Professional Documents
Culture Documents
BASED ON
CHEMICAL ANALYSIS
By
1
COAL
• Plant debris accumulated in these ponds and lakes in alternate sequence of earthen
materials over a large period of time starting from about 300 million years ago.
• These underwent Chemical, Bio-chemical & Physical changes under high pressure and
temperature for a long time to change the plant debris to what is now called peat, lignite and
coal.
3
THE EARLIEST COAL DEPOSIT
• Only a few pre-Cambrian coals are known to-day.
• The earliest true coals formed from the algae during the mid-Proterozoic in
northern- Michigan (USA) and South Eastern Greenland.
• The first coal-bed developed from land based vegetation during the late Devonian
in North Russia and on bears Islands (near Pits-Bergen).
4
GLOBAL COAL DEPOSITS
5
GEOLOGICAL PERIOD OF INDIAN COAL DEPOSITS
Gujrat, Rajastan,
The coals of ECL, BCCL, CCL, MCL Jammu, Assam & Other NEC,
WCL, NCL,SECL & SCCL Neyveli Lignite
6
Map showing the coalfields of India
7
COMPOSITION OF PLANT
• Coal is a product of plant debris associated with certain percentages of inherent as well as
external mineral matter.
• Plant (debris) contain carbohydrates like cellulose, ligno-cellulose, starch etc. chlorophyl,
cuticles, spore-exines, oils, fats and waxes, resins, tannis, proteins, alkaloids etc.etc. and of
course water.
• Average composition of hard plant wood is as follows :
Group percentage
Cellulose 45-55
Lignin 25-35
Hemi-celluloses 4-6
Fats, waxes and resins 0.5-2
Water 10-15
8
DEPOSITION & CHANGE OF PLANT DEBRIS TO COAL
• Plant debris were deposited in large lakes, ponds either “in situ” or after being drifted by
streams, rivers. Generally one cycle of deposition of plant debris was followed by deposition
of in-organic matter. This was repeated several times corresponding to cyclic process of
sub-mergence and sedimentation.
• The organic component in the plant experienced chemical (decomposition, hydrolysis etc.),
bio-chemical and physical changes to varying degrees under temperature and pressure to
give various types of coals .
9
DIFFERENT TYPES OF COALS
• SEMI-ANTHRACITE Non-Caking
• ANTHRACITE Non-Caking
10
COALIFICATION SERIES & RANK OF COAL
• It can be inferred that anthracite coal is more matured than the bituminous.
11
NATURE OF INDIAN COAL DEPOSITS (Contd.)
• Indian coals are mostly of drift origin and hence contain high mineral
matter.
• The coals of Gujarat Rajasthan and Assam etc. are of Marine origin.
12
DEFINITION OF COAL
“Coal is a rock, composed of different kinds of organic matter which vary in their proportion
in different coal and no two coals are absolutely identical in nature” (Hendricks)
“Coal is a compact stratified mass of metamorphosed plants which have , in part, suffered
arrested decay to varying degrees of completeness” (Stopes, and Wheeler and modified by
Fox)
“Coal may be defined as a stratified mass of plant debris which has been modified
chemically (by oxidation, reduction, hydrolysis , condensation and the effects of heat, and
pressure in the presence of water) and physically (including reduction in strength of woody
cell structure by the development of colloidal properties, causing increase in hardness and
brightness), by natural agencies (the action of bacteria and fungi) interspersed with small
amounts of inorganic matter. (Wilfrid Francis)
13
CHEMICAL STRUCTURE OF COAL
• Plant debris (and associated mineral matters ) have undergone varying degrees of changes
during coalification to form coal.
• A no. of authors have suggested a no. chemical structure of coal. The ones suggested by
Scientists in recent times have been shown in the following slide .
• As the rank increases, number of fused benzene ring increase in the coal unit and the
functional groups and side chains decreases giving rise to basic difference in the coal unit.
14
CHEMICAL STRUCTURE OF COAL
15
CHEMICAL STRUCTURE OF COAL (Contd)
16
Chemical Structure of Coal (Contd.)
17
COAL REPOSITORY OF INDIA AS ON 01.04.2010
Lignite 68.98
Coal extracted so far = 10.34 billion tonnes ( Coal Controllers Organization, 2009-10)
18
SAMPLING OF COAL
• Bulk samples collected are subjected to crushing at proper size followed by coning and
quartering to reduce the quantity of the samples.
