CN106348371A - method for removing volatile organic compounds from degradation-resistant water - Google Patents

method for removing volatile organic compounds from degradation-resistant water Download PDF

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Publication number
CN106348371A
CN106348371A CN201611011861.5A CN201611011861A CN106348371A CN 106348371 A CN106348371 A CN 106348371A CN 201611011861 A CN201611011861 A CN 201611011861A CN 106348371 A CN106348371 A CN 106348371A
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heat storage
superheated steam
heat
volatile organic
steam
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CN201611011861.5A
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CN106348371B (en
Inventor
苏继新
王路瑶
程倩
程一倩
张晓霞
王国庆
潘齐
冯承湖
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Shandong University
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Shandong University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048Purification of waste water by evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22GSUPERHEATING OF STEAM
    • F22G1/00Steam superheating characterised by heating method
    • F22G1/14Steam superheating characterised by heating method using heat generated by chemical reactions
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/04Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00Waste heat recuperation
    • F23G2206/20Waste heat recuperation using the heat in association with another installation
    • F23G2206/203Waste heat recuperation using the heat in association with another installation with a power/heat generating installation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00Specific waste
    • F23G2209/10Liquid waste
    • F23G2209/101Waste liquor
    • 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
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/12Heat utilisation in combustion or incineration of waste

Abstract

The invention discloses a method for removing volatile organic compounds from degradation-resistant water. Waste water enters an evaporator; mixed steam which is generated by waste water evaporation and contains the volatile organic compounds enters at least three groups of heat accumulation bodies through a steam compressor; the mixed steam enters a combustion unit through the first group of heat accumulation bodies first; the combustion unit, on the one hand, heats and combusts the organic compounds in the steam, and on the other hand, enables the heat accumulation bodies to accumulate heat; the mixed steam becomes overheated steam after the volatile organic compounds are burnt off; the overheated steam returns to the evaporator through the second groups of heat accumulation bodies, and supplies heat to the evaporator; meanwhile, the overheated steam purges the residual mixed steam in the third group of heat accumulation bodies; then the mixed steam enters the next heat accumulation body in sequence to purge the next heat accumulation body. According to the method, by means of combining the waste water evaporation and high temperature heat accumulation, a certain amount of oxygen is supplemented to a high temperature region to complete oxidization of the organic compounds; the method is flexible to operate; the organic compounds can be thoroughly removed, and the aims of saving energy and reducing consumption are fulfilled.

