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

 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]

1. 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.

2. 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.

1.1. 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.

1.1.1. 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.

1.1.2. 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.

3.1 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.

3.2.1 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.

3.2.2 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.

2. 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.

[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__INDUSTRIES_ijariie2
064.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.