Waste Management Strategies

Development of Zinc Oxide Deposited Tiles for Photocatalytic Water Treatment

By

Quindra Kyle V. Bagabaldo

Ivy M. Galamiton

Michael Alex S. Mabao

Nheilian N. Roque

Dr. Shierlyn S. Paclijan

Adviser
 December 11, 2018

Introduction

The production of ceramic tiles starts with body preparation. In the body

preparation stage, the raw materials are mixed in a ball mill for 10-12 h before

transforming into slip and being taken to a spray dryer. The slip is dehydrated and

combined in the form of small balls with 67% humidity. Thereafter, they fall to the dryer

bottom and are then transported via a conveyor system to be stored in a silo. Coating

material is prepared by mixing the raw materials (zinc oxide, and polyethylene glycol) in

a mixing tank.

Ceramic tiles are then formed by a pressing operation using a hydraulic press

with a metal mould, 30cm x 30cm in size, before being conveyed to the extension plant

for coating. The machine used in the plant for coating is a roller printer and is set at 100

rev/min. After that the coated ceramic tiles (ZnO-DT) are now being conveyed to the kiln

for drying. The dryer used in the plant is a tunnel kiln and the temperature is set at
approximately 100°C. Tiles are dried in the kiln for 28 h. The thermal energy for the

tunnel kiln is from LPG combustion. After being dried, the tiles are put in a protective

box, or “saggar,” before being put into another tunnel kiln for firing. The temperature in

the kiln is 990°C and the firing time is approximately 29 h. LPG is used as the kiln fuel.

After being fired, the ceramic tiles are conveyed to the quality checking and size

separator station. The tiles are classified as either Grade A or Grade B, and those

remaining are regarded as damaged tiles. The tiles are then packed in cardboard boxes

glued by workmen and then put on pallets for transportation on to dealers.

Resource Consumption

The resources needed for this design are water, energy and the raw materials

such as Zinc Oxide and Polyethylene Glycol. Water, in this design, is used for cooling

and equipment cleaning purposes only. Water consumption can be reduced if the water

is treated and reused several times in cleaning. The processes involved are not water-

intensive but the equipment consumes so much energy. Ceramic industries are noted

for great percentage of the energy cost in the total production cost. More than 50% of

total cost of energy cost in ceramic manufacturing comes from the kiln firing and drying

processes [1].

Electric energy and chemical energy are the two types of energy used in ceramic

industries. Electric machineries (e.g. motor, fan) use electric energy and thermal energy

is used in heating kilns and furnaces. Of these processes, the firing process is the

greatest energy consumer. About 50% of the energy input into the firing process is lost
through the kiln combustion flue gas and cooling gas stacks, as shown in the figure

below.

Figure 1 Sankey Diagram of Kiln Process (Adapted from Kaushik et al, 2016)

The drying process in the ceramic industry is the greatest energy consumer

second to the firing process. Drying means loss of moisture from the surface of the

substance by evaporation, and the drying speed depends on the temperature and

humidity.

Energy conservation in industries starts from operation and process control, then

extends into equipment and process improvement. Some of the energy conservation

techniques in the ceramic industry are shown below.

 Figure 2 Energy Conservation Techniques (Adapted from UNIDO Ceramic Industry

Handy Manual)

The choices of energy source, firing technique and heat recovery method are

some of the most important factors affecting the environmental performance and energy

efficiency of the manufacturing process. [2]

Materials Targeted

In the production of Zinc Oxide deposited tiles, grinding and mixing process is

involved. Due to the high power/speed requirement of the mixer and grinder

produces dust from the raw material being fed.The solid waste generation in the

whole process is mainly contributed by one of the raw material which is the Zinc
 Oxide. Zinc oxide (ZnO) which naturally appears as white colored powder is an

oxidic compound and mostly insoluble in water. It is also optically transparent

under visible range and at ambient conditions, the ZnO crystalized in a wurtzite

structure (Lam et. al., 2012; Raoufi, 2013).It is widely used in many applications

and ZnO nanoparticle have presented photocatalytic and oxidizing capabilities

against biological and chemical species.

On-site Treatment.

