EIJES31089

INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCES Volume 3, No 2, 2012

Copyright by the authors - Licensee IPA- Under Creative Commons license 3.0

Research article ISSN 0976 4402

Received on August 2012 Published on September 2012 895

Heavy metal fate during co-incineration of organic waste of pharmaceutical

industry Narsimha Reddy M

1, Sripathi S

1, Mohan Reddy C

2, Venkateswara Reddy V

3

1 - EHS Department Hetero Labs Limited (Unit-I) , Medak - Dist., Pin Code No: 502 319,

Andhra Pradesh, India

2- Director (Operations) Hetero Labs Limited (Unit-I).

3- Professor in Department of Civil Engineering (Environment Section), JNTUH,

Hyderabad- 500 084

[email protected]

doi:10.6088/ijes.2012030132017

ABSTRACT

During the production of the life saving drugs in a pharmaceutical industry, there will be

generation of the organic waste which is inevitable. The safe disposal of the waste is a

pressing issue for these industries; though the incineration process is available such industries

are looking for the more eco friendly disposal methodologies. Energy recovery by means of

combustion in Waste-to-Energy or conservation of fossil fuels by the replacement in the

energy intensive production process such as cement industries is a viable possible

application. Currently, there are various norms for co-incineration and concern for heavy

metal fate in view of the possible bio magnification. The results demonstrated no variability

in the heavy metal effects to the environment either through emissions or in the form of the

solid waste. The result suggests not only technical and economic feasibility of

co-incineration method, but also the feasibility of adopting the co-incineration process for the

disposal of the pharmaceutical waste.

Keywords: Co-incineration, Pharmaceutical Organic Waste, Heavy Metals, Cement Rotary

kilns, Toxicity Leachate Procedures, SW846.

1. Introduction

Today the pharmaceutical industry can be characterized as high technology industry with

very deep historical roots which were less scientific at lease when considered with todays

measures dating back to the ancient Egyptians. Over the last three decades the Indian

pharmaceutical industry has transformed into a world leader in the production of high quality

generic drugs. The Indian pharmaceutical products are exported to more than 200 countries

around the globe including highly regulated markets of USA, Europe, Japan, Africa and

Australia. Significant growth was witnesses in the therapeutical segments like cardiac,

diabetes and Central Nervous system (CNS). India is also increasingly emerging as one of the

most globally preferred outsourcing destination for pharmaceutical. This trend can be largely

attributed to India's inherent competencies in terms of manufacturing cost, vast talent pool

having outstanding chemistry skills, diverse patient pool, and strong support from auxiliary

industries such as bio-informatics, clinical data management etc and a favorable regulatory

environment. Indian pharmaceutical industry is now broadening the scope of its service

offerings by providing a wide range of services spanning the entire pharmaceutical value

chain. With such a rapid pace of development, pharmaceutical industries are also keeping

tremendous efforts on waste management.

Heavy metal fate during co-incineration of organic waste of pharmaceutical industry

Narsimha Reddy. M, Sripathi. S, Mohan Reddy. C, Venkateswara Reddy. V International Journal of Environmental Sciences Volume 3 No.2, 2012

896

Pharmaceutical industries generate the organic waste during the reaction and distillation

process, these wastes on performing comprehensive analysis is found to have calorific values

ranging above 5000 Kilocalories and are hazardous in nature as per the Hazardous waste

management (HWM) rules, 2008 Government of India, the average the analysis reports is

given in table 1, Hence, these Pharmaceutical Organic Wastes (POW) are to be properly

disposed by incineration. Present trend is the disposal of the waste by direct incineration by

captive incinerator or disposed to common incineration facility.

Table 1: Average the analysis results for pharmaceutical organic wastes (POW)

S. No Parameter Unit Method Average Results

1 pH -- SW-846 9045C 6.07

2 Loss on Ignition at 550o C % APHA 2540 93.37

3 Paint filter liquid Test -- SW-846 9095A Fail

4 Bulk density / Specific

Gravity g/cc ASTM D 5057-90 1.24

5 Calorific Valve Cal/gm IS: 1350-1970 5997.33

6 Flash Point oC SW-846 1020A 30.50

7 Total halides as Cl- % SW 846 5.27

This disposal method involves the air emissions, green house gas generations and certain

amount of solid waste in the form of ash. The ash generated is again to be disposed to the

secured landfill which will create burden on the land. In view of the same pharmaceutical

industries is looking for the cost reduction, energy conservation and eco-friendly option to

minimize the environmental impacts. Co-incineration in cement kilns provided a viable

option, wherein the pharmaceutical waste replaces a part of the traditional fuels.

Cement kilns have traditionally been fired by coal but use of the pharmaceutical organic

waste as alternative fuels offer the joint benefits of improved performance and lower

production costs. The fact that the energy costs have a considerable influence on a large part

of the production costs (the share amounts to about one third) leads many manufacturers to

reduce consumption of conventional sources of energy in favor of alternative fuels. In other

words, alternate fuels also offer conservation of traditional fuels.

The following reasons underline the advantages of using the rotary kiln for the co-

incineration of these fuels along with the traditional fuels coal/coke:

1. High temperature in the fuels and in the gas phase;

2. Long staying (residence time of 4-5 minutes) of the fuels in the oxygen rich burning process (favoring a complete burning);

3. Counter current flow of raw material and flue gases - Intense contact and interactions between solid and gas phases in the heat exchanger system;

4. Kiln lines are equipped with efficient pollution control equipment;

5. Any acid gases are neutralized by the raw material being of an alkaline nature and subsequently incorporated into the cement clinker;

6. The recycling (ashes) resulting from the burning are absorbed in the clinker in an idle manner and practically irreversible manner;



897

7. Use of alternative fuels is estimated to contribute a global average reduction in CO2 emissions from the cement industry of 12% by 2020.

