CHEMICAL CLEANING OF EQUIPMENT AND PARTS OF DESALINATION PLANTS FOULED BY OIL SPILLS1

P.C.Mayan Kutty and Abdul Ghani I. Dalvi

ABSTRACT Chemical contamination of seawater feed by oil spills is a major threat to the safe operation of desalination plants. Tar or residue which constitute about 55- 60% of oil content if camed over to plant may deposit on the various parts of the plants adversely affecting product quality and equipment performance. Therefore, one should be able to clean the affected parts of the plant effectively and rapidly to avoid unscheduled plant shut down. This report describes the studies camed out to find an effective solvent for easy and safe cleaning of plant equipment contaminated by oil spills. Laboratory scale experiments were carried out to evaluate several solvents such as xylene, hexane, carbontetrachloride, and trichloroethane as safe, fast and cost effective decontaminating agent. Suitability of these solvents from health, toxicity and waste disposal aspects were also examined. Out of the four solvents tried it was found that carbon tetrachloride is superior to other chemicals in almost all aspects i.e. solubility of tar kinetics, health, toxicity and cost. This study was carried out as per the requirement of the R&D Center research and development task #5. 1. INTRODUCTION Contamination of seawater feed to desalination plants by oil spills in the vicinity of intake area, may pose a major threat to the safe operation of the plants. Some of the problems created by oil spills are: (i) Contamination of feed seawater and equipment by toxic contents of oil viz hydrocarbon and their derivatives,

1 Issued as Technical Report No. SWCC (RDC)-29 in October, 1993.

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(ii) (iii) (iv)

Carry over of these toxic chemical to product water thereby making the product water unpotable. Endangering the biological life in seawater. Oil tar and residues, if carried over to plant, will coat on vital equipments such as pumps, travelling screen filters, chlorine generating cells, deaerator, tubes, demister, flash chambers, and piping etc. in MSF plants, micron filters and multimedia filters in reverse osmosis (RO) plants.

Most of the organic substances other than those of simple structure and low boiling point when pyrolyzed yield dark , generally viscous liquid termed as tar and pitch. When the product is liquid of fairly low viscosity at ordinary temperature it is regarded as tar and if it is very viscous, semisolid it is called pitch. The distillation of crude petroleum yield a pitch-like residue termed as bitumen or asphalt. Largest source of tar and pitch is the pyrolysis or carbonization of coal. The terms tar and pitch are synonymous with coal tar. The residual tar if it reaches the intake bay could eventually block the screen filters and other flow through system retarding the flow of feed to plants, and in extreme cases, may cause total failure of the plants. Thus it becomes essential firstly to prevent the oil from entering the intake area by booms, oil dispersion chemicals and by other means. In spite of all precautions some oil and oil tar may reach plants intake area and may deposits on screens. As a result of continuous operation build up of tar may occur on various parts of the plants, especially screen filters etc and may result in plant shut down. Under these circumstances, one should be able to clean the affected parts quickly. Physical removal by brush is not onlytedious but also very time consuming. Best way is to treat the contaminated parts with some solvents that can dissolve and remove the oil constituents easily and rapidly. Aim of the present task is to screen some commercially available organic solvents to find suitable chemical agents for decontamination of the parts of desalination plants affected by oil spills. This report describes the laboratory scale experiments carried out to evaluate the effectiveness of some solvents as safe, fast and cost effective decontaminating agent. The principal question addressed by this study was the effectiveness of tar removal by the solvents from contaminated parts due to oil spills. In order to evaluate this, solubility of tar in various tested solvents, spectral studies of tar in these chemicals, and their kinetic behaviour were determined. Further, their suitability from economic, health and waste disposal aspects was also examined.

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2. 2.1

EXPERIMENTAL Chemicals Four commercial grade solvents viz (i) Hexane (2) Xylene (3) l,l,l trichloroethane and (4) Carbon tetrachloride were selected for the study.