For the treatment on the grinding process. A close capture hooding will be

installed in the grinder and these close capture hooding will be connected to a

tank for the storage of ZnO dust in order to for reuse. For the mixing process,

enclosed mixing tank will be used. Also for the transportation of the raw material,

covered conveyor belt will be used for potentially dusty raw material.

Gaseous emissions

Air emissions may be generated from storage and handling of raw materials and

during firing or drying of ceramics. In the latter case, emissions may be derived from

the raw materials and / or from the fuels employed for heat and power generation.

The production of ZnO-DT heavily relies on the series of processes. These

processes are grinding, mixing, drying, and firing. Some of which produced gaseous

emissions which are harmful and toxic fumes. Hence, devising a waste management
plan is vital in order to comply with the rules and regulations as stipulated by the

national government with regards on the disposal of hazardous chemicals.

Gaseous emissions arise during the firing or drying of ceramics and may be

derived from the raw materials as well as fuels contribute gaseous pollutants. Carbon

oxides, nitrogen oxides, sulphur oxides, inorganic fluorine and chlorine compounds, as

well as organic compounds are of importance among the gaseous emissions.

Sulphur dioxide and other sulphur compounds

The concentration of SOX (mainly SO2) in flue-gases is closely related to the

sulphur content of the raw material, and of the fuel. Ceramic materials may contain

sulphur in the form of pyrite (FeS2), gypsum and other sulphates, and organic sulphur

compounds. Gaseous fuels are virtually sulphur-free, but solid fuels and fuel oils

contribute sulphur oxides on combustion. It should be noted that basic compounds

from raw materials (e.g. CaO formed by dissociation of CaCO3 during firing) can

reduce sulphur emissions by reacting with sulphur oxides. The reaction products are

retained within the body of the ware.

Oxides of nitrogen and other nitrogen compounds

NOX is mainly produced by thermal ‘fixation’ of nitrogen and oxygen from the

combustion air. This reaction is favoured by high temperatures (especially>1200 ºC)

and by excess oxygen. Fixation can occur within hot flames, even when the actual kiln

temperature is below 1200 ºC.

Carbon monoxide (and carbon dioxide)

Carbon monoxide, CO, arises from the combustion of organic matter in the

ceramic body – especially under low oxygen conditions. It may also be formed by the
 reaction of ‘fixed carbon’ in the body with carbon dioxide (CO2) released by the

thermal dissociation of alkali and earth alkali carbonates, for instance calcium or

magnesium carbonate during firing:

• CaCO3 —› CaO + CO2

• C + CO2 —› 2CO

Carbon dioxide forms as above and is the main oxide of carbon formed during the

combustion of fossil fuels.

Volatile organic compounds (VOCs)

Ceramic raw materials may themselves contain organic matter, and a wide

range of organic materials are added in the form of binding agents, pore-forming

agents, drying aids, adhesives, body fuels, burnout additives, etc.

During the early heating process especially in the coating process of ceramic tiles with

ZnO-PEG mixture, carbonization of organic compounds may occur with the release of

a complex range of VOCs.

On-site treatment

For the fumes being produced in the extension plant, exhaust ducts can be

utilized to suck out the possible fumes present in the working area. These suction

ducts can be installed in critical areas of the manufacturing processes which will then

be subjected to gas scrubbing before releasing unto the atmosphere. Air flows

turbulently through ducts at between 2,000-6,000 feet per minute (fpm). Ducts can be

made of galvanized metal, fiberglass, plastic, and concrete. Friction losses vary

according to ductwork type, length of duct, velocity of air, duct area, density of air, and
 duct diameter. [4] These ducts would then be connected to gas scrubbers where the

acid fumes would be contacted with water stripping the acid from the fumes.

Biofilters are widely used for odor and air pollution treatment, most particularly

for volatile organic compounds (VOCs) with high flow rates and pollutants

concentration less than 1,000 ppm. Compared to the conventional technology,

biofliters are cost competitive, with no secondary pollutants produced. [5]

Through the following treatment, gas emissions would be degraded into a much

safer and less toxic substances before releasing unto the atmosphere. The pilot plant

does not produce a large amount of gaseous emissions since there is no presence of

combustion nor gas streams being produced aside from fumes in the manufacturing

processes.