• Sample quantity is further reduced to about ½ Kg. by repeated mixing, coning and quartering.
• This ½ Kg. sample so reduced is passed through 72 mesh sieve (211 micron), put in a air tight
bottle, properly leveled and is sent for determining different parameters for its characterization.
19
SAMPLING OF COAL (Contd.)
• Coal bands are characterized visually whether it is bright, dull coal with thin
laminations of bright (DCTLB), dull coal recording if there is any visible minerals
incrustated in it etc.
• Non-coals are further visually seen whether it is shaly coal, carb. sh., grey sh.
• Thickness and weight of each band are recorded in the proper format.
• Representative sample of Individual bands are prepared (72 mesh) and sent to
laboratory for analysis (moist% and ash%)
20
CONFIRMATION OF LITHO-UNITS BY CHEMICAL ANALYSIS
• Coking coals :
Litho-units Ash %
Coal < 35
Sh. C. >35 - < 50
Carb. Sh. >50 - < 75
Grey Sh. > 75
• Non-coking coals :
Litho- units (Moist + Ash)%
Coal < 40
Sh.C. > 40 - < 55
Carb. Sh. >55 - < 75
Grey Sh. >75
21
Preparation of Seam Overall samples
• Based on whether the bore hole coal core are from a coking coalfield or non-coking coalfield
the following representative seam overall samples are prepared.
22
COAL CHARACTERISATION
PROXIMATE ANALYSIS
23
COAL CHARACTERISATION (Contd)
24
COAL CHARACTERISATION (Contd)
•Ash %
i) Very good quality coal <10% ash
ii) Good or selected quality coal 10-20% ash
iii) Fair quality coal 20-25% ash
iv) Inferior quality coal 25-35% ash
25
COAL CHARACTERISATION (Contd)
26
CHARACTERISATION OF COAL (Contd.)
• MOISTURE AT 96% RH & 40 C : From the proximate analysis of coal, we are able to know
whether the particular coal is low moisture(<2% moisture) coal or high moisture (>2%
moisture) coal. For high moisture coal, moisture % is determined at 60% RH & 40 C a
standard condition for expressing proximate analysis at 60% RH & 40 C by calculation.
CALCULATION OF USEFUL HEAT VALUE (UHV) : For gradation of Coal for its marketing
purposes, UHV is calculated from Moisture and Ash percentages expressed at 60% RH &
40 C as follows:
For high ash low moisture coal also, Gradation is done by calculating UHV from the
following formula :
UHV = 8900 - 138x (A + M) -150x( 19 - VM)
27
CHARACTERISATION OF COAL (Contd.)
• Calorific Value : The heat liberated during complete combustion of unit mass of coal in the
presence of sufficient quantity of oxygen and entire system maintained at standard condition
is called calorific value or Gross Calorific Value (GCV) of coal. Gross C.V. is determined by
Bomb Calorimetric method. It is expressed as K. Cals /Kg or B.T.U./lb.
• Net Calorific Value : Net calorific Value (NCV) is the quantity of heat liberated by the
complete combustion of of unit mass of coal, when the water produced is assumed to
remain as a vapour and heat is not recovered ( heat of condensation).
28
CHARACTERISATION OF COAL (Contd.)
• 2nd factor, 138, is for the correction for the actual availability of heat value available from a particular coal
for the industry, This was calculated long back when Lancashire boilers were in operation . Now coals
are burnt using different technologies in which this correction factor is not correct and it gives erroneous
figures.
• When the (M+A) of coal becomes 64.5% , UHV becomes zero. But captive power plants use coal having
(moist. + ash)% > 64.5 . Here gradation of coal is not possible and marketing will not be possible unless
alternate gradation system is available.
• To eliminate the above ambiguity, gradation of coal based on GCV was suggested by CFRI.
• The equivalency chart of gradation based on UHV and GCV is given in the following slide.
29
CHARACTERISATION OF COAL (Contd).
