WEALTH FROM WASTE(WW)

GREEN TECHNOLOGY INITIATIVE

Professor (Dr) V.V.Mahajani(0251) 249 6885

vvmahajani@gmail.com 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

3V.V.MAHAJANI

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

4V.V.MAHAJANI

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).

5V.V.MAHAJANI

Oxidation Reactions results in acids formation:

Acetic acid

BVC Acids (none & nol)

Maleic , phthalic acids, citroconic acid

Aromatic acids : Benzoic, isophthalic, phthalic acid.

6V.V.MAHAJANI

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

7V.V.MAHAJANI

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%.

8V.V.MAHAJANI

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.

9V.V.MAHAJANI

V.V.MAHAJANI 10

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.

V.V.MAHAJANI 11

Stack Air contains volatile HC has to be

incinerated to have a green plant.

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

12V.V.MAHAJANI

GASEOUS EMISSION : H2S

Absorption in alkali adds to pressure of

marketing NaHS/ Na2S.

Why not convert H2S into S, at near room

temperature?

13V.V.MAHAJANI

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

14V.V.MAHAJANI

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.

15V.V.MAHAJANI

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.

16V.V.MAHAJANI

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).

17V.V.MAHAJANI

TREATMENT OF CHLOROPHENOL bearing AQUEOUS WASTE STREAM :

CHLOROPHENOLS ARE TOXIC TO MICROBES

THE WASTE IS ALKALINE AND ALSO CONTAINS NaCl

18V.V.MAHAJANI

Hydrogenation of halogenated aromatics:

dehalogenation

benzene ring saturation

19V.V.MAHAJANI

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)

20V.V.MAHAJANI

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.

21V.V.MAHAJANI

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:

22V.V.MAHAJANI

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

23V.V.MAHAJANI

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

24V.V.MAHAJANI

Acetic acid, Acetone

Maleic acid, Oxalic acid

n-paraffin, Trichloroethane

Fenton is not effective for

25V.V.MAHAJANI

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.

26V.V.MAHAJANI

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

27V.V.MAHAJANI

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

28V.V.MAHAJANI

29V.V.MAHAJANI

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)

30V.V.MAHAJANI

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.

31V.V.MAHAJANI

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

32V.V.MAHAJANI

COAL IMPORTED FROM AUS. & INDONESIA IS

COSTLIER DUE TO CARBON TAX.

2. USE FLUE GAS FOR NEUTRALIZINGALKAINITY IN EFFLUENT STREAM.

3. MANUFACTURE DRY ICE

33V.V.MAHAJANI

V.V.MAHAJANI 34

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).

35V.V.MAHAJANI

Price = β ( Project Cost) + Gross Cost of Production

(CAPEX) (OPEX)

β = includes ROI etc.,

GREEN TECHNOLOGY MUST RESULT IN ACCEPTABLE β

36V.V.MAHAJANI

V.V.MAHAJANI 37

Chemical PROJECT ECONOMICS

V.V. MAHAJANI & S.M.MOKASHI

1. Macmillan India Ltd& now

2. TRINITY ( Laxmi Publications Pvt Ltd)

INNOVATION IS ANYTHING THAT PRODUCES MONEY