Context Distillery _ Science of Incineration

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Presentation on CPCB`s Contradictory Directives
ON INCINERATION IN DISTILLERIES
SOME OF THE REFERENCES ARE ABSTRACTS OF INFORMATION AVAILABLE ON INTERNET
V. A. Kumar
Head - Coordination
COVARM
Coordinator for Value Addition and Resource Management
www.covarm.com , mail at : va.kumar@covarm.com / covarmcare@gmail.com
call at : 91-98733-49421 / 91- 98730-79221
COMMITMENT OF PROFIT & PROTECTION THROUGH VALUE ADDITION & RESOURCE MANAGEMENT
COVARM
SCIENCE OF INCINERATION
Coordinator for Value Addition and Resource Management
HOW SPENTWASH IS GENERATED
• Sulfur dioxide, chlorine, ammonium bisulfite or commercial FDA-approved biocides are sometimes used to
disinfect cane juice.
• Milk of lime (a slurry of calcium hydroxide) and phosphoric acid is added to cane juice during the clarification
step; however, lime is mostly removed by filtration during clarification.
• Several other chemicals are used in sugar manufacturing process at different stages.
• Molasses are one of the final by-product of sugar manufacturing.
• Fermentation followed by distillation is the most common naturally occurring biological process used to
manufacture ethanol.
• Yeast strains are traditionally used to perform the alcoholic fermentation of diluted molasses. Other genetically
modified microorganisms or enzymes are also used sometimes in the process.
• The pH of the fermentation broth may be lowered (pH = 4–5) using sulfuric acid to minimize the risk of bacterial
contamination.
• In addition, antibiotics (e.g., penicillin) and bactericides (e.g., chlorine dioxide) are potentially added to control
bacteria present in the molasses feedstock.
• Most of the above steps & process additives are involved in generation of spent wash from cane molasses.
CPCB GUIDELINES ON INCINERATION
SCIENCE OF INCINERATION
COMMON INCINERATION FACILITIES
• As the common incineration systems will be handling wastes having varying heat
value, and while ensuring TOC and LOI requirements in the ash/slag, there are
possibilities for sudden rise of temperatures in the kiln. Therefore, the facilities may
like to have thermal refractory bricks and insulation capable of withstanding a
minimum temperature of 1,300°C (typically, corundum / chromium bricks).
COMBUSTION CHAMBERS (Rotary Kiln and Secondary Combustion Chamber)
Rotary Kiln
• In the rotary kiln, the temperature shall be maintained at 800+°C in order to ensure
complete burning of solid waste. Controlled flow of air shall be maintained for
complete volatilization of solid waste.
Secondary Combustion Chamber
• Minimum temperature requirement in the secondary combustion chamber is 1100° C.
COVARM
SCIENCE OF INCINERATION
Coordinator for Value Addition and Resource Management
ALL DISTILLERY SLOP BURNING BOILERS ARE C0MMON INCINERATION BOILERS
USING SOLID WASTE BAGASSE OR R/H OR COAL ETC AND LIQUID SLOP AS FUEL.
IN DISTILLERY INDUSTRY, EXCEPT WHERE SUGAR BOILERS ARE USED FOR
UTILITY IN SUGAR SEASON, COMMON BOILER PRESSURE IS TYPICALLY 10 TO
45 KG. OVIOUSLY TEMPERATURES ARE ALSO LOW.
OPERATING RANGE OF INCINERATION BOILERS OFFERED BY DIFFERENT
SUPPLIERS IN INDIA ARE IN THE RANGE:
•
•
•
•
OPERATING CAPACITY- 10 TO 75 TPH
PRESSURE
- 10 TO 66 KG/CM G
TEMPERATURE
- SATURATED OR FROM 350 TO 4800 C
SUPPORT FUELS
- INDIAN COAL, IMPORTED COAL, WOOD
CHIPS, PETCOKE AND BAGASSE
CPCB GUIDELINES ON INCINERATION
SCIENCE OF INCINERATION
POLLUTION CONTROL DEVICES
• Pollution control devices are required to comply with prescribed standards for
particulate matter, HCl, SO2, CO, Total Organic Carbon, HF, NOX (NO and NO2
expressed as NO2 ), Hydrocarbons, Dioxins/Furans, Cd +Th (and its compounds), Hg
(and its compounds), Sb + As + Pb + Cr + Co + Cu + Mn + Ni + V (and their
compounds).