Coal grade Based on UHV (Moist. + ash)% Based on GCV at 5% moist level
(K.Cals/Kg.) (K.Cals/Kg)
B >5600 but < 6049 19.6 - 23.8 >6062 but < 6466
C >4940 but < 5600 23.9 - 28.6 >5610 but < 6062
D >4200 but < 4940 28.7 - 34.0 > 5101 but < 5610
E >3360 but < 4200 34.1- 40.0 > 4536 but <5101
F >2400 but < 3360 40.1- 47.0 >3877 but < 4536
G >1300 but < 2400 47.1 - 55.0 >3124 but < 3877
30
CHARACTERISATION OF COAL (Contd.)
• Coal companies are suggesting for taking coal on no loss no profit basis.
• If coals are marketed on GCV gradation basis, sometimes the producers have to sell
better grade coal in the same price. So coal companies will incur heavy loss.
• In the above gradation basis, coals having GCV less than 3113 K.Cals/Kg. have not
been graded. But these coals are used in captive power plants.
• Grade bands in coal gradation based on GCV in the previous table is not uniform.
31
COAL CHARACTERISATION (Cond.)
32
CHARACTERISATION OF COAL (Contd.)
• ULTIMATE ANALYSIS : It is the complete chemical analysis of the organic part of coal :
ULTIMATE ANALYSIS
33
CHARACTERISATION OF COAL (Contd.)
Inorganic carbon
34
CHARACTERISATION OF COAL (Contd)
• Hardgrove Grindability Index (HGI) : This parameter defines the ease of grinding of coal. 50
gm. Coal (passed though 30 ASTM and retained by 16 ASTM sieve) is taken in a HGI
machine and subjected to grinding the coal in a bowl by 6 balls of standard weight and size
under pressure of 29.0 Kg. for 3 minutes for 60 revolutions.
• The weight of coal retained by 200 ASTM sieve is measured. The HGI is calculated by the
following formula :
HGI = 13 + 6.93 M
35
CHARACTERISATION OF COALS ( Contd.)
• After getting results of proximate analysis results, it is ascertained whether a particular coal
is caking or non-caking.
• If the coal is of caking nature, its caking propensities are characterised by the following
parameters :
– GK LT Coke Type
– Free Swelling Index
– Gieseler Plastometric Test
– Sapozhnikov’s Maximum Thickness of Plastic Layer (MTPL)
36
CHARACTERISATION OF COAL (Contd)
• GKLT COKE TYPE : Coal (20 gm.) is taken in a retort, spread to length of 15 cm. and
given a semi-cylindrical shape , charged in Coke Type apparatus maintained at 600 C and
heated for 15 minutes . Cooled and coke pencil left in the retort is matched with standard
coke pencil profile as shown in the next slide.
• The coke pencil matching most with the standard profile will be the GK LT CT of the sample.
37
CHARACTERISATION OF COAL (Contd.)
38
CHARACTERISATION OF COAL (Contd.)
• Free Swelling Index : 1gm. Coal in a Swelling Index crucible. Charged at 850 C for not less
than 2 ½ minutes or till the VM. ceases to come out. The coke button left is matched with
standard profiles. The standard profile matching most is the F.S.I. of the sample. Standard
profiles are in the next slide.
39
CHARACTERISATION OF COAL (Contd.)
40
CHARACTERISATION OF COAL ( Contd.)
• Ash Analysis : Silica, alumina, titania, phosphorus pentoxide , iron oxide, calcium oxide,
magnesium oxide, sodium oxide, potassium oxide , sulphate percentages are determined in
coal ash sample
• Ash Fusion Temperature Range : Four temperatures are determined ; Initial Deformation
Temperature (IDT), Sphere Temperature (ST), Hemi-sperical Temperature (HT) and Flow
Temperature.
• Phosphorus%
• Chlorine%
41
CHARACTERISATION OF COAL (Contd)
• PETROGRAPHIC PARAMETERS
42
CHARACTERISTICS OF COAL (Contd)
Composition of Moisture
•In case of low moisture coal ( with <2 % moisture), 100% water.
•In case of high moisture coals, may contain very small quantity
of pyrolysis products.
43
CHARACTERISATION OF COAL (Contd)
Silica - SiO2
Alumina – Al2O3
Ferric Oxide - Fe2O3
Titania - TiO2
Calcium oxide – CaO
Magnesium oxide - MgO
Phosphorus pentoxide – P2O5
Sulphate -SO3
Potassium oxide – K2O
Sodium oxide – Na2O
45
CHARACTERISATION OF COAL (Contd)
Composition of VM
H2 = 52 – 58%
CH4 = 26 – 30%
CnH2n+2 = 5 - 6 %
CO = 4 – 6%
CO2 = 2 – 3%
N2 = 6 -10%
O2 = <1 %
C.V. = 450 – 500 BTU/Cu ft.
