1.

2 Background of the Study

Spent bleaching earth (SBE), a solid waste material, is generated as part of the refining

process in the industry of vegetable oil. Approximately 112 million pounds of bleaching earth

(clay) are used per year in the United States alone for the processing of edible vegetable oil. A

typical refining process for vegetable oil includes pretreatment of the crude vegetable oil with

acid and/or caustic soda, bleaching and deodorization.

1.2.1 Raw Materials for Soybean Oil Processing

In the manufacturing process, the raw material for making soybean oil, soybean (or

soya bean), is a low oil content crop, generally 11-20%. It is planted in many countries and

areas like Argentina, Korea, Zambia, Mauritius, Ghana, Tanzania, Canada, China, etc. The

extraction of Soybean oil from soybean flakes requires large amounts of hexane solvent and

results in significant losses and energy consumption during the distillative removal of the

solvent. The crude soybean oil still contains many oil-insoluble and oil-soluble impurities that

needs to be removed. The oil-insoluble material are removed with filtration and the soluble

materials is removed with different processes including degumming (removing of

phosphatides), alkali refining (washing with alkaline solution to remove free fatty acids,

colorants, insoluble matter and gums) and bleaching with bleaching earth to remove color and

other impurities.

1.2.2 Soybean Oil Manufacturing and Products

Soy protein products are mainly used as ingredients in formulated foods and seldom

are seen by the public. They consist of four broad categories. (1) Most soy proteins are derived

from “white flakes,” made by dehulling, flaking and defatting soybeans by hexane extraction.

These may then be milled into defatted flours or grits containing ∼50–54% protein; extracted
with ethanol or acidic waters to remove flavor compounds and flatulence sugars, producing

soy protein concentrates containing 65–70% protein; or processed into soy protein isolates

containing 90+% protein by alkali extraction of the protein, removal of fiber by centrifugation

and reprecipitation and drying of the protein. (2) Full-fat products are made in enzyme-active

and in toasted forms. (3) Various dried soyfoods, including soy milk and tofu, are produced.

(4) Mixtures of soy proteins with cereals, dried milk or egg fractions, gelatin, stabilizers and

emulsifiers are offered for specific baking, whipping, breading and batter applications.

Texturized products, resembling meat chunks or bacon chips, are made by extrusion of flours

and concentrates or spinning of isolates. Soy protein ingredients are used in compounded foods

for their functional properties, including water and fat absorption, emulsification, aeration

(whipping) and heat setting and for increasing total protein content and improving the essential

amino acids profile.

1.2.3 The need for Recovery of Spent Bleaching Earth

In fat and oil industry, bleaching process is very significant. This process can improve

the shelf-life of the oils. It also ensures that the product will meet the requirement which is

necessary. Bleaching earths are composed of up to different types of clay minerals such as

sepiolite, bentonite, and attapulgite. These three minerals act as absorbers which is dependent

on its surface area, particle size distribution and porosity. For more than a hundred years,

bleaching earth has been widely used for the removal of color pigment and impurities such as

phosphatides, trace metals, carotenoids and free fatty acids and oxidized products from the oil

(Kheoh, 1987).

Spent bleaching earth is an excess solid waste coming from the oil industry which

comprises almost 2 million tons per year. It typically contains entrained oil of around 30 to

50% by weight. The Spent Bleaching Earth are difficult to manage and dispose of because it
contains water soluble substances and have a very diverse composition. Due to the high oil

content of the spent bleaching earth, it is very susceptible to combustion. Since it is prone in

catching fires, the disposal of Spent Bleaching Earth can cause environmental hazards.

Waste disposal, particularly through landfilling, is still a disagreeable and is not

advisable especially in this kind of solid waste (European Council 1999). The excess solid

waste cannot be dispose through storage because of ecological reason that these Spent

Bleaching Earth may penetrate into ground water(Murray 1989). The handling of SBE is also

an operating expense because of the lost value of oil. The need to lessen the environmental

impact is of great importance and concern of any oil industries.

The availability of large volume of waste itself is of great advantage. Instead of

disposing this SBE, further extraction of the residual oil from SBE can be done. It can also be

processed and reused to make a new product which can be very useful in our society today.

1.2.4 Technologies and Processes for oil recovered from SBE

1.2.4.a Recovery of oil and free fatty acids from spent bleaching earth using sub-critical

water technology supported with kinetic and thermodynamic study

The bleaching earth used in this work was supplied by EL MANAR plant, El-

Nobareyya city, El-Beheyra governorate (province), Egypt. Distilled water prepared in the

Chemical Engineering department, Minia University, was used as an extracting solvent in

subcritical water extraction. Ethanol was used (as solvent) for titration to determine free fatty

acids, methanol was used as solvent for Thin Layer Chromatography (TLC) analysis to

determine mono-, di-, and triglycerides, chloroform was used as solvent for TLC analysis to

prove the existance of the mono-, di-, and triglycerides; and NaOH was used as a catalyst and

in titration of the free fatty acid. The TLC paper was the product of TLC, Kieselgel 60 f254

precoated plates, E. Merck, Darmstadt, Germany.