• Designed treatment scheme shall comprise of following equipment, in combination,
with adequate efficiencies to meet the emission standards:
• Dioxins: Keeping De-novo synthesis in the backdrop, steps must be taken to prevent
reformation of dioxins by rapidly lowering the flue gas temperatures, particularly from
500° C to less than 200° C by adopting rapid quench / catalyst / adsorption by
activated carbon etc.
MOST IMPORTANT GUIDELINE NOT COMPLIED AT ALL
Access shall be provided, online, to see the continuous monitoring data by the local regulatory
Board/ Committee and annual environmental report giving complete details of operation &
compliance with regulatory requirements need to be published and made available to the public.
CPCB DIRECTIVES ON INCINERATION
SEARCH GOOGLE FOR
“GENERAL ANALYSIS OF SPENT WASH AFTER EVAPORATION,”
ON 1ST PAGE SL. 8 WILL APPEAR
USE OF HAZARDOUS WASTE AS FUEL - PowerShow.com
www.powershow.com/.../USE_OF_HAZARDOUS_WASTE_AS_FUEL_..
Spent Wash generation depends on: Type of fermentation process (Batch
or Continuous) Type of distillation process (Atmospheric or Multi-pressure)
... – A free .
WHEN YOU OPEN THIS A PowerShow.com PAGE WILL OPEN UP AND THIS
PPT. PRESENTATION OPEN UP
SLIDE 1
SLIDE 52
SCIENCE OF INCINERATION
INCINARATION AS PROMOTED IN INDIA
ETHANOL INDUSTRY IS BEING FORCED TO GO
FOR A TECHNOLOGY SOLUTION
FOR ZERO DISCHARGE
WHICH IS NOT A REAL SOLUTION
AND NEED A LOT MORE RESEARCH
BEFORE BEING ACCEPTED AS A FINAL SOLUTION
SCIENCE OF INCINERATION
CPCB AGREES THAT SPENT WASH IS HAZARDOUS EFFLUENT
IN SLIDE 29 CPCB HAVE ADMITTED THAT since June 2008 many distilleries
have been directed to adopt either concentration-incineration system or
co-processing for achieving ZLD.
IN SLIDE 42 & 43 CPCB AGREES THAT DISTILLERY SPENT WASH
CONTAIN ABOVE 2% CHLORINE & APPROX. 0.004% Cu
BUT RESEARCHES HAVE PROVED THAT
ANY EFFLUENT (SPENT WASH IN THIS CASE) CONTAINING
HALOGEN COMPOUNDS & COPPER TRACES,
IF INCINERATED, PRODUCES DIOXIN.
AND DIOXINS ARE PROVEN CANCEROUS COMPOUNDS.
COVARM
Coordinator for Value Addition and Resource Management
WHAT IS DIOXIN
Dioxin is the common name for a class of 75+ chemicals.
Dioxins have no commercial use.
It is a toxic waste product formed when waste containing chlorine is burned.
Dioxin particles emitted with smokestack of incinerator does not readily break down in
the environment and are carried by the wind.
• Grazing animals and fish ingesting dioxin, cannot break it down, so it travels up the food
chain.
• Continual low-level exposure may leads to a "build up" in tissues resulting into several
health problems.
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•
•
•
•
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smokestacks of the incinerator. Dioxin particles are then carried by the wind until they drop onto land or
water. We now know that dioxin can travel thousands of miles. Grazing animals and fish ingest the dioxin, but
•
they cannot break it down, so it then travels up the food chain. Ninety percent of human exposure to dioxin
•
•
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occurs through our diets of meat, dairy products, eggs and fish.
Dioxin builds up in fatty tissue. Because of the high fat content of breast milk, nursing infants are exposed to
about 50 times the adult dose and may receive more than 10 percent of their total lifetime exposure during the
•
nursing period, a time when they are most vulnerable to the toxic effects of dioxin.
•
Every person has some amount of dioxin in their body. This is because dioxin, like DDT, does not readily break
•
down in the environment. It also accumulates in the body. Continual low-level exposure leads to a "build up" in
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tissues.