46
CHARACTERISATION OF COAL ( Contd )
47
CHARACTERISATION OF COKE
• Proximate analysis
• Porosity
• Hardness
– M40
– M10
• CSR.
• CRI
48
BASES OF REPORTING OF ANALYTICAL RESULTS
• Basis of results must be mentioned while reporting the results. The following are different
bases are in practice for proper interpretation of the results :
– As received basis
– Dry basis
49
CHARACTERISATION OF COAL (Contd.)
CLASSIFICATION OF COAL
Class & Type Nature Basic Parameters Supplementary parameters CT CSN
Mean Ro% VM% GCV Moisture at 40 C m.m f basis
(K Cals/Kg.) 96% RH 60% RH Lignite Non-caking >0.28 - 0.38 >45
>6150 – 6950 >30 >24
HV-bituminous Weakly caking >0.65-0.84 32 -43 >7800 – 8100 5-9 4-7 C-D 1-3
MV-bituminous medium coking >0.85 -0.94 27-33 >8250-8500 <4 <2.5-3 E-G 3 3-6
MV – bituminous M.V strongly caking >0.95 – 1.19 22-28 >8500-8900 <2 <2 G-G1 4-6
• Chemical analysis
– Proximate analysis
– Ultimate Analysis
– Phosphorus %
– Gross CV
– LTGK CT
– Swelling Index
– Petrographic Analysis
– Maceral composition
– Average Vitrinite Reflectance ( Ro%)
51
CHARACTERISATION OF COKE
– Proximate analysis
– Gross CV
– Porosity
– Hardness
• M4o
• M10
– CSR
– CRI
– Na2O & K2O
– Sulphur %
– Phosphorus %
52
CHARACTERISATION OF COAL (Contd.)
– Proximate analysis
– GCV
– HGI
– Ash analysis
– AFTR
– Maceral composition
53
INDUSTRIAL IMPORTANCE OF DIFFERENT PARAMETERS
• Proximate Analysis : Moisture, ash, VM & FC.
• GCV
• Ash analysis : SiO2, Al2O3,TiO2, P2O5, Fe2O3, CaO, MgO, SO3, Na2O, K2O.
– Acidic oxides : SiO2, Al2O3,TiO2, P2O5, SO3 : Responsible for high ash fusion
– Basic oxides : Fe2O3, CaO, MgO Na2O, K2O: Responsible for low ash fusion
54
PARAMETERS OF COKING COALS FOR STEEL INDUSTRY
55
PARAMETERS OF COKING COALS (Contd.)
• Petrographic Properties
56
PROPERTIES OF METALLURGICAL COKE
57
PROPERTIES OF NON –COKING COALS FOR C.D.I
• Coals for CDI are mostly non-coking coals fed though the TUYERS in the Blast Furnace
Parameters Limit
Coal size Min. 80% passing 200 mesh ASTM
Moisture % (a) No upper limit
(b) 2.5-6.0 for best results
© Dried coal not more than 1.5%
Ash% As low as possible but not more than 17 %
VM% (a) 25- 30% preferred but not exceeding 35% d.b.
(b) 29-35% dmf. & not exeeding 40% (dmf)
GCV (a) 6000 K Cals/Kg. (a.d.)
(b) 7200 – 8000 K. Cals/Kg ( dmf)
AFTR (a) IDT >1200 C, HT >1400 C, FT ~ 1500 C
HGI 55-65 preferred.
58
NON-COKING COALS FOR METALLURGICAL INDUSTRY – SPONGE
IRON MAKING
• Iron is also manufactured via- DRI route using non-coking coals. Properties are given
below: (IS: 11860 -1998)
Parameters Limit
Moist% 4 (Max)
Ash % Max. 24
VM (as recd.) 25 – 35
Sulphur% 1 (max)
Caking Index <3
F.S.I 1 (max.)
IDT >1150 C (MRA) des. >1250 C(MRA)
Reactivity towards CO2 > 1.75 cc of CO/gm of C/sec.
