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Process related aspect of Cleaner Production "A Case study on two important products".

Dr. MAHENDRA SADARIA

SAN ENVIROTECH PVT. LTD. AHMEDABAD
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Meaning of waste
Waste is nothing but undesirable byproduct generated from process arising from inefficiency of the process. Two examples were studied for innovation in production process by way of waste exchange and improving the efficiency of unit operations. Innovations not only improve wastewater characteristics or reduce the waste but also increase the yield in terms of quantity and quality.
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Important point for Cleaner mechanism

Good housekeeping Input materials Better process controls Equipment modification On site recycling and material recovery Energy conservation Environmental Benefit Commercial benefit

Chemical reaction of H. Acid

Sulphonation
SO3H H2SO4 H2SO4 SO3H SO3H 165oC SO3H HO3S SO3H SO3H SO3H

Nitration
SO3H Conc. HNO3/H2SO4 HO3S SO3H HO3S SO3H HO3S NO2

Neutralization
HO3S NO2 CaCO3+Na2SO4 HO3S SO3H
NaO3S

NaO3S

NO2

+
SO3Na

CaSO4

Chemical reaction of H. Acid

Reduction
NaO 3S NO2 Fe+HCl NaO 3S SO 3Na NaO 3S SO3Na NaO 3S NH2

Fusion
NaO 3S NH2 NaOH NaO 3S SO3Na NaO 3S SO3Na ONa NH2

Isolation
ONa NH2 H2SO 4 NaO 3S
SO3Na

OH

NH2

HO 3S

SO 3H

M ass balance of H - Acid INPUT Naphthale ne Sulphuric acid Wate r Ole um KG 1400 2000 157 3000 Sulphonation OUTPUT KG

Nitric acid

1000

Nitration

NOx (Scrubbuing)-ETP 350

LSP Glaube r salt Wate r

5000 3570 8570 Neutralizer CO2 2200

Wate r

7140

Filtration

Gypsum(73%) (Sludge )

13180

Ste am CI Powde r Ace tic acid Soda ash

5430 930 60 430 Reduction Waste wate r 3930

Filtration Wate r 5710

Iron Sludge (70%) (Sludge )

1950

Evaporator

Re c.wate r

8570

Caustic Flake s Me thanol

1785 600

Fusion

Me the nol(Re c)

515

Spe nt acid Sulphuric acid Wate r

8930 1000 4750 Isolation SO2 SBS(450 KG) 708

Filtration

Mothe r liquor MME + INC

27435

Centrifuge

Mothe r liquor

957

H - Acid M ass balance 61462

We t cake (60%)

1667 61462

Chemical reaction of Vinyl Sulphone

Acetylation
NH2 NHCOCH3

CH3COOH

H2O

Sulphonation
NHCOCH3 NHCOCH3

+ 2ClSO3H+ SOCl2
SO2Cl

+ HCl + SO2

Chemical reaction of Vinyl Sulphone

Reduction
NHCOCH 3 NHCOCH 3

+ 3NaOH + NaHSO 3
SO2 Cl

+ Na2SO 4 + NaCl + 2H 2O
SO2 Na

Condensation

NHCOCH3

NHCOCH 3 O H2C CH2

+
SO2Na

+ H 2SO4
O 2S

+ Na2SO4 + H 2O

OH

Esterification
NHCOCH 3 NH2 H2SO 4 O 2S

+
O 2S

+ CH3COOH

OH

OSO3H

M ass Balance for Vinyl Sulphone INPUT Ace tanilide Thinoyl chloride KG 555 Sulphonation 500 OUTPUT HCl S.B.S. Slurry KG 320 340

Chloro sulphonic acid1470

Ice Wate r

3300 2200

Drownings

Mothe r liquor Wash wate r

2115 3110

SBS slurry SBS Caustic lye

340 125 660 Reduction Salts 315

Ethyle ne oxide Spe nt acid

250 830 Ethoxylation

Wash wate r

1670 Condensation

Mothe r liquor Wash wate r

1670 2575

Wash wate r Centrifuge

600

Drying

Sulphuric acid

345

Esterification

Ace tic acid

200

Final Product Total 12245

1000 12245

Waste exchange mechanism

H. Acid

Synergy in manufacturing of H. Acid and V.S.