COVARM
Coordinator for Value Addition and Resource Management
EFFECT OF DIOXINE ON HUMAN HEALTH
CANCER: DIOXIN IS A PROVEN HUMAN CARCINOGEN ( INTERNATIONAL AGENCY FOR RESEARCH ON CANCER (IARC).
DIOXIN CAUSES LIVER, LUNG, STOMACH, SOFT AND CONNECTIVE TISSUE CANCERS AS WELL AS NON-HODGKINS’S
LYMPHOMA.
IMMUNE SYSTEM EFFECTS: LOW EXPOSURES TO DIOXIN RESULT IN INCREASED SUSCEPTIBILITY TO BACTERIAL, VIRAL
AND PARASITIC DISEASES.
REPRODUCTIVE AND DEVELOPMENT EFFECTS : DIOXIN EXPOSURE CAUSES HUMAN STUDIES REPORT LOWERED
TESTOSTERONE LEVELS IN HUMAN AND BIRTH DEFECTS IN THEIR CHILDREN. NURSING HUMAN INFANTS EXPOSED TO
HIGH DIOXIN CONCENTRATIONS HAD SIGNIFICANTLY LOWER LEVELS OF THE THYROID HORMONE NECESSARY FOR
DEVELOPMENT OF THE BRAIN.
HORMONE DISRUPTION: DIOXIN BEHAVES LIKE A HORMONE BY ATTACHING TO A RECEPTOR AND ALTERING THE
GENETIC ACTIVITY IN CELLS. SINCE HUMAN HORMONES CAN EXERT EFFECTS AT LEVELS OF PARTS PER TRILLION,
SMALL AMOUNTS OF DIOXIN COULD CAUSE A CHAIN REACTION IN THE BODY.
OPEN ON GOOGLE SEARCH
http://www.ncbi.nlm.nih.gov/pubmedcommons/
THE SITE THAT OPENS UP IS
This is PublMED.gov site and official site of
US National Library of Medicine & National Institutes of Health
PubMed Commons enables authors to share opinions and information about scientific publications in
PubMed.
This research paper is available on this site.
Dioxin formation from waste incineration.
Shibamoto T1, Yasuhara A, Katami T.
SCIENCE
OF
INCINERATION
MORE RESEARCH WORK IS AVAILABLE ON GOOGLE SITES
SCIENCE OF INCINERATION
YOU NEED TO ENLARGE ABSTRACT OF THIS WORK PASTED BELOW,
WHICH SAYS CERTAIN VERY IMPORTANT THINGS OTHERWISE IGNORED
WHILE ISSUEING DIRECTIVES FOR INCINERATION TO DISTILLERIES.
ADDITIONALLY, DIRECTIVE 2000/76/EC OF THE EUROPEAN PARLIAMENT
AND OF THE COUNCIL of 4 December 2000 on the incineration of waste
from Official Journal of the European Communities need to be studied
before such directives.