Size ~ 25 mm to fines
59
PROPERTIES OF COALS FOR POWER PLANTS
• Power plant boilers use non-caking coals essentially for generation of electricity.
60
PROPERTIES OF COAL FOR FERTILIZER INDUSTRY
Nitrogen based fertilisers such as ammonium sulphate, ammonium nitrate etc. produced by
using mostly high ash fusion non-caking coals. Hydrogen is drawn from synthesis gas
produced by reacting coal with water and oxygen by any of the commercially available
processes like Lurgi, Winkler and Kopper –Totzek. Coals accepted by these are as follows :
Nitrogen is drawn from atmosphere. Nitrogen and hydrogen are made to react to give
ammonia.
61
PROPERTIES OF COALS FOR CEMENT INDUSTRY, TEA DRYING,
GLASS INDUSTRY, POTTERY & REFRACTORY INDUSTRIES, GAS
PRODUCERS, TOWN GAS PLANT
All these industries need heat intensive LONG FLAME COALS having following
characteristics (IS; 770- 1964)
62
CHARACTERISTICS OF COAL FOR DOMESTIC CONSUMPTION
63
COAL FOR BRICK BURNING
Parameter Limit
Moist% >2
Ash% >35
VM % <32
64
INTERCORRELATIONS OF SOME PARAMETERS OF COAL
• Some parameters of coals can be inter correlated mathematically. These help in better
understanding of coal and its behaviour. A few important correlations are given below:
M.M. = 1.09A + 0.5 S pyritic + 0.8 CO2 -1.1 SO3 (ash) + SO3 (coal) + 0.5 Cl. [KMC]
GCV (for coals having moist% <2%)K. Cals/Kg = 97.7 F + 75.6 ( V-0.1 A) – 60 M
GCV (for coals having moist% >2%) K. Cals/Kg. = 85.6 [ 100- (M+1.1A] - 60 M
65
CALCULATION OF SOME PARAMETERS
66
THIS IS ALL ABOUT THE
DISCUSSION!
THANK YOU !!
67
Quality Requirements for Non- Caking Coals
in Iron Making & Resource Potential of It.
68
Quality Requirements for Non- Caking Coals in Iron Making
more than 1200 deg. C and FT should be >1400 deg. C but not
exceeding 1500 deg. C, so that the coals may not pose problem in
slagging in the race-way.
74
Quality Requirements for Non- Caking Coals in Iron Making
Summarised specification of coals for C.D.I.
Parameter Range
Coal size Min. 80% passing through 200 mesh (ASTM)
Moisture% a. No upper limit
b. 3-6 for best results
c. The dried coal should not contain > 1.5
Ash% As low as possible. Preferably ~10% but
not exceeding 17+ 0.5%
VM% a. 25-30% preferred but not exceeding
35% on dry basis
b.29-30% on unit coal basis preferred but
not exceeding 40%
CV a. 6000 K. Cals/Kg. on air dried basis
b. 7200 – 8000 K.cals/Kg. on unit coal
basis
AFTR(Deg. C) a. IDT ~1200 , b. HT >1400 , FT ~1500
HGI >45, preferably >55 75
Quality Requirements for Non- Caking Coals in Iron Making
Chemical Reactions take place at different zones of the Blast Furnace.
Many chemical reactions take place. But the ones generating heat and reduction of iron are
being discussed here.
a.Tuyere Zone : Carbon & Hydrogen are broken from the coal unit:
Cx Hy = xC +1/2 H2 (Endo-thermic)
Oxidation of Carbon & Hydrogen takes place to give CO2 & H20 ; both the
reactions being exothermic generates heat.
b.Race-way : 100% combustion efficiency is not achieved. Some carbon escapes through
the race-way; this carbon reduces CO2 & H2O so formed as follows because atmosphere is
reducing at this zone.:
CO2 + C = 2CO
H2O + C = H2 + C
c.Stack- zone : Unburnt carbon reacts as in the following and rest of the unburnt carbon is
carried away by the hot gases.
2 H2 + O2 = 2 H2O
FeO + H2 = Fe + H2O
FeO + C = Fe + CO ; CO2 + C= 2 CO 76
Quality Requirements for Non- Caking Coals in Iron Making
• SPONGE IRON MANUFACTURING :
• In order to see the viability of alternate route of steel making, western countries
developed a technology using either gas or non-caking coal to manufacture iron
during mid 50s. The operating temperature ( 950-1050 deg. C) is much below the
melting point of iron. The product when viewed through microscope, resembles
like honey bee structure and appear spongy, hence the name sponge iron.