2.2

Experimental Methods The solubility of tar in the selected solvent and its dissolution kinetics were determined as follows:

2.2.1

Kinetic studies In 200 ml beaker 100 ml of the solvent was taken and beaker is placed on magnetic stirrer. The solvent was stirred at slow and constant speed using a Teflon stirring bar. In an aluminium boat 20 gm of tar was weighed and the boat along with tar was placed in the solvent inside the beaker. At the end of 1 minute approx. 5 ml solution was withdrawn from the beaker and kept separately for spectral measurement. The experiment was repeated again with fresh solvent, only this time solution was withdrawn at end of 2 minutes stirring. Several experiments were conducted in similar way collecting samples at various intervals of time ranging from 0-10 minutes. The experiments were repeated under identical conditions using all four selected solvents. After collecting the samples for different interval of time separately, their spectra were recorded in the region 190 - 600 mm. Photometric data were also recorded at 410,330,300 and 280 nm to cover the broad absorption peaks due to dissolved tar in these solvents. For all the above experiments, the parameters chosen are given below:

(i) (ii) (iii)

Instrument Wave length (a) Spectrum scan (b) Photometric Slit

UV 2100 S Shimadzu Recording Spectrophotometer. 190 : nm - 600 nm 410,33,300 and 280 nm 0.5 nm

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2.2.2 Solubility Studies The determination of solubilities of tar in the solvents were determined as follows: 10 ml of the chemical was taken in a 50 ml preweighed beaker placed on a magnetic stirrer. Small aluminium planchette (preweighed) was taken and 5 gm of air dried tar was weighed into it. Whole planchette along with tar was placed in beaker containing the solvent and stirred. After about 1 to 1.5 hr of stirring and no more tar was getting dissolved, the solution was decanted. Planchette was removed from beaker and kept for drying at room temperature. Planchette was then weighed along with the remainder of tar in it. Solubility of tar in the solvent was calculated from the difference in weights. Correction was also applied if any undissolved tar was found to stick to the beaker by weighing the air dried beaker after the experiment. 3.0 RESULTS AND DISCUSSION Composition of coke-oven tars varies according to their origin see Table 1. The main constituent, irrespective of their origin, is found to be medium soft pitch (55% or more) with significant quantities of naphthalene and phenanthrene, As it is not felt necessary to study the solubilities of the individual constituents in the tested solvents, samples of weathered and air dried tar balls collected from the beaches near Al Jubail intakes were used for the present study. The composition of these samples was not available in the literature. 3.1 Physical Parameters of the Solvents Physical parameters of the solvents viz molecular weight, density, melting point, boiling point and their solubility in other solvents are given in Table-II. It can be seen that boiling point ranges between 69 to 144oC whereas melting point lies between -95oC to -23oC. Further one can note that densities of hexane and xylene are less than water whereas densities for trichloroethane and carbon tetrachloride are higher. All solvents are soluble in alcohol and ether while carbon tetrachloride is slightly soluble in water as well. 3.2 Solubility Table III shows solubility of tar in the 4 solvents determined as described in para 2.2.2. It can be seen from the table that tar has maximum solubility in carbon tetrachloride (124 gm/litre) whereas hexane dissolves only 0.8