There has been great concern about dioxins-polychlorinated dibenzo dioxins (PCDDs), polychlorinated dibenzo furans (PCDFs), and polychlorinated biphenyls (PCBs)-causing contamination in the environment because the adverse effects of these chemicals on human health have been known for
many years. Possible dioxin-contamination has received much attention recently not only by environmental scientists but also by the public, because dioxins are known to be formed during the combustion of industrial and domestic wastes and to escape into the environment via exhaust gases from
incinerators. Consequently, there is a pressing need to investigate the formation mechanisms or reaction pathways of these chlorinated chemicals to be able to devise ways to reduce their environmental contamination. A well-controlled small-scale incinerator was used for the experiments in the core
references of this review. These articles report the investigation of dioxin formation from the combustion of various waste-simulated samples, including different kinds of paper, various kinds of wood, fallen leaves, food samples, polyethylene (PE), pol ystyrene (PS), polyvinyl chloride (PVC),
polyvinylidene chloride, polyethylene tetraphthalate (PET), and various kinds of plastic products. These samples were also incinerated with inorganic chlorides (NaCl, KCl, CuCI2, MgCl2, MnCl2, FeCl2, CoCl2, fly ash, and seawater) or organic chlorides (PVC, chlordane, and pentachlorophenol) to
investigate the role of chlorine content and/or the presence of different metals in dioxin formation. Some samples, such as newspapers, were burned after they were impregnated with NaCl or PVC, as well as being cocombusted with chlorides. The roles of incineration conditions, including chamber
temperatures, O2 concentrations, and CO concentrations, in dioxin formation were also investigated. Dioxins (PCDDs, PCDFs, and coplanar-PCBs) formed in the exhaust gases from a controlled small-scale incinerator, where experimental waste samples were burned, were analyzed by gas
chromatography/mass spectrometry. Formation of total PCDFs was much higher than that of PCDDs in all samples. The total PCDFs comprised 70%-90% of the total dioxin formed. The amount of total PCDFs formed ranged from 0.78 ng/g (newspaper) to 8,490ng/g (PVC burned in high CO
concentration). The amount of total PCDDs formed ranged from 0.02ng/g (newspaper) to 430ng/g (PVC). Coplanar PCBs were found at the lowest level of the dioxins formed. Their formation levels ranged from 0ng/g (newspaper) to 77.6ng/g (PVC). It is obvious that the samples with either inorganic or
organic chlorides produced much more dioxins than the sample without chlorides when incinerated under similar conditions. It is not clear how inorganic and organic chloride contribute differently to dioxin formation. Among the metals examined, copper seems to have higher activity toward dioxin
formation than other metals. It acted not only as a catalyst but also as a transmitter of heterogeneous chlorine. The toxicity equivalence quantity (TEQ) values generally correlated with the amount of chlorine content in the samples and the amount of di oxin formed in exhaust gases from an incinerator.
When the same sample was incinerated at different temperatures, however, the sample burned at low temperature yielded a higher TEQ value than did the sample burned at high temperature. The samples that did not contain chlorine or were not combusted with chlorides exhibited low TEQ values. In
contrast, samples with high chlorine content, such as PVC (51.3%), gave high TEQ values. Combustion temperatures may play an important role in dioxin formation in exhaust gases from the incineration of waste materials. However, no significant relationship between dioxin formation and chamber
temperatures was reported in the core articles. However, It is obvious that dioxin formation occurred at temperatures above 450'C and was reduced significantly at temperatures above 850 degrees C. The reaction occurring in an incinerator is extremely complex, and there are many factors in addition
to combustion temperature influencing dioxin formation. Even though it is possible to hypothesize reasonable formation mechanisms of dioxins produced in exhaust gases according to the results obtained from experiments in classical chemistry, the reactions involved in an incinerator are extremely
complex and heterogeneous. More detailed investigation of the many individual factors influencing dioxin formation is needed to find ways to reduce their formation in individual and municipal incinerators.
SCIENCE OF INCINERATION
EUROPEAN COMMISSIONS COMMENT ON INCINERATION OF HALOGENOUS SUBSTRATES
Definitions
• For the purposes of this Directive:
• (1) ‘waste’ means any solid or liquid waste as defined in Article
1(a) of Directive 75/442/EEC;
• (2) ‘hazardous waste’ means any solid or liquid waste as defined
in Article 1(4) of Council Directive 91/689/EEC of 12 December
1991 on hazardous waste (1).
• (3) ‘mixed waste’ means waste from households as well as
commercial, industrial and institutional waste, which because of
its nature and composition is similar to waste from households,
but excluding fractions indicated in the Annex to Decision
94/3/EC (4) under heading 20 01 that are collected separately at
source and excluding the other wastes indicated under heading
20 02 of that Annex;
• (4) ‘incineration plant’ means any stationary or mobile technical
unit and equipment dedicated to the thermal treatment of
wastes with or without recovery of the combustion heat
generated. This includes the incineration by oxidation of waste
as well as other thermal treatment processes such as pyrolysis,
gasification or plasma processes in so far as the substances
resulting from the treatment are subsequently incinerated.
This definition covers the site and the entire incineration plant
including all incineration lines, waste reception, storage, on site
pretreatment facilities, waste- fuel and air supply systems, boiler,
facilities for the treatment of exhaust gases, on- site facilities for
treatment or storage of residues and waste water, stack, devices
and systems for controlling incineration operations, recording and
monitoring incineration conditions;
• (5) ‘co-incineration plant’ means any stationary or mobile plant
whose main purpose is the generation of energy or production of
material products and:
— which uses wastes as a regular or additional fuel; or
— in which waste is thermally treated for the purpose of disposal.