Offsite treatment

For the gaseous emission control of the pilot plant, there is no need for an

involvement of third-parties since there are no presence of serious gaseous emissions

like flue gas and such in the pilot plant. The only observable hazardous emissions are

due to fumes coming from possible pipeline leakage and transport of materials.

Utility Wastewater

Water plays a very important role with specific technological functions in ceramic

manufacturing industries, in which it is used as a raw material or in auxiliary functions

and the quantity of water being used varies among sectors and processes. However,

focusing on the extension of an existing ceramic plant, specifically the production of

functional tiles such as ZnO deposited on tiles, process wastewater is mainly generated

from equipment cleaning, simply auxiliary usage.

Process wastewater are collected from the equipment cleaning which mainly

came from the mixer and roller printer, which needs water to remove the remaining

contents of polyethylene glycol (PEG) and zinc oxide (ZnO) mixture adhered to the

surface of the mixing vessel and roller. The arising wastewater in the process usually

exhibits turbidity and color owing to the very fine suspended particles of the mixture for

coating operations. The PEG 600 used is a transparent liquid with a pH of 6 and is a

slightly toxic at higher concentration when ingested and considered to be irritant to skin

when in contact (MSDS). The ZnO is a white powdered solid. The coating mixture form

white sticky liquid, when washed with water, produced white colored water. Without

prior treatment of the wastewater may cause harm to aquatic life in Imus river, Cavite

and the public community that depends on the river. The plant Eurotiles Industrial

Corporation Ceramic plant is located in Silang, Cavite where there treated wastewater is

disposed in the Imus river.

The ZnO at nanoscale may posed threat to aquatic life when ingested with longer

exposure in the fish’s system causing damage to their internal organs and alter DNA.

This when released to the river may cause great loss in area’s agriculture. The trophic

transfer of ZnO to humans through consuming contaminated fish needed special care.

Therefore, disposal of ZnO deserves more attention since bioaccumulation of these

elements may occur on aquatic species with impact on both human and environmental

health (Beegam, 2016). Therefore, the wastewaster from the plant should be treated to
lessen the contribution to water pollution while following the standards set by the

authorities and protecting the environment.

On-site treatment method

Since cleaning of equipment are not daily scheduled in the process, the amount

of the ZnO and PEG coating mixture washed with water would not be at great amount.

However, the constituents inside the wastewater may posed threat to the environment.

Pretreatment of the wastewater using the flocculants and coagulants maybe used in

order to form large particles and subjected to filter press to separate the formed solid

from the water.

Off-site treatment method

The washed coating mixture containing mostly ZnO and PEG still have the

potential to clean wastewater as well. The presence of the ZnO photocatalyst can

degrade other organic contaminants. Other plants for their wastewater can use the

washed water from the equipment.

Conclusion

An effective waste management system involves operational procedures that integrate

continual improvements in waste management operations to ensure continued

compliance with environmental laws. If the elements of an overall waste management

system are not regularly inspected, maintained, improved, and evaluated for efficiency,
even the best designed unit might not operate efficiently. Implementing an effective

waste management system can also reduce long- and short-term costs, protect

workers and local communities, and maintain good community relations.

References

[1] Kaushik, S., & S.R.Shah, P. (2016). Energy Utilization of Ceramic Tiles Industries.

Retrieved from

http://ijariie.com/AdminUploadPdf/ENERGY_UTILIZATION_IN_CERAMIC_TILES__IND

USTRIES_ijariie2064.pdf

[2] UNIDO (1994). “Output of a Seminar on Energy Conservation in Ceramic Industry”

[3] European Commission (2007). “Reference Document on Best Available Techniques

in the Ceramic Manufacturing Industry”. Retrieved from

http://eippcb.jrc.ec.europa.eu/reference/BREF/cer_bref_0807.pdf

[4]"Occupational Safety and Health Administration," [Online]. Available:

https://www.osha.gov/dts/osta/otm/otm_iii/otm_iii_3.html#iii:3_3. [Accessed 27

November 2017].

[5]H. Elmrini, N. Bredin , Z. Shareefdeen and M. Heitz, "Biofiltration of xylene emissions:

bioreactor response to variations in the pollutant inlet concentration and gas flow rate.,"

Chemical Engineering Journal, 2004.