Description

The minimizing technology of volatile organic matter in a kind of difficult degradation water
Technical field
The present invention relates to a kind of method for removing volatile organic matter in difficult degradation water, belong to sewage disposal technology neck Domain.
Background technology
The kind of waste water that difficult degradation is processed is more, and more typical such as garbage leachate, coking chemical waste water, chemical industry, medicine produce Waste water etc..In water, also species is various for hardly degraded organic substance, and water quality is complicated, the complexity such as high salt, abnormal flavour, high-load volatile organism Situation proposes challenge to conventional biodegradation technique.
The process of high salt used water difficult to degradate also can directly adopt wet method high-level oxidation technology to process, but related engineering practice is still Have no report.Though direct combustion degradation is feasible technological means it is contemplated that the amount of waste water is big, the high latent heat of vaporization, highly energy-consuming, height The factors such as cost, case history is also quite rare.
In industrial wastewater, salt density change is complicated, and organism kinds are various, and traditional waste water treatment process typically adopts Larger regulating reservoir, the concentration of salt and Organic substance in homogenizing waste water, and net using the low organic concentration after biodegradation Change the water outlet of water Macrodilution regulating reservoir, to meet microorganism own growth and degradation of organic substances needs.From existing a large amount of works Journey practice is seen, the treatment effect as coking, pharmacy, pesticide, chemical industry, the even industry-specific typical case in the portion such as garbage leachate waste water is equal It is difficult to meet the requirement of increasingly stricter wastewater discharge standard, be badly in need of new handling process.
Part new technique starts to avoid the impact to growth of microorganism for the high salinity in waste water, after desalination in advance or processing The method of desalination, obtains the waste water of less salt, so that follow-up Biochemical method.But more economical reverse osmosis deaslination processes and is subject to The impact of the factor such as Organic substance, too high in salinity, therefore Some Enterprises are forced the evaporative desalination technique taking cost higher.No matter It is triple effect evaporation or mvr (mechanical compress re-evaporation) desalination system, the effect of the desalination of process is preferable, but in water there is volatility Machine thing, particularly water solublity volatile organic matter can enter in condensed water with follow-up condensation, and the Organic Pollution of condensed water is special It is not that the problem that refractory organic pollutes still exists.
High temperature incineration is clearly the fast and effectively method of organics removal, and particularly rto (thermal accumulating incinerator) is wider The general removal for the Organic substance in waste gas, by the evaporation process containing Organic substance high-salt wastewater and rto technology in that context it may be convenient to The latent heat utilization of waste water evaporation process and the coupling of high-temperature oxydation burning process are optimized, substantially reduces Organic substance in high-salt wastewater Processing cost.
However, the high-temp combustion removal process containing volatile organic compounds for the tradition does not need the supplement of oxygen, and waste water The gaseous component of evaporation is mainly vapor, and pyroprocess can be only formed the thermal cracking of Organic substance in itself, and is converted primarily into co And h2It is impossible to complete the final process of Organic substance.
Content of the invention
The present invention is directed to the deficiency that in existing difficult degradation water, volatile organic matter removal technology exists, and proposes a kind of operation spirit The minimizing technology of volatile organic matter in work, the difficult degradation water of low cost, the method utilizes the heat accumulating type of waste water volatilization process to steam The method that eliminating water middle and high concentration volatile organic matter is removed in vapour burning, has reached energy-saving purpose.
The minimizing technology of volatile organic matter in the difficult degradation water of the present invention, be:
Waste water enters vaporizer, and the mixed vapour containing volatile organic matter that waste water evaporation produces enters heat storage, stores Hot body, at least provided with three groups, is first entered by first group of heat storage and burns unit, and the accumulation of heat heating using first group of heat storage Mixed vapour, burns the Organic substance that unit heating is burned in steam, and mixed vapour is heated to be superheated steam, superheated steam warp The sensible heat of steam is discharged by the process crossing second group of heat storage, heats second group of heat storage, returns thereafter vaporizer, for evaporation Device provides heat, and meanwhile superheated steam is to the remaining mixed vapour purging in the 3rd group of accumulation of heat body;When superheated steam is Inlet temperature t1 (entering temperature during heat storage by burning unit) of two heat storages is with outlet temperature t2 (by heat storage heel row The temperature going out) temperature difference when reaching 20 DEG C, switching mixed vapour passes through second group of heat storage and enters to burn unit, superheated steam warp Cross the 3rd group of heat storage and return to vaporizer, pass through superheated steam to the remaining mixed vapour purging in first group of accumulation of heat body simultaneously; When superheated steam the 3rd group of heat storage outlet temperature t2 and the mixed vapour inlet temperature t1 temperature difference reach 20 DEG C when, switching is mixed Close steam and pass through the 3rd group of heat storage entrance burning unit, superheated steam returns to vaporizer through first group of heat storage, leads to simultaneously Cross superheated steam to the remaining mixed vapour purging in second group of accumulation of heat body;When superheated steam is in first group of heat storage and outlet temperature Degree t2 and when reaching 20 DEG C of inlet temperature t1, make mixed vapour pass through first group of heat storage again and enter burning unit;So follow Ring, until wastewater treatment finishes;