THE EUROPEAN PARLIAMENT AND THE COUNCIL OF THE EUROPEAN
UNION,
Having regard to the Treaty establishing the European Community, and
in particular Article 175(1) thereof,
(17) Member States should take into account Council Directive
1999/30/EC of 22 April 1999 relating to limit values for sulfur dioxide,
nitrogen dioxide and oxides of nitrogen, particulate matter and lead in
ambient air (4) when implementing this Directive.
(18) The incineration of hazardous waste with a content of more than 1
% of halogenated organic substances, expressed as chlorine, has to
comply with certain operational conditions in order to destroy as many
organic pollutants such as dioxins as possible.
(19) The incineration of waste which contains chlorine generates flue gas
residues. Such residues should be managed in a way that minimizes their
amount and harmfulness.
(27) The co-incineration of waste in plants not primarily intended to
incinerate waste should not be allowed to cause higher emissions of
polluting substances in that part of the exhaust gas volume resulting
from such co-incineration than those permitted for dedicated
incineration plants and should therefore be subject to appropriate
limitations.
(28) High-standard measurement techniques are required to monitor
emissions to ensure compliance with the emission limit values for the
pollutants.
SCIENCE OF INCINERATION
• As per Shibamoto T1, Yasuhara A, & Katami T
• The reaction occurring in an incinerator is extremely complex.
• Inorganic and organic chloride contribute differently to dioxin formation. Among the metals
examined, copper seems to have higher activity toward dioxin formation than other metals. It
acts not only as a catalyst but also as a transmitter of heterogeneous chlorine.
• Combustion temperatures may play an important role in dioxin formation in exhaust gases from
the incineration of waste materials. Other key players in dioxin formation could be O2
concentrations, and CO concentrations.
FOR INCINERATION OR CO-PROCESSING :
• MAXIMUM PCDD/F FORMATION OCCURS AT 300-400 °C, LITTLE CAN BE DETECTED BELOW 250
OR ABOVE 500 °C.
• BOILER NEED TO BE SUITABLY OF HIGH TEMPERATURE IN CASE CHLORINE IS AVAILABLE IN THE
FUEL MEANT FOR INCINERATION.
• BESIDES RESIDENCE TIME SHOULD BE 4 – 5 SECONDS IN AN OXYGEN–RICH ATMOSPHERE.
• MOST OF THE INCINERATION BOILERS OFFERED TO OR INSTALLED IN INDIAN DISTILLERY DOES
NOT MEETS THE TEMPERATURE CRITERIA TO REDUCE DIOXINE FORMATION.
INDUSTRIES UNDER "RED" CATEGORY WITH INTER-RELATED CONCERN
CPCB`S
CONTRADICTORY
DIRECTIVES
1. INDUSTRIES LISTED IN SL. 2, 5, 14,
24, 26, 29, 38, 40 & 57 ARE RED
2. BIOGAS (METHANE) GENERATION
IS ALLOWED WHICH FALLS UNDER
RED CATEGORY.
3. EFFLUENT OF ONE RED
CATEGORY(5) IS SUGGESTED TO
BE CO-PROCESSED IN ANOTHER
RED CATEGORY (2) INDUSTRY
4. RED CATEGORY(5) INDUSTRY IS
ASKED TO INSTALL ANOTHER RED
CATEGORY PLANT(38) FOR
EFFLUENT TREATMENT.
5. INDUSTRY OF HALOGEN & THEIR
COMPOUND IS LISTED AS RED.
2
Cement
5.
Distillery including Fermentation industry
14.
Sugar (excluding Khandsari)
24.
Chlorine, fluorine, bromine, iodine and their compounds.
26.
Common Effluent Treatment Plant
29
Fermentation industry including manufacture of yeast, beer etc.
38.
Incineration plant.
40.
Industrial or inorganic gases namely (a) Chemical gases:
Acetylene, Hydrogen, Chlorine, Fluorine, Ammonia, Sulphur
Dioxide, Ethylene, Hydrogen Sulphide, Phosphine. (b)
Hydrocarbon Gases: Methane, Butane, Ethane, Propane.