V.S.
Chlorosulfonation

Sulfonation Nitration Neutralization Filtration Reduction Na2SO4 Filtration Amino Conc. Acetic Acid NaHSO3

Drowning Filtration Reduction Clarification Condensation Filtration

Alkali fusion Isolation Filtration Drying Packing 10 Dil. H2SO4 Drying Esterification Packing

Why Recycling
Conserve the Natural Resources Reduce Energy Conservation Save clean Air & Water Save money Saving due waste recovery Saving due to reduced treatment

Traditional Production
Material loss Operational cost Personal cost Investment cost Public Authorities Proceeding
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Resource Recovery
Due to above waste exchange and recovery of by product, we get spent Sulphuric acid (25-30 %) and acetic acid (92 %) as by-product, which is reused/sold to actual users. Proper operating air pollution control systems, we get HCl (2528%), where the unit has also provided adequate scrubbing system and solution obtained at the end of scrubbing system is collected and reused/sold. There is also recovery of Glauber salt from the isolation of H. Acid and condensation step of VS product, which can be recovered by Multi effect evaporator and reused/sold to actual users. Now a days gypsum and iron sludge is recovered from H-acid manufacturing, which is sold to cement manufacturers. Considering above cleaner concept, pollution load can be reduced drastically from production of H. Acid and Vinyl sulphone production.
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Reduction in Wastewater
Sr. Products No. Wastewater generation, kL/Tone Convention al process After adoption of waste exchange mechanism 4280 7955 Differen ce Reductio n in volume percent

I. II.

H. Acid Vinyl Sulphone

41242 11245

36960 3290

90 29

Total

52487

12235

40250

77

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Important point for Cleaner mechanism

Good housekeeping Input materials Better process controls Equipment modification On site recycling and material recovery Energy conservation Environmental Benefit Commercial benefit

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Process modification in Dyes Production

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Chemical reaction of Reactive Black-5

Diazotization NH2 + O S O O NaNO2 + 2HCl S O O N N Cl + 2H2O + NaCl SO3Na

SO3H

Vinyl Sulphone Coupling N N Cl 2 O S O O SO3Na +

NH2 OH + HO3S H. Acid SO3H 4NaHCO3

NaO3S

O S O N N NaO3S

NH2 OH N N SO3Na

O S O

SO3Na

+ H2O+ CO2+ 2NaCl

Reactive black-5

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Following process steps are important to produce proper dyes

Known quality of raw materials Possible mole to mole reaction Optimal pH control Optimal Temperature control Standardized the reaction efficiency and try to continuous improve it Avoid filtration of dye if possible and adopt spay drying in house or out sourcing, which will be helpful to reduce the loss of dye and reduce the pollution load on environment
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Typical mass balance of Black-5

TYPICAL MATERIAL BALANCE FOR 1000 Kgs. INPUT
R.M. V.S. HCL NaNO2 Water+Ice MASS 500 Kgs. 200 Kgs. 125 Kgs. 2075 Ltr Vol. 2900

INPUT
R.M. MASS H.Acid 350 Kgs. Soda bicarb 150Kgs. 450

FINAL VOL. 3330 Ltr. EVP 1330 Ltr.

Product = 1000 Kg.

S. D.

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What is happening if reaction is not takes place in proper way?

If mole ration of diazoniam salt is higher than the active aromatic compound like-H-Acid .. Greenish tone will develop If mole ration of diazoniam salt is lower than the active aromatic compound like-H-Acid .. Reddish tone will develop If Optimal Temperature control not maintained Proper dying not takes palace and dye will washed with washing of cloth
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Environmental and Economic Benefits

Product: - Black -5, Batch size:-1000 kg
Raw Materials RM requirement in kg Cost on M:M Basis Cost on conventional basis Cost benefit in Rs. Environmental Benefits

Diazonium salt Vinyl Sulphone (MW-281) Sodium Nitrite HCl Water + Ice Azo coupler H. Acid (MW-319) Soda bicarbonate 283 Kgs. 150 Kgs. 60845 2250 63675 2625 2830 375 500 125 200(30%) 3500 Ltr 69000 3625 400 69000 4350 600 725 200 Raw materials savings and reductions in wastewater discharges.

4130
Better rate of finished products due to better quality Reduction in Energy Consumption Reduction in Manpower
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Environmental and Economic Benefits

Cost benefit v/s Batch size
Bach size in kg (Finished product) 1000 2000 5000 10000 Solid Concentrati on 30% 32% 35% 37% Drying cost Cost benefit benefit Environmental Benefits

Rs 8.33/Kg Rs 7.81/Kg Rs.1.22 Rs 7.15/Kg Rs.1.18 Rs 6.76/Kg Rs.1.57

Resource conservation in terms energy saving

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Why is the diazotization reaction done at zero to five degrees centigrade?

The reaction is done at zero to 5 degrees centigrade because the diazonium ion is so reactive. It reacts with water above 5 degrees giving off nitrogen gas. Also, running the reaction at or near zero degrees Celsius limits the formation of side products and prevents thermal decomposition.

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Why Optimal pH control at dye plant is required?

Two side coupling is required. First at Acidic pH around 2.5 pH.( check completion of st coupling by testing in lab sample against standard sample). Increased the pH by addition Sodium bicarbonate up to 5.0 as fast as possible so that second coupling at 0 to 50C will take place.

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THANKS.

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