WEALTH FROM WASTE(WW)
GREEN TECHNOLOGY INITIATIVE
Professor (Dr) V.V.Mahajani(0251) 249 6885
[email protected] Cell: 900 4266 456
Preamble
GREEN CHEMISTRY principles rest upon
• Atom Economy (Highest Selectivity)
Raw materials, Chemicals & catalyst consumption must be as low as theoretical possible. Direct impact on OPEX.
• SHE complianceProcesses must be inherently Safe, no occupational Health hazard & Environmentally benign.
• ENCON
Global warming (Carbon foot print), ODP
ATOM ECONOMY VIOLATION RESULTS IN WASTE
WASTE GENERATION: T / T of product :
PHARMA / DYES INTERMEDIATES / PESTICIDES > CHEMICALS
> FERTILIZER > > PETROCHEMICALS > REFINERY
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WEALTH from WASTE (W W)
OXO PROCESS :
C3= + ( CO + H2) = n C4 al ( n- butyraldehyde)
+ iso C4 al (iso- butyraldehyde)
OLD Process : Catalyst Co 25% iso C4 al , 250 bar, 150o C
LP OXO (JMDavy) : Catalyst Rh 10% iso C4 al, 16 bar 120o C
R / RP : Biphasic water soluble Rh 2% iso C4 al, 100 bar 120 oC
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UTILIZATION OF iso C4 al (iso- butyraldehyde)
Aldol condensationHCHO + H C (CH3)2 CHO OHCH2 – C(CH3)2- CHO
Basin Ion Exchange Resin
OHCH2 – C(CH3)2- CHO Hydrogenation OHCH2 – C(CH3)2- CH2OH
Hydroxy pivaldehyde Neopentyl glycol
Studies to aid process development for the manufacture of neopentylglycol from isobutyraldehyde: aldol condensation followed by hydrogenation. M. A. Tike, A. M. Gharde, and V. V. MAHAJANI,Asia-Pac. J. Chem. Eng; 3: 333 (2008).
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Oxidation Reactions results in acids formation:
Acetic acid
BVC Acids (none & nol)
Maleic , phthalic acids, citroconic acid
Aromatic acids : Benzoic, isophthalic, phthalic acid.
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Acetic acid : Recover by Reactive Extraction to manufacture CA or CMA
CA: Calcium Acetate CMA : Calcium Magnesium Acetate
BVC ACIDS : Reactive Extraction Manufacture of Lube Esters
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ATOM ECONOMY IS A CHALLENGE IN
ETHYLENE OXIDE MANUFACTURING PROCESS.
C2H4 + O2 H2C CH2
OWith present Silver oxide based catalyst, the
highest selectivity possible is around 85%.
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IN PHTHALIC ANHYDRIDE PROCESS (PAN),
“ ZERO ENERGY B/L PLANT” IS POSSIBLE.
HOWEVER, IF TURBINE EFFICIENCY IS NOT UP TO THE
MARK ONE MIGHTSACRIFICE ATOM ECONOMY TO PRODUCE
POWER REQUIRED BY THE PLANT.
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THE PLANT PRODUCES GASEOUS EMISSIONS FROM SWITCH CONDENSER.
VENTURI SCRUBBER TO MANUFACTURE MAC and then MAN
OR FUMARIC ACID
SOLID PA : MAKE CHEAP PLASTICIZERsDOP (di octyl phthalate)DBA( di butyl phthalate)
Aqueous waste stream contains acids :
anaerobic digestion to get CH4 followed by
aerobic digestion MBR ? Water recovery.
All liquid effluents, if required, should be treated with Fenton Reagent to enhance:
BOD / COD
ANAEROBIC DIGSTER
AIR
AIR
WATER for RECYCLE
BIO GAS, CH4 / CO2 / H2S
WASTE
Membrane bio reactor
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GASEOUS EMISSION : H2S
Absorption in alkali adds to pressure of
marketing NaHS/ Na2S.
Why not convert H2S into S, at near room
temperature?