The condensed water producing in vaporizer is discharged by base of evaporator, and remaining fixed gas can be discharged by vaporizer tail end, steams Send out the concentration salt of waste water remaining after evaporation or concentration saline in device to be discharged by the discharging opening of vaporizer.
Incineration temperature t in described burning unit is set as 700-850 DEG C.
Burning required air in unit is provided by the air pipe line being connected with burning unit, and air capacity is discharged by heat storage The oxygen content of superheated steam determines, oxygen content percent by volume is 0.5-1%.
The present invention, while with reference to waste water evaporation and high-temperature heat accumulation, supplements quantitative oxygen in high-temperature region, completes organic The complete oxidation of thing, the saturated vapor of waste water evaporation process is changed into superheated steam during regenerative oxidation, and in subsequent evaporation The hot fluid side release heat of device unit, the fixed gas in waste gas is then processed by follow-up atmospheric valve emptying, completes high-salt wastewater The evaporation of middle volatile organic matter, burning disposal process.Flexible operation, organic matter removal thoroughly, has reached energy-saving mesh 's.
Brief description
Fig. 1 is the principle schematic diagram. of the removal system of volatile organic matter in difficult degradation water in the present invention.
In figure: 1. vaporizer, 2. vacuum pump, 3. vapour compression machine, 4. circulating fan, 5. oxygen content probe, 6. the first storage Hot body, 7. the second heat storage, 8. the 3rd heat storage, 9. burns unit, 10. combustion gas inlet pipe, 11. air inlet lines, 12. mixed vapours Pipeline, 13. superheated steam pipelines, 14. scavenging pipelines;1a. first intake valve, 1b. second intake valve, 1c. the 3rd intake valve, 2a. first blow down valve, 2b. second blow down valve, 2c. the 3rd blow down valve, 3a. first air outlet valve, 3b. second air outlet valve, 3c. the 3rd Air outlet valve.
Specific embodiment
Realize the system of the minimizing technology of volatile organic matter in difficult degradation water of the present invention, as shown in figure 1, including vaporizer 1st, the first heat storage 6, the second heat storage 7, the 3rd heat storage 8 and burning unit 9.Vaporizer 1 is connected with superheated steam pipeline 13, The outlet of vaporizer 1 is connected with mixed vapour pipeline 12, and superheated steam pipeline 13 is connected with scavenging pipeline 14.Can steam in mixing Vapour compression machine 3 (if can be without vapour compression machine using triple effect evaporation system), scavenging pipeline 14 are connected with vapor pipeline 12 On be connected with circulating fan 4.Oxygen content probe 5 is connected with superheated steam pipeline 13.
First heat storage 6 pass through the first intake valve 1a, the first blow down valve 2a and the first air outlet valve 3a respectively with mixed vapour Pipeline 12, scavenging pipeline 14 and superheated steam pipeline 13 connect.Second heat storage 7 passes through the second intake valve 1b, the second blow down valve 2b and the second air outlet valve 3b is connected with mixing water vapor line 12, scavenging pipeline 14 and superheated steam pipeline 13 respectively.3rd storage Hot body 8 pass through the 3rd intake valve 1c, the 3rd blow down valve 2c and the 3rd air outlet valve 3c respectively with mixing water vapor line 12, scavenging conduit Road 14 and superheated steam pipeline 13 connect.First heat storage 6, the second heat storage 7 and the 3rd heat storage 8 are all with burning unit 9 even Connect, burn unit 9 and be connected with combustion gas inlet pipe 10 and air inlet lines 11.
Generally waste water can be used for the next stage vaporizer of triple effect evaporation process by the vapor that evaporator evaporation produces After thermal source, or entrance vapour compression machine adiabatic heating in mvr system, for the conducting self-heating of waste water in vaporizer, concentrate Vaporizer discharged by salt or concentration saline.In the present invention, it is to introduce the mixed vapour containing volatile organic matter to burn unit 9, After burning the Organic substance in mixed vapour, come back to vaporizer 1.
Details are provided below to volatile organic matter removal in difficult degradation water for said system.
(1) waste water enters vaporizer 1, and the mixed vapour containing volatile organic matter that waste water evaporation produces enters mixing and steams Vapor pipeline 12, enters heat storage by mixed vapour pipeline 12 by vapour compression machine 3, is entered by heat storage and burns unit 9, burns The Organic substance in steam is burned in the heating of unit 9 one aspect, on the one hand makes heat storage accumulation of heat.It is organic that mixed vapour incinerates volatility Become oxygen-containing superheated steam after thing, vaporizer 1 is come back to by superheated steam pipeline 13, provide heat for vaporizer 1, for steaming Send out the heating of waste water in device, the condensed water of generation is discharged by vaporizer 1 bottom, and remaining fixed gas can be passed through by vaporizer 1 tail end Vacuum pump 2 negative pressure is discharged, or is discharged by vent valve through positive pressure system.
Waste water enters concentrating salt or concentrating the discharging opening discharge by vaporizer 1 for the saline of vaporizer 1 remaining after evaporation.
(2) temperature t1 before mixed vapour enters and burns unit 9, in measurement scavenging pipeline 14.
