Agricultural Wastes 8 (1983) 51-63

Treatment of Edible Oil and Soap Processing Wastes

M. F. H a m o d a Department of Civil Engineering,Kuwait University,Kuwait A. Hanza & S. Saad High Institute of Public Health, Alexandria University,Alexandria, Egypt

A BSTRA CT Laboratory batch and conthmous-flow experiments were conducted to study the treatment of oily wastes using a system comprising dispersed (diffused) air flotation and acti~,ated sludge processes. Removal of oil and Su.ipended Solids was eJJectirely accomplished b), air flotation ht conjunction with chemical coagulation. Alum was superior to ferric chloride and lime, especially at low doses. Acid(lication to pH 4, coupled with dispersed air flotat;on, was alsa effective in oil removal but was les~ effectire in Suspended Solids reduction. The activated sludge protests successfully removed soluble organics and oils remaining after air flotation treatment ond was not inhibited by the relatirely high salt content of the waste. Op;imum results were obtained at moderateO, low organic loadings, suggesting the u.w oJ an extended aeration process.

INTRODUCTION The discharge of wastes containing oils into water bodies has received worldwide attention in recent years. In Egypt, the two largest edible oil plants, producing nearly one-third of the gross national production of oils and hydrogenated fats, are located in the city of Alexandria. These are the Salt and Soda and the Extracted Oil Plants. Both discharge about 20000m 3 daily of heavily polluted wastes into Lake Maruit, located south of the city, causing intolerable environmental and public health hazards. 51 Agricultural Wastes 0141-4607/83/$03.00 '~'~Applied Science Publishers Ltd, England, 1983. Printed in Great Britain

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M. F. Hamoda, A. Hanza, S. Saad

This study was initiated to evaluate treatment options of the oily wastes and to establish their treatability parameters. The effects of various proposed treatment conditions on the removal ofoil, as well as Suspended Solids and organic matter, were studied using a treatment system comprising the dispersed air flotation and activated sludge processes. In dispersed air flotation, gas bubbles are generated by introducing the air through mechanical agitation or by sparging air through porous media. The process produces coarser bobbles than dissolved air flotation but consumes considerably less energy (Ramirez, 1979). Air flotal.ion has been used to assist in the removal of oil and grease from domestic sewage (Liptak, 1974). The added diffused air partly de--emulsifies the oil and grease and assists their flotatio~'t. It has also been used as a clarification and/or thic~ ening process for Su'~pende~:tSolids removal. The entrapment of~as bubbl.'s can be promoted by the use ofcoagulating chemicals which inc, ease the flocculent structure of the floated particles and thereby facilitate the capture of rising gas bubbles (Zajic, 1971; Luthy et al., 1978). Aerobic biological treatment of wastewaters containing edible oils and fats has been successful (Gurnham & Nedved, 1974; Young, 1979). However, the impact of oil./materials on the activated sludge process appears to be dependent upol; ~he type of oil and the loading rate (EPA, 1971).

MATERIALS AND METHODS Wastewater samples were collected daily from the edible oil refinery. Laboratory experiments were conducted at room temperature (18--22 C) using flotation and activated sludge treatment systems to evaluate the effect ef different treatment conditions on the removal of oils (floating, emulsified, and saponified), Suspended Solids and BOD. The experimental programme comprised preliminary batch experiments on dispersed air flotation with or without chemical addition. Based on the results of the batch studies, three phases of continuous flow experiments were conducted. Phase I included successive stages of air flotation in conjunction with acidification at pH 4, neutralization and then activated sludge treatment. Phases 1I and III involved air flotation in conjunction with chemical coagulation using 50mg and 100mg per liter of alum respectively, followed by activated sludge treatment. Each