• Tata Steel initiated first R & D in a 10 TPD capacity pilot plant in India.
• R&D in the Tata was successful and was patented in 1978 as TISCO Direct
Reduction (TRD)Technology and commercialized with the opening of Tata Sponge
Iron Limited.
• Sponge Iron India Limited (SIIL) commissioned their 1 st sponge iron plant in 1980.
• The reduction takes place in what are called Rotary Kilns. Iron ore (haematite),
coal and dolomite are charged and the product obtained is in the solid state.
• Odisha Sponge Iron Limited is also a promising sponge iron plant producing
sponge iron and bellets.
• Largest Sponge Iron producer is Jindal Steel & Power Limited. The plants are
mostly located in Chhattisgarh with more than 10 rotary kilns in operation 1350,000
MTPA
77
Quality Requirements for Non- Caking Coals in Iron Making
Quality Requirements for Non-caking coals for Coal based Sponge Iron
Making:
• Size : Coal size should be uniform. Coals with proper size are recommended for
optimum results. For better results, coarse coal is injected through the discharge end of
the rotary kiln so that coal reaches the reduction zone of the kiln and volatile matter
liberated is fully utilized.
• Reactivity towards CO2 : This parameter is very important for coals to be used in the
sponge iron industry. It is reported that bituminous coals having moisture 3-6%, have
the highest reactivity towards CO2. As the maturity of coal increases, reactivity
decreases. This means, lignites have the highest reactivity and anthracites the least.
The more the reactivity of coal, the better will be the coal for sponge iron making.
• Ash : Ash should be as low as possible. But for Indian condition, it should not be more
than 24%
• Coal type: Coals to be utilised should strictly be non-caking.
•Sulphur and phosphorus : Both sulphur and phosphorus should be as low as
possible for obvious reasons.
78
Quality Requirements for Non- Caking Coals in Iron Making
79
Quality Requirements for Non- Caking Coals in Iron Making
Resource Potential:
• In a study in CMPDI, it has been established that majority of the Indian non-
caking coals having low sulphur and producing coal ash with high AFTR are
suitable for sponge iron making, if required bringing down the ash to the
desired level.
• Most suitable among them are the coals from MCL(Talcher CF), SECL
• Some WCL coals contain high sulphur (>1%), barying these, majority WCL
coals are suitable.
• NCL coals also match the specifications.
• Many ECL coals are also suitable for sponge iron making.
• NEC coals are not suitable as these contain invariably high sulphur.
81
Quality Requirements for Non- Caking Coals in Iron Making
Smelting Reduction(SR) Process :
• A German technology, The COREX process is the successful SR process.
• It uses non-caking coals.
• Coal is dried and carbonised to produce Char.
• Oxygen gas is blown through the tuyeres in the reactor to maintain the
gassifier in a stable fluidised bed : C+O2 = CO2 : 2C + O2 = 2 CO
• When the temperature of the reducing dome rises to 1100 deg. C and
temperature of the fluidised bed becomes optimum, high quality reducing gas
containing about 95% (CO + H2 ) is produced. The gas contains about 2-3%
CO2 and the rest methane and nitrogen.
• In the reduction shaft, the iron ore is reduced to sponge iron by the counter
flow system.
• Sponge iron so produced is dropped to the gasifier when it is further heated
and melted giving hot metal and slag at the bottom part of the plant. 82
Quality Requirements for Non- Caking Coals in Iron Making
83
Quality Requirements for Non- Caking Coals in Iron Making
Formed Coke:
• Lignites and non-caking coals are selected for this.
• These are pressed followed by carbonization.
• Briquettes so prepared have been used in small blast furnaces
successfully.
• In western countries formed coke have been manufactured during
mid 80s using wide range of coals ( semi-coking to non-coking)
which have been tested through trial runs in small blast furnaces for
a shorter duration . No major problems were faced in the trial runs.
• In India also, formed coke of good quality have been prepared
using non-coking coals and tar as binder. Unfortunately,
commercialisation of the process has not taken place in India.
84
THIS IS ALL ABOUT THE
DISCUSSION !!
85
86