57.
Potable alcohol (IMFL) by blending or distillation of alcohol.
CPCB DIRECTIVES ON INCINERATION
NOW, PLEASE REVISIT CPCB SLIDE 34 PROMOTING JUSTIFICATION OF
CO-PROCESSING, WHICH SAYS THAT High temperatures (1100 O C)+
and residence time of 4 – 5 seconds in an oxygen–rich
atmosphere ensure the destruction of organic compounds.
SLIDE 48
IN SLIDE 48, CPCB SAYS
• * For Particulate matter: As per consent order
issued by concerned SPCB.
- For CO. TOC, NOx, HCl, SO2, HF, Total dioxins
and furans, Cd+Tl+ their compounds, Hg and
its Compounds, Sb+AS+Pb+Co+Cr+Cu+Mn+Ni+V+ their compounds:
Emission values during co-processing should not exceed the base
line emissions i.e. from pre co-processing levels.
POWERS OF POLLUTION CONTROL AGENCIES
PLEASE READ ABOUT THE POWER CONFERRED TO SPCB`S
• EVEN IF YOU AGREE FOR CONVERTING YOUR
• WATER POLLUTANT INTO
• AIR POLLUTANTS.
ARE YOU SAFE & ASSURED
ABOUT YOUR INVESTMENT IN INCINERATION PLANT ?
DON`T YOU FEEL THAT MORE RESEARCH IS NEEDED
BEFORE A FINAL & GREEN DECISION ON ZLD OPTION
COVARM
Coordinator for Value Addition and Resource Management
21[22A. POWER OF BOARD TO MAKE APPLICATION TO COURT FOR
RESTRAINING PERSON FROM CAUSING AIR POLLUTION.
(1) Where it is apprehended by a Board that emission of any air pollutant, in excess of the standards laid down by the
State Board under clause (g) of sub-section (1) of section 17, is likely to occur by reason of any person operating an
industrial plant or otherwise in any air pollution control area, the Board may make an application to a court, not inferior to
that of a Metropolitan Magistrate or a Judicial Magistrate of the first class for restraining such person from emitting such
air pollutant.
(2) On receipt of the application under sub-section (1), the court may make such order as it deems fit.
(3) Where under sub-section (2), the court makes an order restraining any person from discharging or causing or
permitting to be discharged the emission of any air pollutant, it may, in that order,-
•
•
(a) direct such person to desist from taking such action as is likely to cause emission;
(b) authorize the Board, if the direction under clause (a) is not complied with by the person to whom such direction is
issued, to implement the direction in such manner as may be specified by the court.
(4) All expenses incurred by the Board in implementing the directions of the court under clause (b) of sub-section (3)shall
be recoverable from the person concerned as arears of land revenue or of public demand.
IT IS TIME TO ASK QUESTIONS ON
CPCB DIRECTIVES ON INCINERATION
IN INCINERATION
WATER POLLUTION IS CONVERTED INTO
AIR POLLUTION
EVEN IF YOU AGREE FOR CONVERTING
YOUR WATER POLLUTANT
INTO AIR POLLUTANT.
YOUR INVESTMENT DECISION
IN INCINERATION IS
VULNERABLE
TILL TIME, WHEN A PROVEN SOLUTION IS OFFERED TO INDUSTRY, RECOVERING WATER USING SUITABLE TECHNOLOGY AND
SCIENTIFICALLY MANAGING BIO-COMPOSTING PROCESS TO ACHIEVE ZERO LIQUID DISCHARGE IS STILL BEST SOLUTION.
AND WE CAN PROVE THIS.
THANKS
FOR YOUR ATTENTION
IT`S TIME TO WORK TOGETHER
OUR NEXT EFFORT WILL BE TO PROVE THAT BIO-COMPOSTING CAN BE DONE YEAR – ROUND AND
WE WANT TO WORK ON APPROVAL OF CPCB FOR 330 DAY`S PERMISSION WITH BIO-COMPOSTING .
COVARM : COMMITMENT OF PROFIT & PROTECTION THROUGH VALUE ADDITION & RESOURCE MANAGEMENT
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