Treatment o.]"edible oil and soap processing wastes

53

phase of the study included three consecutive series of the experiments, conducted at different hydraulic flow rates, to study the effects of detention time or waste loading on the tested process performance. 'rhe batch system consisted of six 20-liter rectangular jars fitted with diffusers connected to air pumps. Ten liters of waste were placed in each jar. Batch flotation experiments were conducted using alum, ferric chloride and lime as conditioning agents and a control was run in each case to examine the effect of the added coagulants and to determine the optimum dose of each chemical used. The effect of pH adjustrnent on destabilization of the oil emulsions was also tested using HC1. The control experiments represent plain flotation whereas those using chemicals for coagulation or acidification represent chemical flotation. Wastewater samples containing oil at concentrations ranging between 100 and 1000 mg liter - ~ were used. The continuous flow system comprised a flotation-clarification unit followed by an activated sludge unit; both were made of Plexiglas:i. The flotation unit was 50cm 25 cm with a liquid depth of 60 cm. It had two interconnected compartments of equal size, one for chemical trea.'.ment and the other for flotation. The level of liquid was adjusted from the inlet to the outlet to allow continuous withdrawal of flotable matter fro~aa the surface to a side channel attached to the unit. Compressed air was introduced to the flotatio,a unit at a constant rate of about 30 cm 3 rainthrough porous diffusers mounted near the bottom of the unit. Chemical additions for acidification (HCI) or coagulation (alum solution) were controlled by peristaltic pumps adjusted to maintain a predetermined pH or alum dosage. The influent flow to the flotation unit was controlled by peristaltic pumps and the clarified effluent was discharged by gravity to the activated sludge unit. The activated sludge aeration--sedimentation unit had two adjacent compartments with a total length of 120cm (100cm for aeration and 20cm for sedimentation), a width of 25cm and a liquid depth o~"~i0cm. The effluent end compartment, used for settling, was partially separated from the aeration compartment by a sliding baffle adjusted to leave a slot opening at the bottom for the back flow of settled 'return sludge'. Compressed air was supplied at the bottom of the aeration compartment through porous air diffusers. Operation of the flotation and the activated sludge units was controlled by adjusting the influent flow rate to obtain hydraulic detention times of 3 to 7.5 h in the flotation unit and corresponding detention times of 12 to

54

M. F. Hamoda, A, Hanza, S. Saad

30 h in the aeration compartment of the activated sludge unit. In each case the units were run continuously to reach stable (steady-state) conditions before results were reported. Chemical and physical analyses of the wastewater influent and effluent of each treatment were performed according to the Standard Methods Jor the Examination o f Water and Wa.stewater (A PHA, 1975), wherever feasible.

RESULTS AND DISCUSSION Wastewater characteristics The wastewater used in the continuous flow experiments was generated from the E~ tracted Oil Company which specializes in oil hydrogenation, soap manufacture and glycerine refining. The wastewater produced contains reh~tively high levels of saponified oils. In the manufacturing processes, direct contact of water with the oil is inherent so that, when the products are purified, a direct transfer of the impurities is made to the wastewater stream together with additional oilwater emulsions. Oil is wasted through leaks, spills, clean-up, drainage of pipes to make repairs and other non-controllable household operations. In addition to oils, large amounts of water-soluble complex organic materials, originally present in the raw oil, find their way to the waste. Table 1 summarizes the average characteristics of composite samples of edible oil wastewater during the phases of this study. Wastewater characteristics varied slightly during the period of study but daily variations were moderate compared with other types of industrial wastewaters (Eckenfelder, 1970). However, discrete sz~.mples showed a wider range of values for pit, conductivity and salinity of 5.5-7.6, 3500 95001mahoscm ~ and 1900---7000ppm, respectively. The chloride and sulfate concentrations varied; between 870-2000 m g l i t e r ~and 170 400 mg liter " t respectively. This indicates the relatively high salinity and salt content of the raw waste. High salinity is attributed to dumping of "salting out" wastes after alkaline refining of edible oil and dumping of concentrated salt solution during hydrogenation by electrolysis. The Total Solids and Suspended Solids ranged between 3010 and 7805mg liter ~ and 417 and ll00mgliter--~, respectively. The average volatile portion of the Total Solids was about 25',!o, which reflects the high inorganic salt content of the waste.

Treatment of edible oil and soap processing wastes

55

=~~,__

i',4

o 6 ~ 6 6 6 o 6 b

56

M. F. Hamoda, A. Hanza, S. Saad

The oil content of the raw waste was in the range 145-960 mg literThe B O D values reported ranged between 300 and 2600 mg liter- ~. The raw wastewater showed an average B O D s / C O D ratio of 0.6, indicating that the waste is fairly biodegradable (Eckenfelder, 1970).

Preliminary tests
The results obtained from batch tests on the removal of pollutants from the oily waste by plain dispersed (diffused) air flotation are shown in Table 2. The mean oil removal was 45 ~ , which is relatively low. Acidification of the waste improved oil removal by this process. Maximum removal of oil was achieved at pH 3, as shown in Fig. I, and averaged 90'7,,, with parallel reductions in SS, B O D and T O C of 84"/, /o 50 '/; and 49 '),;, respectively. Acidification to this pH seems to eliminate lhe strong negative charge on the free acid carboxyl groups, resulting in a reduction of solubility and consequently a better chance for oil globule coalescence and flotation. However. acidification to pH 2 did not improve the oil removal efficiency, apparently due to the reverse o f charge and formation of a stable emulsion rather than the separable oil. Addition of a chemical coagulant (e.g. alum, ferric chloride, lime) increased the rising rate of ttocculated oil droplets during dispersed air flotation. Oil removals of up to 9 7 % were achieved by each of TABI.E 2 l']ticicncy of Plato Dispersed Air Flotation t No Chcmical Addition) lt'ast~,water characteristics ling liter t ) Oil .S'S ''"~ BOD'~ ~ 7()('"' ;10 150 210 405 420 521) q~0 960 982 159 178 238 515 618 721 1173 1235 1305 172 183 249 548 789 683 1320 1320 1412 83 98 249 245 258 358 684 682 692
Oil Remocal tfltciem'y {'!,,) SS BOD s TO("

37 27 128 50 36 46 57 58 55

32 25 36 48 32 42 49 43 48

30 32 35 39 28 40 43 42 40

30 31 31 47 30 44 47 48 52

(a) Suspended Solids. (b) Biocl:emical Oxyden Demand 15 daysL (c) Total ,.)rganic carbon.

Treatment of edible oil and soap processing wastes

57

the coagulants in conjunction with dispersed air flotation when high coagulant doses were used, as shown in Fig. 1. The corresponding SS, BOD and TOC removals were up to 95 % for both alum and ferric chloride, but were slightly lower in the case of lime. In general, the coagulants studied proved to be effective in destabilizing the emulsified oils as well as coagulating and precipitating the majority of the complex organic pollutants of the waste. However, the dose of alum required for the effective removal of pollutants was found to be appreciably lower than that of ferric chloride or lime. Moreover, the effluent coloration problem associated with the application of high ferric chloride doses, the handling and pH increase problems associated with the use of high lime doses, as well as the considerable increase in sludge production and effluent salt content in these cases, may also favour the use of alum at lower doses. The multiple regression technique was applied to the data obtained from the various coagulants tested in the dispersed air flotation batch

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PH VALUE SOO

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60

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/. OiL REMOVAL (b) A L U M ADDITION

FERRIC CHLORIDE D O b E ( m v I I ) 000-m ~00

LiME DOSE ( m g l l ) .

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% OIL REMOVAL LIME ADDITION

Fig. I. Oil removal by chemicalflotation.

58

M. F. Hamoda, A. Hanza, S. Saad

system at different levels of initial oil content in the waste. Prediction models were developed which related the oil removal percentage (Y) to the initial oil content in milligrams per liter (X~) and to the dose of alum, ferric chloride or lime, whichever was applicable, in milligrams per liter (Xz). The following models were obtained with a good statistical fit to the data, as indicated by the high R 2 (coefficient of determination) value in each case: Alum Addition/Air Flotation: Y = 78.630 - 0.015Xt + 0,083X 2 Ferric Chloride Addition/Air Flotation: Y= 71"727 - 0.013X t + 0.058X z Lime Addition/Air Flotation: Y=71.318--0.014X~ + 0 . 0 7 I X 2
(R 2 = 0.777) (R 2 =0.780) ( R 2 = 0.886)

C O N T I N U O U S - F L O W TESTS Dispersed air flotation The performance of continuous flow dispersed (diffused) air flotation in conjunction with acidification was studied in Phase I experiments. Based on the results of preliminary studies, acidification to a practical pH value of 4 was adopted in Phase I experiments. Also, dispersed air flotation in conjunction with chemical coagulation was investigated using 50 mg and 100rag per liter of alum in Phases 11 and 111 experiments, respectively. The results of Phases I, 11 and III experiments are summarized in Tables 3 to 5. These results generally contirm those obtained in the prelimi~ary batch experiments. Acidification to pH 4 and air flotation removed about 70":;ii of oil (Table 3). The overall efliciencies of SS and BOD removal were low if comp~red with oil removal. Chemical coagulation using 50 mg per liter of alum and air flotation, studied in Phase I1 (Table 4), resulted in about 85 ),~,oil removal, which is higher than obtained in Phase I. This was also true for SS and BOD removals which were improved considerably because of alum coagulation. Better removal efficiencies for oil, SS and BOD were obtained using a higher alum dose ( 1 0 0 m g l i t e r ~) as shown in Table 5. Alum

Treatment o f edible oil and soap processing wastes

TABLE 3 Summary of Results~-Phase I Experiments*

Treatment
pH Series I: AF 4~ AS ~ Overall Series 2: AF AS Overall Serie:; 3: A F AS Overall 4.8 6.5 4,5 6.4 4,3 6.2

Effluent characteristics ~a~(mg l i t e r ~)

TS 5655 5 300 5121 4984 3441 3 327 SS 360 118 450 142 456 166 VS 990 776 935 792 732 575 BOD~ 222 37 199 38 325 77

Oil
85 19 75 19 I06 30

l~emoval percentage (%) SS BOD s Oil

55.3 -$5.4 52.5 85.0 48.3 -81.2 44,5 83,3 90,8 43,9 80,9 89,3 41,2 76,3 86,0 72'7 77.6 93.9 72'0 74.7 92.9 71.2 71.7 91.8

* Acic, ification at pH 4 and dispersed air flotation followed by activated sludge treatment, (a) See Table I for raw wastewater characteristics. (b) AF = air flotation. Ic) AS = activated sludge.

TABI.E 4 S u m m a r y o f R e s u l t s P h a s e I1 E x p c r i n i e n t s *

Treatment 1711
Series I: AI :''' AS '~ Overall Series 2: AF AS Overall Series 3: AF AS Overall 6.1 6.3 ~',.8 (~.6 6.9 7.1

l'ffhwnt characteristics'"' (rag liter -') "IS SS VS BOD S Oil

2431 I 997 2972 2411) 3355 3311 161 52 167 57 175 61 456 375 567 459 831 784 130 19 158 25 169 29 31 7 35 9 46 12

Remot'al percentage s '~i,) SS BOD~ t;il

73.4 91.4 72.6 90.7 72.1 90.2 73.1 85.4 96. I 72'2 84.1 95.6 71.7 82.8 95. I 87.9 77.4 97.3 86.9 74'3 96'6 853 73.9 96.2

* Addition of 50rag per liter of alum and dispersed air llotation followed by activated sludge treatment. (a) See Table I for raw wastewater characteristics. (b) AF = air flotation. (c) AS .~ activated sludge.

