CN118023266A - Method for synergistic treatment of waste lead storage battery by side-blown flue gas acid making smelting coupling multi-pollutant - Google Patents
Method for synergistic treatment of waste lead storage battery by side-blown flue gas acid making smelting coupling multi-pollutant Download PDFInfo
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003546 flue gas Substances 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 238000003723 Smelting Methods 0.000 title claims abstract description 43
- 238000003860 storage Methods 0.000 title claims abstract description 33
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 25
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 230000002195 synergetic effect Effects 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 23
- 238000007664 blowing Methods 0.000 claims abstract description 22
- 239000000446 fuel Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 231100000719 pollutant Toxicity 0.000 claims abstract description 15
- 239000011505 plaster Substances 0.000 claims abstract description 11
- 238000010791 quenching Methods 0.000 claims abstract description 10
- 230000000171 quenching effect Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 31
- 229920003023 plastic Polymers 0.000 claims description 27
- 239000004033 plastic Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 15
- 230000003009 desulfurizing effect Effects 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 10
- VQTGUFBGYOIUFS-UHFFFAOYSA-N nitrosylsulfuric acid Chemical compound OS(=O)(=O)ON=O VQTGUFBGYOIUFS-UHFFFAOYSA-N 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 229920000858 Cyclodextrin Polymers 0.000 claims description 9
- 238000007670 refining Methods 0.000 claims description 9
- 230000001172 regenerating effect Effects 0.000 claims description 9
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 239000002918 waste heat Substances 0.000 claims description 7
- 238000005275 alloying Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000000571 coke Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 238000007885 magnetic separation Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 239000000779 smoke Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract 4
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- -1 copper iron ions Chemical class 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for cooperatively treating a plurality of pollutants by side-blown flue gas acid making and smelting coupling of a waste lead storage battery, which is characterized by comprising the following steps: crushing materials, carrying out water conservancy separation, collecting waste lead plaster mud, removing impurities from the waste lead plaster mud, carrying out side-blown smelting, carrying out flue gas treatment and the like; the invention realizes the control of dioxin production from source materials through fuel selection of a side blowing furnace and impurity removal treatment of waste lead plaster, realizes the control of dioxin in the smelting process by utilizing the temperature control of the side blowing furnace, and realizes the tail end control of dioxin by utilizing a flue gas quenching procedure to quickly cool the flue gas in 1s to a temperature interval of dioxin production in the flue gas treatment process.
Description
Technical Field
The invention relates to the technical field of storage battery recovery, in particular to a method for cooperatively treating multiple pollutants by side-blown flue gas acid making and smelting of a waste lead storage battery.
Background
Compared with primary lead smelted from ores, regenerated lead smelted from waste storage batteries has lower energy consumption and less pollutant emission in the production process, and meets the requirements of low carbon and environmental protection. More than 85% of the regenerated lead raw materials in China come from waste lead storage batteries, and more than half of the consumed lead in the lead storage battery industry comes from regenerated lead, so that the cyclic development of the lead storage batteries and the regenerated lead becomes the growth main force of the regenerated lead industry in China. The lead recovery of waste lead-acid batteries mainly comprises two modes of pyrometallurgy and hydrometallurgy, and the main current regenerated lead enterprises all adopt pyrometallurgy technology.
Along with the development of technology and the wide application of high-efficiency automatic equipment, the technology of the cremation secondary lead of the waste lead storage battery in China is developed rapidly, and advanced technologies such as oxygen-enriched side-blown smelting, oxygen-enriched bottom-blown smelting, low-temperature continuous smelting and the like are formed, however, the pollution problem of the cremation lead smelting is always focused on in various communities and industries of society, and particularly pollutants discharged by smelting flue gas comprise sulfur dioxide, nitrogen oxides, dioxin, heavy metals (lead, arsenic, antimony, bismuth and the like), particulate matters and the like, and the invention has the characteristics of a large number of types and complex components. At present, most of treatment on multi-pollutants of regenerated lead flue gas mainly adopts tail end treatment, such as flue gas tail end purification technologies of wet/semi-dry/dry desulfurization, SNCR/SCR denitration, electric bag dust removal, secondary oxygen combustion and quenching/adsorbent adsorption for removing dioxin and the like. Although the terminal treatment can eliminate pollution and slow down the environmental pollution and damage caused by production activities to a certain extent, along with the acceleration of the industrialization process, the limitation of the terminal treatment is increasingly highlighted, such as the problems of large investment in facilities, high operation cost and incomplete treatment caused by the transfer of pollutants, and no relation to the effective utilization of resources. Therefore, the source reduction and the process control are combined to truly solve the problem of pollution control of smelting flue gas, and the flue gas treatment system engineering is formed by coupling with the actual production process.