(3) three heat storages coordinate its three valve alternate cycles connecting to use, and complete burning and heat exchange.Single accumulation of heat Three valve groups on body, can only open one in work, other two is to close.In namely working, the first heat storage 6 On the first intake valve 1a, the first blow down valve 2a and tri- valve only one of which of the first air outlet valve 3a open-minded;On second heat storage 7 The second intake valve 1b, the second blow down valve 2b and tri- valve only one of which of the second air outlet valve 3b open-minded;On 3rd heat storage 8 3rd intake valve 1c, the 3rd blow down valve 2c and the 3rd air outlet valve 3c only one of which are open-minded.
Mixed vapour enters the first heat storage 6 through the first intake valve 1a first, and (now the first blow down valve 2a and first gives vent to anger Valve 3a is to close), heat and rise to the first heat storage 6 top through the first heat storage 6, enter and burn unit 9.Burn unit Temperature t in 9 is 700-850 DEG C, burns the Organic substance in degraded mixed vapour in incineration area.Superheated steam after purification, warp Second heat storage 7 and the second air outlet valve 3b leave burning unit 9, and (now the second intake valve 1b and the second blow down valve 2b is to close ), superheated steam cools down when the second heat storage 7, then enters vaporizer 1 by superheated steam pipeline 13.Meanwhile, to the 3rd The remaining mixed vapour purging of heat storage 8, ON cycle blower fan 4, open the 3rd blow down valve 2c, circulating fan 4 passes through scavenging conduit Clean superheated steam in superheated steam pipeline 13 is delivered to the 3rd heat storage 8 by road 14, and stripping the 3rd heat storage 8 inner pore is empty Interior mixed vapour containing Organic substance;The mixed gas producing enter burns unit 9, with the mixing rising through the first heat storage 6 Steam completes Organic substance burning process.
The temperature difference when steam (saturated vapor) inlet temperature t1 and outlet temperature t2 (temperature discharged after heat storage) When reaching 20 DEG C (namely superheated steam passes through the temperature difference of temperature t2 during the second heat storage 7 and saturated vapor t1), make second Heat storage 7 switches to mixed vapour to rise heating passage, that is, closes the first intake valve 1a, closes on the second heat storage 7 Second air outlet valve 3b, opens the second intake valve 1b, makes mixed vapour pass through the second heat storage 7 and heat and burn.Mistake after purification Vapourss leave burning unit 9 (now the 3rd intake valve 1c and the 3rd blow down valve 2c through the 3rd heat storage 8 and the 3rd air outlet valve 3c It is to close), superheated steam cools down when three heat storages 8, then enters vaporizer 1 by superheated steam pipeline 13.Meanwhile, Remaining mixed vapour purging to the first heat storage 6, ON cycle blower fan 4, open the first blow down valve 2a, circulating fan 4 passes through Clean part superheated steam in superheated steam pipeline 13 is delivered to the first heat storage 6, stripping first accumulation of heat by scavenging pipeline 14 Mixed vapour containing Organic substance in body 6 inner pore space;The mixed gas producing enter burns unit 9, and through the second heat storage 8 The mixed vapour mixing rising completes Organic substance burning process.
When superheated steam reaches 20 DEG C in outlet temperature t2 of the 3rd heat storage 8 with the temperature difference of inlet temperature t1, then make 3rd heat storage 8 switches to mixed vapour to rise heating passage, that is, closes the second intake valve 1b, closes the 3rd heat storage 8 On the 3rd air outlet valve 3c, open the 3rd intake valve 1c, make mixed vapour pass through the 3rd heat storage 8 and heat and burn.After purification Superheated steam again through the first heat storage 6 and the first air outlet valve 3a leave burning unit 9 (now the first intake valve 1a and first blows Sweeping valve 2a is to close), superheated steam cools down when the first heat storage 6, then enters vaporizer by superheated steam pipeline 13 1.Meanwhile, the remaining mixed vapour purging to the second heat storage 7, opens the second blow down valve 2b, circulating fan 4 passes through scavenging pipeline The clean superheated steam of superheated steam pipeline 13 interior part is delivered to the second heat storage 7 by 14, and the mixed gas of generation enter burns Burn unit 9, complete Organic substance burning process with mixing through the mixed vapour that the 3rd heat storage 8 rises.
When superheated steam the first heat storage 6 outlet temperature t2 and saturated vapor inlet temperature t1 and the temperature difference reach 20 DEG C When, then make the first heat storage 6 switch to mixed vapour to rise heating passage, that is, close the 3rd intake valve 1c, close first The first air outlet valve 3a on heat storage 6, opens the first intake valve 1a, makes mixed vapour pass through the first heat storage 6 and heat and burn.
So, carry out by following moving in circles: mixed vapour enters the first heat storage 6-- and burns unit 9 burning degraded -- Superheated steam is discharged and the 3rd heat storage 8 is purged by the second heat storage 7 -- and mixed vapour enters the second heat storage 7-- and burns list Unit 9 burns degraded -- superheated steam is discharged and the first heat storage 6 is purged by the 3rd heat storage 8 -- mixed vapour and enters the 3rd storage Hot body 8- burns unit 9 burning degraded-superheated steam and is discharged and the second heat storage 7 is purged by the first heat storage 6.
The unlatching logical relation of each control valve is determined by electromagnetic valve logic controller.
Burning required burning oxygen in unit 9 is provided by the air inlet lines 11 burning unit 9 top, burns in unit 9 When temperature t does not reach 700-850 DEG C of interval of setting, from combustion gas inlet pipe 10 and air inlet lines 11 to top burner additional heat To design temperature.Required air quantity is used for the superheated steam discharged by heat storage 6 of measurement by being arranged on superheated steam pipeline 13 Oxygen content probe 5 measure after determine, oxygen content percent by volume be 0.5-1%.