60

M , F. H a m o d a , A. H a n z a , S. S a a d

TABLE 5
S u m m a r y o f R e s u l t s - P h a s e 111 E x p e r i m e n t s * Treatment pH Series 1: AF ~b~ AS~'~t Overall Y, eries 2: AF AS Overall Series 3: AF AS Overall 6.4 6.5 7.1 7.1 7.1 7,1 Effluent characteristics c~ (rag liter - t ) TS SS VS BOD 5 Oil 3016 2418 4147 4 028 5141 4607 101 36 160 60 133 51 458 292 620 432 736 667 120 7 153 12 120 11 18 4 24 6 29 8 Remoral percentage (%) SS BOD s Oil 83,4 -94, I 82.0 93.3 8t.8 ~93.0 75.0 92,2 94.2 I 77,8 98.5 98, 3 73.8 91,5 92. I 75,0 97.9 97,9 72,1 90,8 90,8 72,4 97.4 97,5

* Audition of 100mg per liter of alum and dispersed air flotation followed by activated sludge treiltmelll. (a) See Table 1 for raw wastewater characteristics. (b) AF = air flotation. (c) AS = activated sludge.

proved to be effective in destabilizing the emulsified oils as well as coagulating and precipitating the majority of Suspended Solids and ccmplex organic pollutants of the waste. However, recovery of reusable oi ~,is somewhat difficult since the separation of oil from the chemical sludge : equires special treatment, e.g. sulfuric acid addition to release the oil from the sludge. Like other clarification processes, the dispersed air flotation process performance is affected by the hydraulic detention time. However, only slight improvements were found at longer detention times, suggesting no practical advantage in increasing the detention time beyond 3 h. It should be pointed out, however, that the adoption of longer detention times was particularly beneficial in the case of acidification in conjunction with air flotation, due to partial neutralization of the treated effluent in the flotation tank. Tables 3 to 5 clearly show that dispersed air flotation was highly effective in oil removal, especially when alum coagulation was used in conjunction with air flotation. Th.e latter process was also effective, but to ~ lesser extent, in removing BOD. This calls for a subsequent biological treatment for the removal of the remaining BOD. Perhaps a combination of acidification to pH 3, pH adjustment and alum coagulation in conjunction with dispersed air flotation could be, although not tested, a bette~ ~ystem for complete treatment of oily w~tstes. However, excessive

Treatn ent o f edible oil and soap processing wastes

61

chemical treatment of the waste could considerably increase its inherently high inorganic salt content.
Activated sludge treatment

The results obtained from the activated sludge unit in Phases I, II and III are presented in Tables 3 to 5. These results indicate that biological treatment would be an effective method for removal of BOI') and oil remaining after dispersed air flotation treatment. The high BOD removals obtained demonstrate that the waste is fairly biodegradable. This supports recent findings (Groenewold et al., 1982) which show that the biodegradability of edible oils is almost twice that of typical municipal wastewater and considerably higher than that of petroleum oils. No apparent toxicity was demonstrated by the relatively high salinity and inorganic salt content of the waste over the study period. This is in agreement with the results of Tokuz (1979) who reported that high salinity wastes did not affect the performance of the activated sludge process. The hydraulic detention times employed in these experiments (12 to 30 h) and MLSS concentrations ( 1530-2250 mg liter- 1) corresponded to organic loadings (F:M ratio) between 0.12 and 0.6kg BOD 5 per kg MLSS per day, The performance of the activated sludge process was affected by the organic loading, as illustrated in F~g. 2. Higher loadings resulted in lower BOD and oil removal efliciencies. Figure 2 defines an optimum loading range suggesting the use of an extended aeration system operated at moderately low loading (about 0.2 kg BOD 5 per MLSS per day) for the tinal design of the activated sludge system.
| oo

w er

8O

o~

oJ

0.1

0,1

or,

0,5

0,6

0.7

Kg B O D s / K g MLSS_DAY

Fig. 2.

Effect of organic loading on BOD removal by activated sludge.

