | 2018-11-30 | 2019-04-02 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor regenerated acid technique |
| CN112176356A (en) * | 2019-07-03 | 2021-01-05 | 宝钢新日铁汽车板有限公司 | Environment-friendly acid liquor purification method and system |
| CN110330199A (en) * | 2019-07-29 | 2019-10-15 | 中冶南方工程技术有限公司 | A kind of stainless steel mixed acid waste liquor sludge harmless treatment method |
| CN210528729U (en) * | 2019-07-29 | 2020-05-15 | 中冶南方工程技术有限公司 | Stainless steel acid-mixed waste liquid sludge harmless treatment system |
| CN111088412A (en) * | 2019-12-16 | 2020-05-01 | 霸州环瑞节能科技有限公司 | Acid pickling sludge resource utilization method |
| CN111560522A (en) * | 2020-05-22 | 2020-08-21 | 四川君和环保股份有限公司 | Stainless steel pickling sludge treatment method |
| CN111704344A (en) * | 2020-06-05 | 2020-09-25 | 中冶南方工程技术有限公司 | Acid pickling process waste zero-emission recycling treatment device and process |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023019719A1 (en) | 2023-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021017940A1 (en) | Method for hazard-free treatment of sludge from spent solution of mixed acids after acid washing of stainless steel | |
| CN107475542B (en) | Method for treating rare earth concentrate | |
| CN104384167B (en) | A kind of comprehensive reutilization method of discarded titanium-based vanadium system SCR catalyst | |
| CN101503762B (en) | Desulphurization and vanadium extraction technique for calcinated vanadium ore | |
| CN209124595U (en) | A kind of aluminium ash harmless treatment device | |
| CN106048230B (en) | The separation of tungsten and vanadium, recovery method in a kind of useless SCR denitration | |
| CN103526031A (en) | Recovery method for SCR waste flue gas denitration catalyst | |
| CN210528729U (en) | Stainless steel acid-mixed waste liquid sludge harmless treatment system | |
| CN107299223B (en) | A kind of compound alkaline-leaching and vanadium extraction method of bone coal and its system | |
| CN112077124A (en) | Treatment method for harmless comprehensive utilization of secondary aluminum ash and preparation method thereof | |
| CN106521160A (en) | Method for extraction of vanadium from waste SCR catalyst and preparation of activated titanium silicon tungsten powder | |
| CN105399116A (en) | System for treating waste acid with organic matters and treatment method and application of system | |
| CN105274341A (en) | Method for leaching metallic vanadium and metallic tungsten in waste selective catalytic reduction (SCR) denitration catalyst | |
| CN104611564A (en) | Method for recycling metal oxides from waste SCR (selective catalytic reduction) catalyst | |
| CN111663044B (en) | Acidic sludge and waste acid recycling device and process | |
| CN109553152A (en) | A kind of stainless steel mixed acid waste liquor regenerated acid technique | |
| CN104178636A (en) | Method for recovering Ti, V, Mo and Si in SCR (selective catalytic reduction) waste catalyst by combination of activation calcination and acid leaching | |
| CN110775998A (en) | System and method for producing nano zinc oxide by industrially recycling zinc | |
| CN104451152A (en) | Continuous recovery device and continuous recovery process of vanadium, molybdenum and titanium in SCR (selective catalytic reduction) waste catalyst | |
| CN113943871B (en) | Method for treating magnesium ammonium phosphate slag containing tungsten | |
| CN107267784B (en) | System for handle rare earth concentrate | |
| CN113774213A (en) | Recycling method and system of stainless steel mixed acid pickling sludge | |
| CN102560158A (en) | Transformation method for mixed rare earth concentrate and concentrated sulfuric acid low-temperature roasted ore | |
| CN109467065A (en) | A kind of stainless steel mixed acid waste liquor regenerated acid equipment | |
| CN212505011U (en) | Acid sludge and waste acid resource recovery device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |