CN108655157A - A kind of detoxification treatment process for changing blacklead - Google Patents

A kind of detoxification treatment process for changing blacklead Download PDF

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Publication number
CN108655157A
CN108655157A CN201810440900.6A CN201810440900A CN108655157A CN 108655157 A CN108655157 A CN 108655157A CN 201810440900 A CN201810440900 A CN 201810440900A CN 108655157 A CN108655157 A CN 108655157A
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level
liquid
solid
blacklead
sent
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CN201810440900.6A
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CN108655157B (en
Inventor
刘宗宽
顾兆林
李进
牛加新
尹晓虎
张余清
孙贵之
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72465 Troops Of Ji'nan Military Region Of Chinese People's Liberation Army
Xian Jiaotong University
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72465 Troops Of Ji'nan Military Region Of Chinese People's Liberation Army
Xian Jiaotong University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00Destroying solid waste or transforming solid waste into something useful or harmless
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09BDISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B5/00Operations not covered by a single other subclass or by a single other group in this subclass
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/82Recycling of waste of electrical or electronic equipment [WEEE]

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fertilizers (AREA)

Abstract

A kind of detoxification treatment process for changing blacklead, the blacklead that changes scrapped is sent into through the lock hopper at the top of lock hopper formula liquid-solid reactor in liquid-solid reactor, deenergize hydrolysis with the KOH solution counter current contacting ejected in lye injection pipe, reaction solution enters level-one from the discharge port of reactor and pond is mixed, and aluminium removal KH is added2PO4Reaction, reaction solution pass through level-one cyclone hydraulic separators by the Al (OH) of generation3Sedimentation removal;Supernatant enters back into two level mixing pond and deleading agent potassium ferrate is added to be reacted, and reaction solution passes through two level cyclone hydraulic separators by the Fe (OH) of generation3And PbO2Sedimentation removal;The supernatant of two level cyclone hydraulic separators enters stripper, the organic matters such as benzene homologues are carried away by water vapour, tower reactor discharging is by being concentrated by evaporation, concentrate enters preparing pool and is mixed with flushed residue, humic acid and phosphorus acid for adjusting pH is added, the discharging of preparing pool is used for industrial production directly as liquid fertilizer;The present invention, which realizes, scraps deenergize detoxification and the recycling environmental protection utilization that change blacklead.

Description

A kind of detoxification treatment process for changing blacklead
Technical field
The present invention relates to scrap propellant powder safe disposal and application technology as the second resource field, and in particular to one kind is black for changing The detoxification treatment process of lead.
Background technology
Change blacklead be one kind based on cellulose and nitroglycerine, RDX be high energy additive propellant, both can guarantee Propellant has higher energy, and can realize the smokeless emission of propellant.Other than nitrocellulose, nitroglycerine and RDX, Change and also added aluminium powder, dimethyl acardite and o-amino benzoyl lead plumbate in blacklead.Basic hydrolysis is used for the blacklead that changes scrapped Method, scrap nitro or nitroso on ammunition with hydroxyl substitution at a certain temperature, reach the purpose deenergized.Buck The substances such as the potassium nitrate, potassium nitrite and the potassium carbonate that are generated in solution preocess can be used as nitrogenous fertilizer and potash fertilizer to be used for agricultural production, with The recycling that deenergizes for changing blacklead is scrapped in realization.
In addition, that scraps changes blacklead alkaline hydrolysis process also and can generate that potassium metaaluminate, plumbous acid potassium and benzene homologues etc. are toxic to be had Evil substance makes metal ion be enriched in crops if crops can directly be polluted by functioning as fertilizer without processing, so that Threaten the health of the mankind.
Currently, being mainly the precipitation method, coacervation, absorption method and ion-exchange for the removal of lead ion.In recent years, About the method using magnetic iron ore absorption, work well, but in natural troilite magnetic iron ore and pyrite separation Process is comparatively laborious, heavy workload, limits its practical application.Industrially mostly using sulfide solution reacts generation with lead ion Vulcanized lead precipitates, but sulfide inherently noxious material, for example vulcanized sodium decomposable asymmetric choice net in acid generates toxic gas vulcanization Hydrogen, being stained on skin can cause to burn, and have high toxicity to aquatile.It can require relatively high to operation in this way, be easy to draw Send out peril.In addition, preferably being gone for the potassium metaaluminate and benzene homologues proposition that change the generation of blacklead alkaline hydrolysis process not yet Except method.
Invention content
In order to overcome the disadvantages of the above prior art, the object of the present invention is to provide a kind of detoxifications for changing blacklead Treatment process, realization scrap change blacklead propellant deenergize, detoxification, recycling environmental protection utilize.
In order to achieve the above object, the technical solution that the present invention takes is:
A kind of detoxification treatment process for changing blacklead includes the following steps:
The first step, pending scrapping change the top that blacklead is sent to lock hopper formula solid-liquid reaction device 2 via belt conveyor 1, It is flowed into lock hopper formula solid-liquid reaction device 2 by level-one lock hopper, is 20% with the mass concentration ejected from lye injection pipe 21 KOH solution counter current contacting complete macromolecule alkali for hydrolysis, the temperature in control lock hopper formula solid-liquid reaction device 2 is 90 DEG C, and KOH solution adds Enter amount and changes the mass ratio control of blacklead addition in 5-7:1, the heat that macromolecule alkali for hydrolysis process releases passes through in chuck Heat transferring medium water is taken away;
Second step, macromolecule alkali for hydrolysis liquid are sent into from the 2 top export mouth outflow of lock hopper formula solid-liquid reaction device via the first pump 4 Pond 8 is mixed to level-one and remove reactive aluminum, macromolecule alkali for hydrolysis residual residue and partial reaction liquid from lock hopper formula solid-liquid reaction The bottom discharge mouth of device 2 discharges, and is sent into solid-liquid separator 5 via screw conveyor 3, by 40 mesh in solid-liquid separator 5 Sieve 51 solid residue and reaction solution are detached, solid residue flows into washer 7, is rushed via the vibrations of vibrating screen panel 71 It washes, the solid residue after flushing flows into preparing pool 22;Flushing liquor in solid-liquid separator 5 in clear liquid and washer 7 passes through respectively It is sent to level-one by the second pump 6 and third pump 12 and is mixed in pond 8;
Third walks, and is mixed in pond 8 toward level-one and aluminium removal KH is added2PO4, operating condition is that every cubic metre of clear liquid is added 10g KH2PO4, temperature is 50 DEG C, stirring intensity 0.8kW/m3Liquid;Level-one be mixed pond 8 in reaction residual liquor via 4th pump 9 is sent to the top of level-one cyclone hydraulic separators 10, by settling Al (OH)3It precipitates from the bottom of level-one cyclone hydraulic separators 10 Portion discharges, and supernatant is overflowed from the top of level-one cyclone hydraulic separators 10, and being sent into two level via the 5th pump 11 is mixed Pond 13 removes the lead ion in reaction solution;
The feed inlet in pond 13 is mixed with 30g/cm in two level in 4th step2Ratio potassium ferrate (K is added2FeO4), PH is controlled in 8-10, stirring intensity 0.9-1.2kW/m3Liquid;The reaction residual liquor in pond 13 is mixed via the in two level Six pumps 14 are sent to the top of two level cyclone hydraulic separators 15, by flocculating setting Fe (OH)3And PbO2Sediment divides from two level spinning liquid From 15 bottom discharge of device, and supernatant is overflowed from 15 top of two level cyclone hydraulic separators, and stripping tower is sent into via the 7th pump 16 17 upper feed inlets;
5th step, the stripping fluid that stripper 17 uses is water vapour, and the water vapour that temperature is 240-250 DEG C is with 1.5m3/ The rate of min enters the feed liquid counter current contacting entered with tower top from the bottom of tower of stripper 17, and 99% benzene homologues is made to have with other Machine object is enriched in the gas phase from the top discharge of stripper 17, is then stored in after condensation process in organic matter storage tank 18, The discharging 50% of 17 bottom of tower of stripper flows back into 17 tower top of stripper, and remaining 50% is sent to evaporation and concentration via the 8th pump 19 In tower 20;
6th step is concentrated by evaporation tower 20 using 140-150 DEG C of steam heating, and 60% moisture is steamed from tower top, so After carry out condensation process;Evaporation concentrated solution discharges from bottom of tower, is sent into preparing pool 22 via the 9th pump 21;It is pressed in preparing pool 22 Volume ratio is that humic acid is added in 7-8%, phosphoric acid is added, pH value of solution is adjusted to 7-7.5, and the solid residue flowed into washer 7 is mixed It closes;The discharging of regulating reservoir 22 is used directly as liquid fertilizer in agricultural production.
Temperature control system is set in the lock hopper formula solid-liquid reaction device 2.
Sieve 51 in the solid-liquid separator 5 is to be obliquely installed, and inclination angle is 15 °, ensures the solid being retained down Particle is flowed out from discharge port.
Vibrating screen panel 71 in the washer 7 is front and back vibrations so that solid residue moves forward with vibrations.
Downflow weir is all arranged in the feed inlet of the level-one cyclone hydraulic separators 10 and two level cyclone hydraulic separators 15 so that feed liquid It can slowly flow into two cyclone hydraulic separators.
Compared with prior art, beneficial effects of the present invention are:
1, KH is utilized2PO4Aluminium ion is removed, can not only adjust solution ph, the PO added4 3-Phosphate fertilizer is also used as, Reduce the dosage of regulating reservoir phosphoric acid.
2, lead ion is removed using potassium ferrate, avoids the use of sulfide, reduce dangerous generation in operating process Possibility.
3, the organic matters such as benzene homologues are removed using steam stripping so that there is enough water to deposit always in stripper 17 It ensure that the safety of operating process.
4, lead element removal is placed on behind aluminium element removal, avoids and adjusts pH repeatedly, and in removal lead element During the potassium ferrate that adds will produce the Fe (OH) of Fe (III) and adsorption function with excellent flocculating function3, not only It can help PbO2Precipitation, complete Al (OH) will can not also be precipitated in the last stage3Further precipitation increases aluminium element Removal rate.
Description of the drawings
Fig. 1 is the flow diagram of present invention process.
Specific implementation mode
The invention will be further described with reference to the accompanying drawings and examples.
Referring to Fig.1, a kind of detoxification treatment process for changing blacklead, includes the following steps:
The first step, pending scrapping change the top that blacklead is sent to lock hopper formula solid-liquid reaction device 2 via belt conveyor 1, It is flowed into lock hopper formula solid-liquid reaction device 2 by level-one lock hopper, is 20% with the mass concentration ejected from lye injection pipe 21 KOH solution counter current contacting complete macromolecule alkali for hydrolysis, in order to reach basic hydrolysis purpose, in control lock hopper formula solid-liquid reaction device 2 Temperature is 90 DEG C, and KOH solution addition and the mass ratio for changing blacklead addition are controlled in 5-7:1, the release of macromolecule alkali for hydrolysis process The heat gone out is taken away by the heat transferring medium water in chuck;
Second step, macromolecule alkali for hydrolysis liquid are sent into from the 2 top export mouth outflow of lock hopper formula solid-liquid reaction device via the first pump 4 Pond 8 is mixed to level-one and remove reactive aluminum, macromolecule alkali for hydrolysis residual residue and partial reaction liquid from lock hopper formula solid-liquid reaction The bottom discharge mouth of device 2 discharges, and is sent into solid-liquid separator 5 via screw conveyor 3, by 40 mesh in solid-liquid separator 5 Sieve 51 solid residue and reaction solution are detached, solid residue flows into washer 7, is rushed via the vibrations of vibrating screen panel 71 It washes, the solid residue after flushing flows into preparing pool 22;Flushing liquor in solid-liquid separator 5 in clear liquid and washer 7 passes through respectively It is sent to level-one by the second pump 6 and third pump 12 and is mixed in pond 8;
Third walks, and is mixed in pond 8 toward level-one and aluminium removal KH is added2PO4, operating condition is that every cubic metre of clear liquid is added 10g KH2PO4, temperature is 50 DEG C, stirring intensity 0.8kW/m3Liquid;Level-one be mixed pond 8 in reaction residual liquor via 4th pump 9 is sent to the top of level-one cyclone hydraulic separators 10, by settling Al (OH)3It precipitates from the bottom of level-one cyclone hydraulic separators 10 Portion discharges, and supernatant is overflowed from the top of level-one cyclone hydraulic separators 10, and being sent into two level via the 5th pump 11 is mixed Pond 13 removes the lead ion in reaction solution;
The feed inlet in pond 13 is mixed with 30g/cm in two level in 4th step2Ratio potassium ferrate (K is added2FeO4), PH is controlled in 8-10, stirring intensity 0.9-1.2kW/m3Liquid;The reaction residual liquor in pond 13 is mixed via the in two level Six pumps 14 are sent to the top of two level cyclone hydraulic separators 15, by flocculating setting Fe (OH)3And PbO2Sediment divides from two level spinning liquid From 15 bottom discharge of device, and supernatant is overflowed from 15 top of two level cyclone hydraulic separators, and stripping tower is sent into via the 7th pump 16 17 upper feed inlets;
5th step, the stripping fluid that stripper 17 uses is water vapour, and the water vapour that temperature is 240-250 DEG C is with 1.5m3/ The rate of min enters the feed liquid counter current contacting entered with tower top from the bottom of tower of stripper 17, and 99% benzene homologues is made to have with other Machine object is enriched in the gas phase from the top discharge of stripper 17, is then stored in after condensation process in organic matter storage tank 18, The discharging 50% of 17 bottom of tower of stripper flows back into 17 tower top of stripper, and remaining 50% is sent to evaporation and concentration via the 8th pump 19 In tower 20;
6th step is concentrated by evaporation tower 20 using 140-150 DEG C of steam heating, and 60% moisture is steamed from tower top, so After carry out condensation process;Evaporation concentrated solution discharges from bottom of tower, is sent into preparing pool 22 via the 9th pump 21;It is pressed in preparing pool 22 Volume ratio is that humic acid is added in 7-8%, phosphoric acid is added, pH value of solution is adjusted to 7-7.5, and the solid residue flowed into washer 7 is mixed It closes;The discharging of regulating reservoir 22 is used directly as liquid fertilizer in agricultural production.
Temperature control system is set in the lock hopper formula solid-liquid reaction device 2 so that reaction temperature is controlled at 90 DEG C.
Sieve 51 in the solid-liquid separator 5 is to be obliquely installed, and inclination angle is 15 °, ensures the solid being retained down Particle can be flowed out from discharge port.
Vibrating screen panel 71 in the washer 7 is front and back vibrations so that solid residue moves forward with vibrations.
Downflow weir is all arranged in the feed inlet of the level-one cyclone hydraulic separators 10 and two level cyclone hydraulic separators 15 so that feed liquid It can slowly flow into two cyclone hydraulic separators.

Claims (5)

1. a kind of detoxification treatment process for changing blacklead, which is characterized in that include the following steps:
The first step, pending scrapping change the top that blacklead is sent to lock hopper formula solid-liquid reaction device (2) via belt conveyor (1), It is flowed into lock hopper formula solid-liquid reaction device (2) by level-one lock hopper, is with the mass concentration ejected from lye injection pipe (21) 20% KOH solution counter current contacting completes macromolecule alkali for hydrolysis, and the temperature in control lock hopper formula solid-liquid reaction device (2) is 90 DEG C, KOH Solution addition and the mass ratio for changing blacklead addition are controlled in 5-7:1, the heat that macromolecule alkali for hydrolysis process releases passes through folder Heat transferring medium water in set is taken away;
Second step, macromolecule alkali for hydrolysis liquid are sent into from export mouth outflow at the top of lock hopper formula solid-liquid reaction device (2) via the first pump (4) Pond (8) are mixed to level-one to carry out except reactive aluminum, macromolecule alkali for hydrolysis residual residue and partial reaction liquid are anti-from lock hopper formula solid-liquid It answers the bottom discharge mouth of device (2) to discharge, is sent into solid-liquid separator (5) via screw conveyor (3), by solid-liquid separator (5) sieve (51) of 40 mesh in detaches solid residue and reaction solution, and solid residue flows into washer (7), via vibrations The vibrations of sieve (71) are rinsed, and the solid residue after flushing flows into preparing pool (22);The interior clear liquid of solid-liquid separator (5) and flushing Flushing liquor in machine (7) is sent to level-one via the second pump (6) and third pump (12) respectively and is mixed in pond (8);
Third walks, and is mixed in pond (8) toward level-one and aluminium removal KH is added2PO4, operating condition is that 10g is added in every cubic metre of clear liquid KH2PO4, temperature is 50 DEG C, stirring intensity 0.8kW/m3Liquid;The reaction residual liquor in pond (8) is mixed via the in level-one Four pumps (9) are sent to the top of level-one cyclone hydraulic separators (10), by settling Al (OH)3It precipitates from level-one cyclone hydraulic separators (10) Bottom discharge, and supernatant overflows at the top of level-one cyclone hydraulic separators (10), and two level is sent into via the 5th pump (11) The lead ion in pond (13) removal reaction solution is mixed;
The feed inlet of pond (13) is mixed with 30g/cm in two level in 4th step2Ratio potassium ferrate (K is added2FeO4), pH Control is in 8-10, stirring intensity 0.9-1.2kW/m3Liquid;The reaction residual liquor in pond (13) is mixed via the in two level Six pumps (14) are sent to the top of two level cyclone hydraulic separators (15), by flocculating setting Fe (OH)3And PbO2Sediment is revolved from two level Liquid/gas separator (15) bottom discharge, and supernatant overflows at the top of two level cyclone hydraulic separators (15), via the 7th pump (16) It is sent into stripping tower (17) upper feed inlet;
5th step, the stripping fluid that stripper (17) uses is water vapour, and the water vapour that temperature is 240-250 DEG C is with 1.5m3/min Rate enter the feed liquid counter current contacting that enters with tower top from the bottom of tower of stripper (17), keep 99% benzene homologues organic with other Object is enriched in the gas phase from the top discharge of stripper (17), and organic matter storage tank (18) is then stored in after condensation process In, the discharging 50% of stripper (17) bottom of tower flows back into stripper (17) tower top, and remaining 50% is sent into via the 8th pump (19) Into evaporation and concentration tower (20);
6th step is concentrated by evaporation the steam heating that tower (20) uses 140-150 DEG C, and 60% moisture is steamed from tower top, then Carry out condensation process;Evaporation concentrated solution discharges from bottom of tower, is sent into preparing pool (22) via the 9th pump (21);Toward preparing pool (22) It is inside that humic acid is added in 7-8% by volume, phosphoric acid is added, pH value of solution is adjusted to 7-7.5, the solid flowed into washer (7) Residue mixes;The discharging of regulating reservoir (22) is used directly as liquid fertilizer in agricultural production.
2. a kind of detoxification treatment process for changing blacklead according to claim 1, it is characterised in that:The lock hopper formula Temperature control system is set in solid-liquid reaction device (2).
3. a kind of detoxification treatment process for changing blacklead according to claim 1, it is characterised in that:The solid-liquid point It is to be obliquely installed from the sieve (51) in device (5), inclination angle is 15 °, ensures that the solid particle being retained down is flowed out from discharge port.
4. a kind of detoxification treatment process for changing blacklead according to claim 1, it is characterised in that:The washer (7) vibrating screen panel (71) in is front and back vibrations so that solid residue moves forward with vibrations.
5. a kind of detoxification treatment process for changing blacklead according to claim 1, it is characterised in that:The level-one rotation Downflow weir is all arranged in the feed inlet of liquid/gas separator (10) and two level cyclone hydraulic separators (15) so that feed liquid can slowly flow into two In a cyclone hydraulic separators.
CN201810440900.6A 2018-05-10 2018-05-10 It is a kind of for changing the detoxification treatment process of blacklead Active CN108655157B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072435A (en) * 2019-12-18 2020-04-28 湖北航天技术研究院总体设计所 Processing device and processing method for invalid propellant
CN111440050A (en) * 2020-05-14 2020-07-24 西安交通大学 Recovery process of high value-added medical intermediate of scrapped explosives and powders