Claims (3)

1. in a kind of difficult degradation water volatile organic matter minimizing technology, it is characterized in that:
Waste water enters vaporizer, and the mixed vapour containing volatile organic matter that waste water evaporation produces enters heat storage, heat storage At least provided with three groups, first entered by first group of heat storage and burn unit, on the one hand having in steam is burned in heating to burn unit Machine thing, on the one hand makes heat storage accumulation of heat, and mixed vapour becomes superheated steam after incinerating volatile organic matter, and superheated steam passes through Second group of heat storage returns to vaporizer, provides heat for vaporizer, passes through superheated steam to residual in the 3rd group of accumulation of heat body simultaneously Remaining mixed vapour purging;When superheated steam is reached with the temperature difference of saturated vapor inlet temperature t1 in outlet temperature t2 of the second heat storage During to 20 DEG C, make mixing saturated vapor pass through second group of heat storage and enter burning unit, superheated steam is through the 3rd group of heat storage Return to vaporizer, pass through superheated steam to the remaining mixed vapour purging in first group of accumulation of heat body simultaneously;When superheated steam is When outlet temperature t2 of three groups of heat storages and the temperature difference of inlet temperature t1 reach 20 DEG C, mixed vapour is made to pass through the 3rd group of heat storage Enter and burn unit, superheated steam returns to vaporizer through first group of heat storage, pass through superheated steam to second group of accumulation of heat simultaneously Internal remaining mixed vapour purging;The temperature difference when outlet temperature t2 in first group of heat storage for the superheated steam and inlet temperature t1 When reaching 20 DEG C, make mixed vapour pass through first group of heat storage again and enter burning unit;So circulate, until wastewater treatment is complete Finish.
2. in difficult degradation water according to claim 1 volatile organic matter minimizing technology, it is characterized in that: described burn single Incineration temperature t in unit is set as 700-850 DEG C.
3. in difficult degradation water according to claim 1 volatile organic matter minimizing technology, it is characterized in that: burn unit in Required air is provided by the air pipe line being connected with burning unit, and the oxygen content of the superheated steam that air capacity is discharged by heat storage is true Fixed, oxygen content percent by volume is 0.5-1%.
CN201611011861.5A 2016-11-17 2016-11-17 The minimizing technology of volatile organic matter in a kind of water difficult to degrade Active CN106348371B (en)

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CN110566980A (en) * 2019-09-06 2019-12-13 山东理工大学 High-salt high-concentration chlorine-containing wastewater steam recycling high-temperature thermal oxidation equipment and process
CN110937648A (en) * 2019-12-25 2020-03-31 浙江工业大学 Process and device for continuously treating high-concentration organic wastewater

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CN110937648A (en) * 2019-12-25 2020-03-31 浙江工业大学 Process and device for continuously treating high-concentration organic wastewater
CN110937648B (en) * 2019-12-25 2021-03-30 浙江工业大学 Process and device for continuously treating high-concentration organic wastewater

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