Disclosure of Invention
The invention aims to provide a method for synergically treating multiple pollutants by side-blowing flue gas acid making and smelting coupling of a waste lead storage battery aiming at the defects of the prior art, and the method controls the generation of dioxin from source materials through fuel selection of a side-blowing furnace and impurity removal treatment of waste lead plaster, and controls the generation of dioxin in the smelting process by utilizing temperature control of the side-blowing furnace, and in the flue gas treatment process, the flue gas quenching procedure is utilized to quickly cool the interior of flue gas 1s to a temperature interval in which the dioxin is generated, so that the tail end control of the dioxin is realized.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the method for cooperatively treating the waste lead storage battery by side-blowing flue gas to prepare acid and smelting coupled multi-pollutant is characterized by comprising the following steps of:
Firstly, mechanically crushing a waste lead storage battery to be treated, removing iron from the crushed material by a magnetic separation conveying belt, further refining particles by secondary crushing, and then conveying the crushed material to a vibration screening device;
Step two, the oversize materials after vibration screening in the step one are separated by a multi-stage hydraulic classifier, so that lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper are respectively obtained; collecting the waste lead plaster mud of the undersize into a stirring tank;
step three, adding a impurity removal auxiliary agent into the stirring tank in the step two;
Step four, the waste lead paste subjected to impurity removal in the step three is conveyed to a side blowing furnace after being subjected to filter pressing treatment, and crude lead is obtained through continuous smelting at 1100-1300 ℃; the exhaust gas temperature of the side-blown furnace is controlled to be above 500 ℃ after passing through the waste heat boiler, the temperature of the exhaust gas is controlled to be reduced from above 500 ℃ to 200 ℃ in a smoke quenching procedure, and the exhaust gas is sent to a subsequent dedusting and demisting step, so that a resynthesis section of dioxin is avoided;
and fifthly, sending the lead grid and the lead alloy block obtained by sorting in the step two into a low-temperature smelting system to obtain crude lead, and sending the crude lead and the crude lead obtained in the step four into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
As an improvement, the impurity removing agent in the third step comprises a combined solution prepared by surfactant, complexing agent, cyclodextrin and dechlorinated water.
As an improvement, the mass content of the surfactant is 0.5-1%, the mass content of the complexing agent is 2-3%, and the mass content of the cyclodextrin is 1-2%.
As an improvement, the surfactant is a chlorine-free oil-in-water surfactant, which is one or a combination of more of tween-80, fatty alcohol polyoxyethylene ether and polyvinyl alcohol.
As an improvement, the complexing agent is one or a combination of more of EDTA, sodium citrate and phenanthroline.
In the fourth step, the fuel of the side blowing furnace is natural gas, so that source fuel type NOx generated by nitrogen-containing fuel is eliminated from the source; meanwhile, the side-blown furnace adopts O 2、CO2 Or (b) pure oxygen combustion-supporting gas for combustion, so that N 2 in the air is prevented from being oxidized to generate thermal NOx when the temperature is higher than 1200 ℃.
The method is characterized by further comprising an acid preparation step of flue gas, wherein one part of the flue gas after dust removal in the fourth step is used for preparing sulfuric acid in a one-rotation one-suction mode, the other part of the flue gas is used for being concentrated by a desulfurizing tower and a regenerating tower and then is mixed with the acid preparation flue gas, and the acid preparation tail gas is discharged after being treated by the desulfurizing tower.