62

M. F. Hamoda, A. ltanza, S. Saad

At the range ofloadings studied, the sludge volume index (SVI) ranged between 60 and 87 milliliters per gram of MLSS, with the lower values being found at the lower organic loadings. The sludge settleability evaluated by 3VI was good, especially in Phase III in which 100mg per ilter of alum was used in the preceding air flotation treatment. It is apparent that alum coagulation in the flotation treatment has a favourable effect on sludge settleability in the activated sludge system. On the other hand, the dissolved oxygen content in the aeration tank was consistently higher than 4 mg liter- 1. The contact of the waste with air in the flotation unit prior to activated sludge treatment contributed to this high dissolved oxygen content of the waste. The results obtained demonstrated that the activated sludge process performance was good when compared with literature reports (Eckenfelder, 1970) even though the waste contains complex organic constituents. it is thought that oils applied to the activated sludge system are sorbed onto the biological flocs and then degraded. However, at high oil loadings oil may accumulate on the sludge, causing a loss of sludge density al~..d deterioration of sludge settling characteristics. When waste acidification is used in conjunction with air flotation, waste effluent neutralization may b~: required prior to activated sludge treatment in order t,~ preserve the b~Mfering capacity of the activated-sludge system. The overall performance of the dispersed air flota tion--activated sludge system, as shown in Tables 3, 4 and 5, indicates that removals up to 98 '}i,, 96 '!,,;and 94"~,;were achieved for oil, BOD and SS, respectively, when the alum dosage used was ! 001T~gliter - ~(Table 5). Good effluent quality was also attained. ACKNOWLEDGEMENTS This investigation was supported by US EPA Grant No. 3-542-4. The authors gratefully acknowledge the assistance of the technical statt'of the Industrial Waste Research Laboratory at the ttigh Institute of Public Heahh. Alexandria University, Alexandria. REFERENCES APHA (1975). Standard methods ./br cxamimttion of water aml wastewater. AWWA, WPCF. (14th edn.) t!ckcnfclder, W. W.. Jr. (1970). ll'ater quality ettgim'erotg ./or practising engim'ers, Barnes & Noble, Inc., New York.

Treatment o]"edible oil and soap processing wastes

63

EPA (1971). The impact of oily materials on activated sludge systems, US Environmental Protection Agency, Water Pollution Control Research, Series 12050 DSH 03/71. Groenewold, J. C., Pico, R. F, & Watson, K. S. (1982). Comparison of BOD rclationships for typical edible and petroleum oils, Jour. Wa;er Pollution Control Federation, 54, 398-405. Gurnham, G, F. & Nedved, T. K. (1974). Treatability studies of three food processing plant wastewaters, Proe. 2Oth Purdue Industrial Waste Conference, 283--93. Liptak, B. G. (1974). Environmental Engineers ttandbook, Vol. 1, Chilton Book Co., Randor, Pennsylvania. Luthy, R. G., Selleck, R. E. & Galloway, T. R. (1978). Removal of emulsified oil with organic coagulants and dissolved air flotation, Jour. Wazer Pollution Control Federation, 50, 331-46. Ramirez, E. R. (1979). Comparative physicochemical study of industrial wastewater treatment by electrolytic, dispersed air and dissolved air flotation technologies, Proc. 34th Purdue Indus'trial Waste Conference, Ann Arbor Science Publishers, 699--709. Tokuz, R. Y. (1979). The response of activated sludge to high salinity, Proc. 3rd Turkish German Ent'ironmental l~,)zgineering Symposium, Vol. I, Bogazici University, Civil Engineering Department, Istanbul, Turkey. Young, J. C. (1979). Remo~,al of grease and oil by biological treatment processes, .lout'. Water Pollution C~mtrol Fk,deration, 51, 2071-87. Zajic, J. E. (1971). Water nollutJon d~.sposal and reuse, Vol. 2, Marccll Dekker, Inc., New York.