A case study of microwave processing of metal hydroxide sediment sludge

from printed circuit board manufacturing wash water

The large quantity of wash water used in the electroplating and etching process in

the manufacturing of printed circuit boards (PCBs) contains a high level of heavy

metal ions (Cu., Zn..., Ni ..., Cr. ..., Pb...). These potentially toxic ions are removed

from the wash water effluent through a polyelectrolyte flocculation and hydroxide

precipitation process during which a hydroxide sediment sludge rich in metal ions

and polymers is generated. This sediment sludge possesses some unique

characteristics and properties in terms of composition, ne particle size

distribution, high specific surface area, and a tendency to agglomerate after drying.

Direct disposal of this classified ``special waste'' (Department of Environment of

Northern Ireland, The Special Waste Regulations, Northern Ireland, 1998) at landfill

sites may cause serious soil and underground water pollution through a gradual

ionic leaching process. This paper describes an experimental investigation,

exploratory in nature, which employs microwave radiation for detoxication of the

sediment sludge through microwave heating, drying and metal ion immobilization

within the sediment solids. The effectiveness of microwave assisted binding and

immobilization of the metal ions within the sediment solids was studied in

conjunction with an evaluation of microwave energy efficiency in comparison to the

more conventional convective heating and drying processes. Given a sufficient

amount of microwave radiation, leaching of Cu2+ and Pb2+ was reduced by

2700% and 1080%, respectively, over a period of 12 weeks, and further leaching

was not detectable within six months at simulated local landfill aqueous conditions.

This paper also attempts, through experimental observation, to add to the very
limited understanding of the complex interactions and binding of free metal ions

with the polymeric materials and metal hydroxides under the influence of an

electromagnetic field. The high specific surface of the sediment solids and their

adsorption properties were further explored and characterized in a study of

adsorption of reactive dyes by the microwave processed solids.

Application of microwave radiation in the processing of solid materials has been

attracting growing interest with advantageous characteristics in the areas of

sintering and joining of ceramics, synthesis of composites, and polymer curing. In

the area of solid waste treatment and remediation, microwave power has been

explored in vitrification and recycling of electronic circuitry, processing of food

packaging waste, reduction of gaseous air pollutants, and regeneration of activated

carbon.

Although microwave irradiation offers some exciting potential in heating, drying,

and catalysis, commercial use of microwave power in the processing of chemicals

and solid materials, with the exception of foodstuffs, is still very limited because of

perceived high capital and operating costs relative to steam, combustion, electrical,

and other traditional sources of energy. The conceptual understanding of the

microwave effects is at present still controversial even though the end effects are

very encouraging. Some prerequisites have to be met before microwave energy

can be integrated into mainstream material processing.

In the last decade, microwave equipment and component companies have begun

to address the obstacles (complexity of construction, special custom design and

maintenance) in the implementation of microwave processing of materials. This

backdrop provides new opportunities and incentives in developing and applying

novel microwave technology in the processing of materials and solid wastes.

Microwave processing of hazardous industrial sludge

Industrial processes which produce wet solid sludge containing

organic/inorganic toxic compounds are facing increasing restriction and

costs associated with their disposal. The bulk of this type of industrial

sludge is currently disposed of at specialist waste landfills which is not

only expensive, but carries with it the risk of future environmental

liabilities. One of the greatest concerns on the impact of a landfill site is

the pollution of groundwater by leaching metal ions and other toxic

compounds. A small quantity of landfill leachate can pollute a large

amount of groundwater rendering it unusable as potable water.

Contaminated land also has been a serious issue of public and political

concern, and under the new regulations, the clean-up of contaminated

land sites will be the responsibility of the waste producers. It is

anticipated that the landfill disposal route will incur an increasing

economic cost due

to the increase of landfill tax and fewer available specialist sites.

Microwave treatment of hazardous industrial sludge and infectious

wastes is starting to attract growing interest. Differing from conventional

thermal treatment and incineration, the electromagnetic microwaves can

energize, mitigate and assist chemical binding of dipolar molecules and

metal ions within a solid structure. Microwave irradiation may catalyze

chemical reactions by a selective heating and catalysis mechanism.

Microwave assisted emulsion cracking has been successfully explored, at

pilot plant scale, for the segregation of oil from petrol-chemical

processing sludge containing highly stable oil emulsions.

By a special dipolar oscillating and dielectric losses effect, microwave

power offers unique advantages in heating materials selectively, evenly

and rapidly to high temperatures with fast control response. Reversed

temperature gradients can be generated in a microwave field and the

activation energy in sterilization, sintering, and chemical reactions can

be reduced.

Hydroxide sediment sludge generated in PCB manufacturing

The sediment sludge sampled in this study was obtained from a PCB

manufacturer based in County Down, Northern Ireland. Manufacturing of

high quality multilayer PCBs requires that the boards are thoroughly

washed between each electro-chemical process (electroplating and

etching, etc.) to prevent any cross contamination. As a result of this

extensive washing process, approximately 700 m water are used daily.