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gm/litre which is minimum among these solvents. Other two chemicals, xylene and trichloroethane, show intermediate solubilities. These results suggest that carbon tetrachloride is the most suitable solvent from solubility point of view among these 4 chemical agents. 3.3 Spectral Studies Spectral scans carried out in the UV-visible regions using blank solvents indicate the absence of absorption peaks in all four solvents. However, transparency in this region of the spectrum (i.e. 190-600 nm) disappeared when coal tar is dissolved in these solvents as shown in Figure.1 for tar in hexane. A broad absorption peak develops around 280 to 320 nm in all these solvents on tar dissolution. This broad peak is characteristic of coal tar composition. Figure.2-5 show the absorption spectra taken in different solvents containing tar. These figures also show the spectra taken after different time intervals indicating increasing solubilities with contact time as described in para 2.2.2. Figure.6 shows absorptions measured as peak heights at 280 nm in different solvent as a function of contact time. It is seen that trichloroethane reaches saturation solubility between 3-4 minutes whereas it takes about 5-6 minutes for reaching saturation in case of carbontetrachloride. But the slightly low rate of dissolution of tar in carbontetrachloride is more than compensated by its high solubility. The other two solvents show considerably low rates of solubility. Figure. 6 also supports the data obtained in solubility studies where it has been found that coal tar has the maximum solubility in carbon tetrachloride. Furthermore, solubility after1minute is maximum in carbon tetrachloride and much less in other solvents. This suggests that not only solubility but also rate of dissolution of coal tar is quite high in CCl4 compared to other solvents. This aspect of the solvent i.e. capability of dissolving more quantity of tar at a faster rate must be considered as an important criterion of the solvent as a cleaning agent. Solvents which are capable of dissolving or removing tar from contaminated parts of plants easily and rapidly will be preferred over solvents which are slow in this respect. Both these requirements are satisfied by carbontetrachloride. 3.4 Costs of the Solvents Table IV compares the costs of the four solvents as obtained from local suppliers. It can be seen that hexane which has minimum solubility of tar, has maximum cost of 26 SR/kg, thereby indicating unsuitability not only from other aspects but also from economy point of view. Carbon tetrachloride has

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the lowest cost at the rate of 5.5 SR/Kg. Cost of xylene and trichloroethane are slightly higher but comparable to that of CCl4 However, great difference in solubility and slightly lower cost of CCl4 again indicate its superiority over other solvents. 3.5 Health Aspects and Toxicity Toxicity data of these solvents are given in Table V. It can be seen that all the solvents have adverse and chronic effects on human. Hexane is a suspected neurotoxic whereas xylene damages liver and kidney if inhaled. Trichloroethane is known to affect nervous system and CCl4 is carcinogenic. Lowest published lethal concentration for inhalation of xylene is 6125 ppm/l2 hr. and for trichloroethane is 27 gm/m3/l0 min. However, for CCl4 it is 1000 ppm for inhalation and 43 mg/kg of human for oral dose. Maximum contamination level (MCL) in drinking water is lowest for carbon tetrachloride (0.005 ppm) and 0.7 ppm for trichloroethane. Xylene has MCL value of 10 ppm which is the highest. From toxicity data it looks that all solvent show toxicity of varying degree thereby rendering them unsuitable. Still in spite of adverse health aspect these solvents can be used for cleaning purposes, as l,l,l trichloroethane is currently used as an industrial cleaning agent. 3.6 Waste Disposal Usage of chemicals for cleaning purpose will obviously generate a lot of waste. As we are aware that these chemicals are toxic and have adverse effect on human health, one should either store these chemicals safely or find suitable way of disposal. These chemicals can be classified into two categories, one which are inflammable and other non-inflammable. Two different methods can be adopted for disposal of the two types of solvents as mentioned below. 3.6.1 Method - 1 (For Inflammable Waste) Burn the waste in a chemical incinerator equipped with an after burner and scrubber. But exert extreme care in igniting as the material is highly flammable. This method is applicable to hexane and xylene wastes. 3.6.2 Method - 2 (For Non-Inflammable Waste) Dissolve or mix the waste material generated by either trichloroethane or carbontetrachloride

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with a combustible solvent and burn in chemical incinerator with after burner and scrubber. 4. CONCLUSION The results of this study show that out of four chemicals tested hexane and xylene are unsuitable for decontamination of equipment fouled with tar. Both trichloroethane and carbontetrachloride are suitable cleaning agents. Considering several aspects such as solubility, kinetics of dissolution, cost etc carbon tetrachloride appears superior to trichloroethane. Further studies will be carried out on the MSF and RO pilot plants using the two most suitable solvents during the oil carry over tests scheduled on these plants. REFERENCES 1. Robert E. Lenga, The Sigma Aldrich Library of Chemical Safety Date, Vol. I & Vol. II, 1988. 2. EPA, State Drinking Water Programme., HDR Engineering Inc., Char, Published by AWWA-1992.

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