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REACTIONS:
REDUCTION
H2S (G) H2S (L)
H2S + 2 Fe+3 CHEL 2H+ + 2 Fe+2 CHEL + So
OXIDATION
2 Fe+2 CHEL + 1/2 O2 + H2O 2 Fe+3 CHEL + 2 OH-
H+ + OH - H2O
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Neutralization
AQUEOUS PHASE HYDROGENATION
More safe due to presence of water in liquid phase and steam in gas phase.
Ru catalyzed reactions are more attractive in the presence of water.
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Hydrogenation of maleic acid to succinic acid
• Benzene or n- butane can be used as the feedstock to manufacture MAN.
Use water formed and additional Process water to absorb MAN to manufacture maleic acid.
Hydrogenate in aqueous phase to succinic acid on supported Ru catalyst.
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Recover succinic acid (SA) thus formed by crystallization.
Recycle the mother liquor to scrub MAN.
SA can be esterified with Methane SulphonicAcid (MSA) to manufacture diethyl succinate – feed stock for butane diolmanufacture.
Kinetics of aqueous phase catalytic hydrogenation of maleic acid to succinic acid over a Ru/Al2O3 catalyst, P. D. Vaidya and V. V. MAHAJANI,J. Chem.Tech. Biotech., 78 (4) 504 (2003).
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TREATMENT OF CHLOROPHENOL bearing AQUEOUS WASTE STREAM :
CHLOROPHENOLS ARE TOXIC TO MICROBES
THE WASTE IS ALKALINE AND ALSO CONTAINS NaCl
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Hydrogenation of halogenated aromatics:
dehalogenation
benzene ring saturation
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Cl
Cl
OH
H2+ 2 HCl
OH
HCl + NaOH = NaCl + H2O
Pd-Ru / TiO2
• Studies in hydrotreatment as a unit process for treating chlorophenol bearing aqueous
streams using Ru-Pd/TiO2 catalyst,
P. D. Vaidya and V. V. MAHAJANI, App. Catal. B 51(1) 21(2004)
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H2 for recycle
Detoxified waste for further treatment by ADSORPTION on Carbon to recover cyclohexanol
H2
Waste
Reactor
cw
φ - NITRO COMPOUNDS CAN BE CONVERTED INTO AMINO
COMPOUNDS BY CATALYTIC TRANSFER HYDROGENATION
(CTH).
THE CATALYST IS, BY AND LARGE, Pd / C &AMMONIUM
FORMATE ACTS AS HYDROGEN DONOR AT TEMPERATURES
AROUND 80 oC
EXPTs are required to optimize process conditions.
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Catalytic transfer hydrogenation of o-nitro anisole to o-anisidine, some process development aspects,P. Haldar and V. V. MAHAJANI, Chem. Engg.Jl 104 1-3, (2004).
Wet Air Oxidation
Fenton Chemistry
Ultra Violet (UV)
Ozonation
Sonication
ADVANCED OXIDATION PROCESSES:
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OXIDATION POWER OF COMMON OXIDIZING AGENTS
RELATIVE TO OXYGEN
O2 1.00
Cl2 , ClO2 1.06
HOCl 1.24
H2O2 1.48
O3 1.68
OH* (hydroxyl radical) 2.33
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Fenton Chemistry insight:
Generation of HYDROXY radical OH*
H+
H2O2 + Fe+2 Fe+3 + OH* + OH- (1)
OH* and Fe+3 act synergetic ally to oxidize the substrate (COD)
Fe+3
RH + OH* R* + H2O R+ + H2OFe+2
R+ + H2O ROH + H+ (2)
Fenton Reagent = Fe+2 / H2O2 ; Generally FeSO4 is used
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Acetic acid, Acetone
Maleic acid, Oxalic acid
n-paraffin, Trichloroethane
Fenton is not effective for
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TREATMENT THEREFORE EXHIBITS FINITE COD
Please Note:
• Alkaline pH is not as effective as acidic. Fe precipitates
out as Fe(OH)2 under alkaline pH.
• NaCl , Na2SO4 act as free radical scavenger;
Effect of NaCl > Na2SO4
It desirable to optimize process parameters via bench
scale experimentation as the entire process is substrate
& waste specific.