The method is characterized by further comprising a denitration step, wherein a small amount of NOx generated by at least reducing coal and coke mixed in the flue gas acid preparation step can generate nitrososulfuric acid suspended particles through the acid preparation step, and the nitrososulfuric acid suspended particles are captured by a foam capture device and then discharged to a denitration reactor for reduction and denitration treatment.
As an improvement, a branch is branched from a gas path of a SO 2 in a desulfurization regeneration tower in the flue gas acid making step and is connected to a denitration reactor in a denitration process, and nitrososulfuric acid in the denitration reactor oxidizes SO 2 into sulfuric acid and is combined with the acid making process to generate N 2 to realize denitration.
As an improvement, the separator paper obtained in the second step is cleaned and dried to prepare the usable separator paper; the light plastic and the remolded plastic are subjected to cleaning, color selection, modification and granulation treatment to obtain the available regenerated plastic.
The invention has the beneficial effects that:
(1) The side-blown converter takes natural gas as fuel, so that source fuel type NOx generated by nitrogen-containing fuel is eliminated from the source; meanwhile, the side-blown furnace adopts O 2/CO2 pure oxygen combustion-supporting gas for combustion, so that N 2 in the air is prevented from being oxidized to generate thermal NOx when the temperature is higher than 1200 ℃; and then, using an intermediate raw material SO 2 in the self acid making process as a reducing agent, and reducing and denitrating the flue gas NOx source nitrososulfuric acid in a denitration reactor.
(2) The invention adds the impurity removing auxiliary agent in the cleaning and stirring process of the screened waste lead plaster, and aims to efficiently elute chlorine-containing organic molecules (dioxin sources) and copper iron ions (catalysts) in the waste lead plaster through the surfactant and the complexing agent, increase cmc of the waste lead plaster by utilizing cyclodextrin to encapsulate the surfactant and the complexing agent, improve elution efficiency of the chlorine-containing organic molecules and the copper iron ions, and control and reduce dioxin from the source; because the side-blown converter adopts natural gas as fuel, the smelting temperature reaches over 1100 ℃, and the generation of dioxin (the complete decomposition of dioxin at over 850 ℃) in the smelting process is avoided; meanwhile, the exhaust temperature of the waste heat boiler matched with the side-blown furnace is controlled to be more than 500 ℃, and a subsequent smoke quenching procedure is arranged, so that the temperature of the smoke is reduced from more than 500 ℃ to 200 ℃ within 1s, a secondary synthesis temperature region of dioxin is avoided, and the tail end control of the dioxin is realized.
(3) The invention fully utilizes the characteristics of the side-blown flue gas acid making smelting process of the waste lead storage battery, and adopts the technical processes of fuel denitrification, raw material dechlorination, high-temperature pure oxygen side-blowing, flue gas SO 2 self-denitration and the like to reduce the sources of nitrogen oxides and dioxin and embed process control into the production process, thereby controlling and preventing and controlling the multi-pollutants of the flue gas source in a system engineering concept.