The wash effluent contains a high level of heavy metal ions and special

polymers used as chelating agents in the electroplating process. Over

95% of these metal ions are subsequently removed in an effluent

treatment plant employing a sequence of flocculation, pH adjustment

and alkaline precipitation processes. The hydroxide precipitation of the

metal ions is based on the occurrence of the following reaction:

M+++ 2 (OH-) M(OH)2

where M++ represents any divalent heavy metal ion. The metal ion

combines with the hydroxide ion to form the insoluble metal hydroxide

solid. The solubility of the metal hydroxide solid is pH dependent. To

further facilitate the precipitation process, a commercial poly electrolyte

flocculent is added to absorb/complex with the ions and form large

aggregating particulates before the hydroxide precipitation.

Experimental method and materials

The metal ions present in the hydroxide sediment are predominantly copper, lead,

and traces of zinc, chromium, nickel and silver. The sediment was dewatered

through a compression and filtration process before microwave treatment.

The frequency of the microwave was fixed at 2455 MHz and the microwave power

remained at 900 W in all experiments unless otherwise stated. Since the rate of

microwave heating and water diffusion depends strongly on the geometry of the

solid mass, samples of dewatered sediments were placed in the microwave oven

in a manner so that the samples were evenly spread on the turntable with an

average thickness of 1 cm to ensure an even heating and mass transfer process.

In all experiments a sample mass of 100 g was used unless otherwise stated.

RESULTS AND DISCUSSION

Microwave drying of the hydroxide sediments
Heating and drying with microwave radiation is distinctly different from conventional

processes based on heat convection and conduction. Whereas conventional

means depend upon the slow heat transfer from the surface of the material to the

interior as determined by the differential in temperature, heating with microwave

energy is, in effect, bulk and in-depth heating in which the electromagnetic field

penetrates and interacts with the material as a whole. An instantaneous release of

heat is caused by fast microwave interaction with dipolar molecules of high-loss

dielectric properties.

In conventional drying, moisture is initially flashed off from the surface and the

remaining water diffuses slowly to the surface. The potential of energy transfer is

the

temperature gradient. The potential for mass transfer is the mass concentration

gradient existing between the wet interior and the dryer surface. These two drying

mechanisms function in opposite directions which results in a particularly slow

process as high external temperatures are needed to generate the required

temperature differences. The net effect is usually the formation of a crusty surface

that is thermally insulating, and, thus prohibitive to the transmission of heat. The

advantages of deep microwave electromagnetic energy deposition within the

material are, thus, very evident. The speed of heating in a microwave system is a

distinct advantage and can be manipulated from one extreme to the other

depending on the particular application.

Characteristics of the microwaved hydroxide solids

Microwave drying produced a loosely bound conglomerate of solid particles which

could be easily segregated. A vibrating shaker (Endecots Octagon Digital) installed

with trays of classified sieves was used to classify the sizes of the particles. Table 3

presents the size distribution of the hydroxide solid particles. The mass had a

powdery characteristic with a large amount of ne particles in the micrometer size

range. The solids have large surface areas when analyzed by the BET N 2
adsorption method. The bulk density and total porosity of the sediment solids were

also analyzed by employing the method of mercury intrusion porosimetry. An

electron scanning microscopy image of the dried sediment mass is presented in

Fig. 6 which shows the irregular shapes of the dried hydroxide crystals in

the micro meter size range.

Adsorption properties of the microwave hydroxide solids

Apart from having relatively large surface areas, the sediment solids also had a

high carbonaceous content originating from the source of the polymeric chelating

agent used in the electroplating process and from the polyelectrolyte used in the

flocculation process. These characteristics are closely related to adsorption

properties and were further studied by carrying out experiments on adsorption of

reactive dyes from synthesized solutions by the microwaved sediment solids.

Microwave dried sediment solids in the conglomerate state were ground to powder

and placed in sealed glass bottles containing dye solutions.

Conclusions
Microwave radiation has shown a remarkable effect on immobilization of the heavy

metal ions within the sediment solid structure though the underlying mechanism is

unclear. The ion immobilization could be a resultant effect of a much higher drying

temperature combined with the effect of electromagnetic waves which may

facilitate a strong interaction and binding between residual free metal ions and

dipolar polymeric molecules in the hydroxide sediments.

Analysis of the microwaved sediment solids showed that the sediment had some

unique characteristics in terms of fine particle size distribution, high specific surface

area and a tendency to agglomerate after drying.

Investigation of adsorption properties of the microwave processed sediment solids

also revealed a high affinity of the solid surface towards an anionic reactive red

dyes, indicating a net positive surface charge.

Comparison with conventional heat convection at the bench scale shows that

microwave drying is more advantageous in terms of drying rate and energy

consumption. The combination of microwave and hot air heat convection delivered

the fastest drying rate at the cost of a much higher energy consumption per unit

dried mass. It is interesting to note that energy consumption fell with increased

solid mass in the combined heating mode. This finding indicates that energy

utilization at large scale operation could be more efficient with the combined.