All characteristics mentioned above become evident in each cement rotary kiln independently

from the type of kiln. This fact leads to the conclusion that the rotary kiln is really

predestined for the use of these fuels and disposal of the waste.

2. Materials and method

The present study focus on the heavy metal concentration in the basic fuels ( Coal/Coke) and

the hazardous waste and their fate while co-incineration process at cement kilns are reviewed

with focus to the upcoming environmental norms and interests. Cement plant located at

Reddypalem, Tamilnadu is selected for the purpose of the study, whose capacity is 3.8

MMTA and it is having a single stream rotary kiln with four preheaters. The methodology is

based on the mass balance approach and hence the comprehensive analysis of the fuels,

emissions and the clinker had been carried out during the course of the study. It is evident

that the chemical composition of the raw meal, fuels and sludge will greatly influence the

quality of the flue gas emissions from kiln/ raw mill stack. Coal and Coke samples and the

sludge samples were collected before the trial run whereas the raw meal sample is collected

while the trial run is in progress.

3. Sample preparation

Analysis of the fuels/ raw material

A representative sample of the coal/coke, raw meal and the pharmaceutical waste is collected

and are subjected to the proximate and ultimate analysis for the establishment of the metal

constituents. The analysis results of the samples are shown in Table-2, 3, 4 &5.

Table 2: Raw meal - chemical composition

Sr. No. Parameters UOM Results

1 Fluorides as F mg/kg 12.14

2 Sulphates as SO4 mg/kg 29.86

3 Aluminum as Al203 mg/kg 58

4 Silica as Si02 mg/kg 4126.4

5 Iron as Fe mg/kg 19647.8

6 Cadmium as Cd mg/kg 1.1

7 Chromium as Cr mg/kg 47.5

8 Copper as Cu mg/kg 3.5

9 Cobalt as Co mg/kg 0

10 Manganese as Mn mg/kg 250.0

11 Nickel as Ni mg/kg 40.4

12 Lead as Pb mg/kg 90.8

13 Zinc as Zn mg/kg 18.4

14 Arsenic as As mg/kg 12.4

15 Mercury as Hg mg/kg 2.1

16 Selenium as Se mg/kg 2.8

17 Antimony as Sb mg/kg 5.2

18 Vanadium as V mg/kg 61.2



898

Table 3: Fuels Proximate analysis

Sr. No. Parameters UOM Coal Pharmaceutical

Organic Waste

1 Moisture Content % 2.24 8.63

2 Ash Content % 52.46 7.18

3 Volatile Matter % 22.46 91.58

4 Fixed Carbon % 21.24 1.24

Table 4: Fuels Ultimate Analysis

Sr. No. Parameters UOM Coal Pharmaceutical

Organic Waste

1 Mineral Matter % 32.48 NA

2 Carbon % 78.64 48.84

3 Hydrogen % 3.90 3.87

4 Nitrogen % 1.04 4.79

5 Sulphur % 5.46 13.24

6 Oxygen % 10.96 29.26

7 Gross Calorific Value K.Cal/Kg 5240.0 5997.33

8 Chlorine as Cl mg/Kg NA 5.27

9 Fluorine as F mg/Kg NA NA

Table 5: Metal analysis

Sr. No. Parameters UOM Coal Pharmaceutical Organic

Waste

1 Cadmium as Cd mg/Kg 0.32 0.3

2 Chromium as Cr mg/Kg 10.5 5.0

3 Copper as Cu mg/Kg 11.6 5.0

4 Iron as Fe mg/Kg 2314 125.0

5 Cobalt as Co mg/kg 6.8 0.02

6 Manganese as Mn mg/Kg 17.3 5.1

7 Nickel as Ni mg/Kg 173 0.07

8 Lead as Pb mg/Kg 5.5 0.05

9 Zinc as Zn mg/Kg 48.9 56.7

10 Arsenic as As mg/kg 0.46



899

on a heated filter, and gaseous emissions are then collected in an aqueous acidic solution of

hydrogen peroxide (analyzed for all metals including Hg) and an aqueous acidic solution of

potassium permanganate (analyzed only for Hg). The recovered samples are digested, and

appropriate fractions are analyzed for Hg by Cold Vapor Atomic Absorption Spectroscopy

(CVAAS) and for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, P, Se, Ag, Tl, and Zn by

Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and shown results as

Table-6, 7 & 8 also shown Figure-1 for The Heavy metal emission Trend. ICP-AES used for

this analysis is,

Make : Varion Model : Vista

TYPE : CCD Simultaneous mode

Carrier Gas : Nitrogen 99%

Fuel Gas : Argon 99%

Ignition Type : Automatic by RF Power

Range of elements : 23 E, V, As, Hg, Se, Pd, Sn, Mo, Sb, 71/72 elements

Table 6: Results of all metals emissions after co-incineration with 10%

pharmaceuticals organic waste (results in g/nm3)

Samples As Cd Co Cr Cu Hg Mn Ni Pb Sb Se Th Z

n

1 0.9 2.4 2.5 11.

5 6.5 0.5 32.2 8.7 5.0 8 1.9



900

Table 8: Results of all metals emissions after co-incineration with normal fuel = 0% POW,

(results in g/nm3)

Samples As Cd Co Cr Cu Hg Mn Ni Pb Sb Se Th Zn

1 1.1 2.1 3.5 13 6.6 0.5 32.4 8.2 4.8 15.

2 1.5



901

4 Iron as Fe mg/Kg



902

and Dr. P Manikyamba, Retired Professor, Department of Chemistry, Kakathiya University,

Warangal for their valuable suggestions during this study.

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