In conclusion, the method has the advantages of controlling the generation of dioxin in the whole flow in the recovery smelting process of the waste lead storage battery and utilizing the flue gas SO 2 to perform self-denitration.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. indicate orientations or positional relationships are based on the orientations or positional relationships, merely to facilitate description of the present invention and simplify description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
Example 1
The embodiment provides a method for synergistic treatment of multi-pollutant by side-blown flue gas acid making and smelting of a waste lead storage battery, which comprises the following steps:
firstly, crushing a waste lead storage battery to be treated into a crushed material with the diameter of 20-25mm by a primary machine, removing iron from the crushed material by a magnetic separation transmission belt, further refining particles to less than 10mm by a secondary crushing, and then delivering the crushed material into a vibration screening device for screening;
step two, the oversize materials after vibration screening in the step one are separated by a multi-stage hydraulic classifier, and lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper are respectively obtained according to density differences; collecting the waste lead plaster mud of the undersize into a stirring tank, cleaning and drying the baffle paper obtained in the second step to prepare the usable baffle paper; the light plastic and the remolded plastic are subjected to cleaning, color selection, modification and granulation treatment to obtain the available regenerated plastic;
step three, adding a impurity removal auxiliary agent into the stirring tank in the step two;
Step four, the waste lead paste subjected to impurity removal in the step three is subjected to filter pressing treatment, dried and sent to a side blowing furnace, and crude lead is obtained through continuous smelting at 1100-1300 ℃; the exhaust gas temperature of the side-blown furnace is controlled to be above 500 ℃ after passing through the waste heat boiler, the temperature of the exhaust gas is controlled to be reduced from above 500 ℃ to 200 ℃ in a smoke quenching procedure, and the exhaust gas is sent to a subsequent dedusting and demisting step, so that a resynthesis section of dioxin is avoided;
and fifthly, sending the lead grid and the lead alloy block obtained by sorting in the step two into a low-temperature smelting system to obtain crude lead, and sending the crude lead and the crude lead obtained in the step four into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
As an improvement, the impurity removing agent in the third step comprises a combined solution prepared by surfactant, complexing agent, cyclodextrin and dechlorinated water; the method is used for efficiently eluting chlorine-containing organic molecules (dioxin source) and copper iron ions (catalyst) which are mixed and adsorbed in the waste lead paste, and controlling and reducing the generation of dioxin from the source.
As an improvement, the mass content of the surfactant is 0.5-1%, the mass content of the complexing agent is 2-3%, and the mass content of the cyclodextrin is 1-2%.
Preferably, the surfactant is a chlorine-free oil-in-water surfactant, which is one or a combination of more of tween-80, fatty alcohol polyoxyethylene ether and polyvinyl alcohol.
Preferably, the complexing agent is one or a combination of more of EDTA, sodium citrate and phenanthroline.
In the fourth step, the fuel of the side blowing furnace is natural gas, so that source fuel type NOx generated by nitrogen-containing fuel and chlorine-containing organic matters adsorbed in coal fuel are eliminated from the source; meanwhile, the side-blown furnace adopts O 2、CO2 or pure oxygen combustion-supporting gas for combustion, so that N2 in the air is prevented from being oxidized to generate thermal NOx when the temperature is higher than 1200 ℃.
Preferably, the method further comprises a flue gas acid making step, wherein one part of flue gas after dust removal in the fourth step is used for preparing sulfuric acid in a one-rotation one-suction mode, the other part of flue gas is used for being concentrated by a desulfurizing tower and a regenerating tower and then is mixed into acid making flue gas, and acid making tail gas is discharged after being treated by the desulfurizing tower.
Further, the method also comprises a denitration step, wherein a small amount of NOx which is mixed in the flue gas acid making step and is generated by at least reducing coal, coke and the like can generate nitrososulfuric acid suspended particles through the acid making step, and the nitrososulfuric acid suspended particles are captured by a foam capture device and then discharged to a denitration reactor for reduction denitration treatment.