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dil H2SO4
pH Adjustment
FeSO4
dil. H2O2
REACTOR
dil. NaOH
Removal of FeWASTE
Precipitated Fe(OH)2
Effluent
Fenton Process: Block Diagram
BE AWARE You are handling Hydrogen Peroxide, Safety Compliance
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MORE APPROPRIATELY : THERMAL PROCESS.
IT IS SUBCRITICAL OXIDATION PROCESS IN AN AQUEOUS
MEDIUM
Water Tc = 374 oC & Pc = 217.6 atm
OXIDATION OF ORGANIC SUBSTRATE IN PRESENCE OF
MOLECULAR O2 T = 100_250 oC
& Pressure: O2 pressure 5 to 20 atm
O2 Solubility in water is minimum at near about 100oC.
Above 100 oC it is increasing with increase in temperature.
WET AIR OXIDATION, WATER, 2R RECOVER & RECYCLE
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Compressed airEffluent
Treated Waste
Heat transfer Fluid
Wet Air Oxidation: Schematic Diagram
Product Gas
Recommended Readings :
Wet air oxidation.
Mishra, V. S.; Mahajani, V. V.; Joshi, J. B.
Ind. Eng. Chem. Res. 1995, 34, 2.
Studies in treatment of disperse dye waste : membrane-wet oxidation
process.
Dhale A. D.; Mahajani, V. V. ;Waste Mgmt. 2000, 20, 85.
Wet oxidation regeneration of activated carbon loaded with reactive
dye.
Shende, R. S.; Mahajani, V. V. ;Waste Mgmt. 2002, 22, 73.
A novel way to treat refractory waste: Sonication followed by Wet
Oxidation(SONIWO)
Ingle, M. N.; Mahajani, V.V.; Journal of Chemical Technology
Biotechnology. 1995, 64, 80.
Studies in liquid phase mineralization of cation exchange resin
by a hybrid Process of Fenton dissolution followed by wet oxidation.
T.L.Gunale, V.MAHAJANI , P.K.Wattal and C. Srinivas
Chem. Engg Jl 148 371(2009)
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ENCON (CARBON FOOT PRINT):
GREEN HOUSE GAS ( CO2)
1. ALL ACTIVITIES INVOLVING COMBUSTION TO GENERATE
STEAM FOR HEATING PURPOSE AND ALSO VERY HIGH
PRESSURE STEAM FOR POWER GENERATION ARE
REQUIRED TO BE VERY EFFICIENT TO PRODUCE LESS CO2.
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HOW to do this?
USE W/ O EMULSION :
WATER SAY, 5%, EMULSIFIED WITH FURNACE OIL IS FUEL IN A BOILER
OIL
WATER
FINE SUB MICRON FUEL PARTICLES BURN EFFICIENTLY:
LOW NOx,NO SOOT, MORE HEAT is RELEASED Less emission of CO2 / T steam
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COAL IMPORTED FROM AUS. & INDONESIA IS
COSTLIER DUE TO CARBON TAX.
2. USE FLUE GAS FOR NEUTRALIZINGALKAINITY IN EFFLUENT STREAM.
3. MANUFACTURE DRY ICE
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PLANT : NON EDIBLE OIL TREES AROUND &USE OIL AS FUEL IN A BOILER.
VIA CSR, GIVE VILLAGERS EARNING
VILLAGERS CAN EXPEL OIL AND SELL THIS TO POWER STATION.
THE CAKE CAN BE USED AS BIO FERTILIZER.
4.W W ACTIVITY
MANUFACTURE OF ETHYLENE CARBONATE & THEN DMC
H2C(O)CH2 + CO2 H2C CH2
CH3OH O O (CH3O)2 C = O + MEG
C (DMC)
O
Studies in transesterification of ethylene carbonate to dimethylcarbonate over Amberlyst A-21 catalyst. S.M.Dhuri and V.V.MAHAJANI, J.ChemTech Biotech. 81 62 (2006).
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Price = β ( Project Cost) + Gross Cost of Production
(CAPEX) (OPEX)
β = includes ROI etc.,
GREEN TECHNOLOGY MUST RESULT IN ACCEPTABLE β
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