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3778320A (en) * 1972-06-20 1973-12-11 Rockwell International Corp Non-polluting disposal of explosives and propellants
JPH0859383A (en) * 1994-06-06 1996-03-05 Mitsubishi Heavy Ind Ltd Treatment of gunpowder and explosives
CN1279623A (en) * 1997-09-18 2001-01-10 联合讯号公司 Demilitarization of chemical munitions
CN103408341A (en) * 2013-08-14 2013-11-27 中国人民解放军***72465部队 Energy-containing material safe disposal and resource utilization method and system
CN107827684A (en) * 2017-11-30 2018-03-23 西安交通大学 A kind of TNT basic hydrolysis handling process
CN107876548A (en) * 2017-11-30 2018-04-06 西安交通大学 A kind of vehicle-mounted integral is scrapped ammunition and deenergized disposal of resources system

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3778320A (en) * 1972-06-20 1973-12-11 Rockwell International Corp Non-polluting disposal of explosives and propellants
JPH0859383A (en) * 1994-06-06 1996-03-05 Mitsubishi Heavy Ind Ltd Treatment of gunpowder and explosives
CN1279623A (en) * 1997-09-18 2001-01-10 联合讯号公司 Demilitarization of chemical munitions
CN103408341A (en) * 2013-08-14 2013-11-27 中国人民解放军***72465部队 Energy-containing material safe disposal and resource utilization method and system
CN107827684A (en) * 2017-11-30 2018-03-23 西安交通大学 A kind of TNT basic hydrolysis handling process
CN107876548A (en) * 2017-11-30 2018-04-06 西安交通大学 A kind of vehicle-mounted integral is scrapped ammunition and deenergized disposal of resources system

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111072435A (en) * 2019-12-18 2020-04-28 湖北航天技术研究院总体设计所 Processing device and processing method for invalid propellant
CN111072435B (en) * 2019-12-18 2021-06-04 湖北航天技术研究院总体设计所 Processing device and processing method for invalid propellant
CN111440050A (en) * 2020-05-14 2020-07-24 西安交通大学 Recovery process of high value-added medical intermediate of scrapped explosives and powders

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