Furthermore, a branch is branched from a gas path of the SO 2 in the desulfurization and regeneration tower in the flue gas acid making step and is connected to a denitration reactor in the denitration process, SO 2 is oxidized into sulfuric acid by nitrososulfuric acid in the denitration reactor, and the sulfuric acid is combined with the acid making process, and N2 is generated to realize denitration, and the chemical reaction is as follows:
4H2O + 2NOHSO4+ 3SO2→ 5H2SO4+ N2
Example two
For simplicity, only the points of distinction from embodiment one are described below. The second embodiment is different from the first embodiment in that:
In the embodiment, the waste lead storage battery to be treated is transported to a primary crushing device to be crushed into crushed materials with the diameter of 20-25mm, the crushed materials are transported to a secondary crushing device to be further refined into particles with the diameter of less than 10mm after being deironing through a magnetic separation transmission belt, and the particles are sent to a vibration screening device to be screened, and the oversize materials are separated through a multi-stage hydraulic separator, so that lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper are obtained according to the separation of density differences; the plastic is subjected to cleaning, color selection, modification and granulation treatment to obtain available regenerated plastic, the separator paper is cleaned and dried to prepare available separator paper, and the lead grid and the lead alloy block are sent to a low-temperature smelting system to obtain crude lead;
Collecting the waste lead paste mud of the undersize product into a stirring tank, adding a impurity removing auxiliary agent prepared from 1% of Tween-80, 2% of EDTA and 1% of cyclodextrin into the stirring tank, carrying out filter pressing and drying on the impurity removed waste lead paste, then delivering the waste lead paste to a side blowing furnace, adopting pure oxygen for supporting combustion in the side blowing furnace, adopting natural gas as fuel, adopting reducing coal, coke particles and scrap iron as reducing agents, and reducing the waste lead paste into crude lead at 1150 ℃;
the temperature of the exhaust gas of the side-blown furnace is controlled to be 510 ℃ after passing through a waste heat boiler, and the temperature of the exhaust gas is reduced to 190 ℃ after 1s through a quenching procedure, and then dust and mist are removed by an electric bag;
One part of the flue gas after dust removal is subjected to one-rotation one-absorption sulfuric acid production, the other part of the flue gas is concentrated by a desulfurizing tower and a regenerating tower and then is mixed into the acid production flue gas, a foam catcher and a denitration reactor are arranged at the rear end of the acid production process, a branch is separated from a gas circuit of the desulfurizing and regenerating tower and is connected into the denitration reactor, SO 2 of the flue gas is taken as a denitration reducing agent, and the acid production tail gas is discharged after passing through the desulfurizing tower;
And (3) feeding the crude lead obtained after low-temperature smelting of the lead grating and the lead alloy block and the crude lead obtained by the side blowing furnace into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
In the embodiment, the source reduction and process control are embedded into the side-blown waste lead plaster smelting process by the flue gas acid making method, and the detected flue gas pollutant emission indexes are as follows: NOx emission concentration value 3.14mg/m 3, dioxin emission concentration value 0.043ng TEQ/Nm 3, lead (fume) emission concentration 0.133mg/Nm 3, sulfur dioxide emission 5.83mg/m 3.
Example III
For simplicity, only the points of distinction from embodiment one are described below. The third embodiment is different from the first embodiment in that:
Conveying the waste lead storage battery to be treated to a primary crushing device to crush the waste lead storage battery into crushed materials with the diameter of 20-25mm, conveying the crushed materials to a secondary crushing device to further refine particles to less than 10mm after removing iron through a magnetic separation conveying belt, conveying the crushed materials to a vibration screening device to screen, and separating the oversize materials through a multi-stage hydraulic separator to obtain lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper according to density difference separation; the plastic is subjected to cleaning, color selection, modification and granulation treatment to obtain available regenerated plastic, the separator paper is cleaned and dried to prepare available separator paper, and the lead grid and the lead alloy block are sent to a low-temperature smelting system to obtain crude lead;
Collecting the waste lead paste mud of the undersize product into a stirring tank, adding a impurity removing auxiliary agent prepared from 1% of Tween-80, 1% of polyvinyl alcohol, 3% of EDTA and 1% of cyclodextrin into the stirring tank, carrying out filter pressing and drying on the impurity removed waste lead paste, then conveying the waste lead paste to a side blowing furnace, adopting pure oxygen for supporting combustion in the side blowing furnace, adopting natural gas as fuel, adopting reducing coal, coke particles and scrap iron as reducing agents, and reducing the waste lead paste into crude lead at 1150 ℃;
the temperature of the exhaust gas of the side-blown furnace is controlled to be 510 ℃ after passing through a waste heat boiler, and the temperature of the exhaust gas is reduced to 190 ℃ after 1s through a quenching procedure, and then dust and mist are removed by an electric bag;
One part of the flue gas after dust removal is subjected to one-rotation one-absorption sulfuric acid production, the other part of the flue gas is concentrated by a desulfurizing tower and a regenerating tower and then is mixed into the acid production flue gas, a foam catcher and a denitration reactor are arranged at the rear end of the acid production process, a branch is separated from a gas circuit of the desulfurizing and regenerating tower and is connected into the denitration reactor, SO 2 of the flue gas is taken as a denitration reducing agent, and the acid production tail gas is discharged after passing through the desulfurizing tower;
And (3) feeding the crude lead obtained after low-temperature smelting of the lead grating and the lead alloy block and the crude lead obtained by the side blowing furnace into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
The fume pollutant emission indexes of the embodiment are as follows: NOx emission concentration value 2.86mg/m 3, dioxin emission concentration value 0.029ng TEQ/Nm 3, lead (fume) emission concentration 0.134mg/Nm 3, sulfur dioxide emission 5.91mg/m 3.
Comparative example
Conveying the waste lead storage battery to be treated to a primary crushing device to crush the waste lead storage battery into crushed materials with the diameter of 20-25mm, conveying the crushed materials to a secondary crushing device to further refine particles to less than 10mm after removing iron through a magnetic separation conveying belt, conveying the crushed materials to a vibration screening device to screen, and separating the oversize materials through a multi-stage hydraulic separator to obtain lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper according to density difference separation; the plastic is subjected to cleaning, color selection, modification and granulation treatment to obtain available regenerated plastic, the separator paper is cleaned and dried to prepare available separator paper, and the lead grid and the lead alloy block are sent to a low-temperature smelting system to obtain crude lead;
collecting the waste lead paste mud of the undersize product into a stirring tank, carrying out filter pressing and drying on the waste lead paste subjected to stirring and impurity removal in a conventional aqueous solution, then delivering the waste lead paste to a side blowing furnace, adopting pure oxygen for supporting combustion in the side blowing furnace, taking natural gas as fuel, reducing coal, coke particles and scrap iron as reducing agents, and reducing the waste lead paste into crude lead at 1150 ℃;
the temperature of the exhaust gas of the side-blown furnace is controlled to be 510 ℃ after passing through a waste heat boiler, and the temperature of the exhaust gas is reduced to 190 ℃ after 1s through a quenching procedure, and then dust and mist are removed by an electric bag;
One part of the flue gas after dust removal is subjected to one-rotation one-absorption sulfuric acid production, the other part of the flue gas is concentrated by a desulfurizing tower and a regenerating tower and then is mixed into the acid production flue gas, a foam catcher and a denitration reactor are arranged at the rear end of the acid production process, a branch is separated from a gas circuit of the desulfurizing and regenerating tower and is connected into the denitration reactor, SO 2 of the flue gas is taken as a denitration reducing agent, and the acid production tail gas is discharged after passing through the desulfurizing tower;
And (3) feeding the crude lead obtained after low-temperature smelting of the lead grating and the lead alloy block and the crude lead obtained by the side blowing furnace into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
The discharge indexes of the smoke pollutants in the comparative example are as follows: NOx emission concentration value 5.1mg/m 3, dioxin emission concentration value 0.130 ng TEQ/Nm 3, lead (fume) emission concentration 0.134mg/Nm 3, sulfur dioxide emission 6mg/m 3.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The method for cooperatively treating the waste lead storage battery by side-blowing flue gas to prepare acid and smelting coupled multi-pollutant is characterized by comprising the following steps of:
Firstly, mechanically crushing a waste lead storage battery to be treated, removing iron from the crushed material by a magnetic separation conveying belt, further refining particles by secondary crushing, and then conveying the crushed material to a vibration screening device;
Step two, the oversize materials after vibration screening in the step one are separated by a multi-stage hydraulic classifier, so that lead grids, lead alloy blocks, light plastics, heavy plastics and separator paper are respectively obtained; collecting the waste lead plaster mud of the undersize into a stirring tank;
step three, adding a impurity removal auxiliary agent into the stirring tank in the step two;
Step four, the waste lead paste subjected to impurity removal in the step three is conveyed to a side blowing furnace after being subjected to filter pressing treatment, and crude lead is obtained through continuous smelting at 1100-1300 ℃; the temperature of the exhaust gas of the side-blown furnace is controlled to be above 500 ℃ after passing through the waste heat boiler, the temperature of the exhaust gas is controlled to be reduced from above 500 ℃ to 200 ℃ in 1s in the smoke quenching procedure, and the exhaust gas is sent to the subsequent dedusting and demisting;
and fifthly, sending the lead grid and the lead alloy block obtained by sorting in the step two into a low-temperature smelting system to obtain crude lead, and sending the crude lead and the crude lead obtained in the step four into a subsequent refining or alloying process to prepare regenerated refined lead or alloyed lead.
2. The method for synergistic treatment of multiple pollutants coupled with acid making and smelting by side-blown flue gas of a waste lead storage battery according to claim 1, wherein the impurity removing agent in the third step comprises a combination solution prepared from a surfactant, a complexing agent, cyclodextrin and dechlorinated water.
3. The method for synergistic treatment of the coupling multi-pollutant in the acid making and smelting of the side-blown flue gas of the waste lead storage battery according to claim 2, wherein the mass content of the surfactant is 0.5-1%, the mass content of the complexing agent is 2-3%, and the mass content of the cyclodextrin is 1-2%.
4. The method for synergistic treatment of multiple pollutants coupled with acid making and smelting by side-blown flue gas of a waste lead storage battery according to claim 3, wherein the surfactant is a non-chlorine-containing oil-in-water surfactant which is one or a combination of more of tween-80, fatty alcohol polyoxyethylene ether and polyvinyl alcohol.
5. The method for synergistic treatment of multiple pollutants coupled with acid making and smelting by side-blown flue gas of a waste lead storage battery according to claim 3, wherein the complexing agent is one or a combination of more of EDTA, sodium citrate and phenanthroline.
6. The method for synergistic treatment of the acid-making and smelting coupling multi-pollutants by using the side-blown flue gas of the waste lead storage battery according to claim 1, wherein in the fourth step, the fuel of the side-blown furnace is natural gas, and the side-blown furnace burns by adopting O2, CO2 or pure oxygen combustion-supporting gas.
7. The method for synergistic treatment of multiple pollutants in side-blown flue gas acid production and smelting coupling of a waste lead storage battery according to any one of claims 1 to 6, further comprising a flue gas acid production step, wherein one part of flue gas after dust removal in the fourth step is used for producing sulfuric acid in a one-rotation one-suction mode, the other part of flue gas is used for being enriched by a desulfurizing tower and a regenerating tower and then is combined into acid production flue gas, and acid production tail gas is discharged after being treated by the desulfurizing tower.
8. The method for synergistic treatment of multiple pollutants in side-blown flue gas acid production and smelting coupling of the waste lead storage batteries according to claim 7, further comprising a denitration procedure, wherein a small amount of mixed NOx generated by at least reduced coal and coke in the flue gas acid production step can generate nitrososulfuric acid suspended particles through the acid production procedure, and the nitrososulfuric acid suspended particles are captured by a foam catcher and discharged to a denitration reactor for reduction and denitration treatment.
9. The method for synergistic treatment of multiple pollutants coupled with side-blown flue gas acid production and smelting of the waste lead storage battery according to claim 8, wherein a branch line is branched from a SO2 gas path of a desulfurization regeneration tower in the flue gas acid production step and is connected to a denitration reactor in a denitration process, and nitrososulfuric acid in the denitration reactor oxidizes SO2 into sulfuric acid and is combined with the acid production process, and N2 is generated to realize denitration.
10. The method for synergistic treatment of the acid-making smelting coupling multi-pollutants by side-blown flue gas of the waste lead storage battery according to claim 7, wherein the separator paper obtained in the second step is cleaned and dried to prepare the usable separator paper; the light plastic and the remolded plastic are subjected to cleaning, color selection, modification and granulation treatment to obtain the available regenerated plastic.
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