Methodology/Process of Oil Recovery

I. Measuring of Oil Content in the Bleaching Earth

Before starting the experiments, the amount of oil contained in the SBE was measured.

SBE as delivered from EL MANAR plant was extracted by petroleum ether. Five grams of

SBE were contained in a 500-ml container with a sealed cape and 200 ml of petroleum ether

were added to the SBE. The container was then tightly closed and mixed using a magnetic

stirrer over a hotplate adjusted at 45˚C. The SBE was separated from the extraction mixture by

filtration. Then, the extracted oil was recovered by evaporating the solvent.

II. Subcritical Water Extraction (SCE)

The SCE was carried out in a laboratory-built apparatus. It was carried out in stainless

steel pipes SUS 316, i.d. 1.68 cm × 15 cm (with a reactor volume of 34 cm3) with Swadgelock

caps. The bleaching earth was charged into the reactor tube, then the distilled water was added

as an extraction solvent. The reactor was sealed and immersed in a heating bath (Thomas

Kagaku Co. Ltd.). It is important to note here as a safety comment that the sealed tube should

not be overfilled to prevent hydraulic pressure of the expanding liquid from fracturing the tube

vessel. The extraction was carried out in the range of 180˚C - 280˚C, and the pressure inside

the reactor was estimated from the steam table for the subcritical conditions (saturated steam).

After the desired reaction time, the reactor was immediately cooled down by immersing it into

a coldwater bath. The extraction product was separated into three phases: the oil phase, the

aqueous phase (including oil and water), and the solid phase. The three phases were separated

through simple centrifugation and vacuum filtration processes. To recover any traces of oil

from the aqueous phase, we added petroleum ether to extract any oil that could be emulsified

into the water phase. Then, the petroleum ether was evaporated by heating it in a furnace at

80˚C. The extracted oil was then weighed and the data was recorded.
 III. Esterification of Fatty Acid with Glycerol

Esterification reactions were carried out according to the methods and optimum

conditions described elsewhere (Ashraf, 2013) in a laboratory-built apparatus. A laboratory

conical flask of 250 ml with 30 ml working volume was used for the reaction. The temperature

of the reactor was controlled using a hot plate controlled with an internal thermostat. All the

reactants (fatty acid, glycerol and catalyst) were weighed in the desired amount and charged

into the reactor. The temperature was then increased through adjusting the thermostat. The

magnetic stirrer was allowed to operate after 2 - 3 minutes (to allow for heating up of the

mixture). After the desired reaction time elapsed, the heater was closed. The reactor was then

cooled by immersing it into a water bath. When the reaction mixture reached ambient

temperature, samples were taken for analysis.

IV. Thin-layer chromatography for the produced glycosides

Thin layer chromatography (TLC) was used to identify the types of glycerides produced

during the esterification reaction (i.e mono-, dior triglycerides). TLC experiments were carried

out by dissolving one drop of the esterification products into a 0.5-ml mixture of chloroform

and methanol (9:1). A drop from the final mixture was then applied over the TLC paper

immersed into a 100-ml beaker containing 10 ml of a mixture of chloroform and methanol (9:1)

which allows a contact between the edges of the TLC paper with the solvent mixture. The TLC

paper was allowed to stand until the solvent reached a level which must be just below the end

line. The TLC paper was then dried and the bands of the different glycerides produced were

detected under the UV lamp.

Subcritical water has been used as a new pathway for oil extraction from spent

bleaching earth. The esterification of waste oil will provide two major benefits: firstly, it will

make the production of biodiesel more competitive with the existing diesel fuel market, and
secondly, it will produce monoglycerides and diglycerides, the most important emulsifiers used

in food industry.

1.2.4.b Recovery of Oil from Spent Bleaching Earth: State-of-the-Art and Prospect for

Process Intensification

Soya oils undergo numerous refining steps in order to remove undesirable compounds

and produce high quality, stable commercial products. Recovery of oil from spent bleaching

earth is an area where ample opportunities exist for cleaner production and cost saving in the

oil processing industry.

METHODOLOGY/PROCESS

Soxhlet Extraction

Recovery of oil adsorbed in the spent bleaching earth (SBE) can be extracted by

soxhlet extractor using hexane as the solvent (Huang and Chang, 2010).The process of

extraction begins with a sample placed on a thimble holder filled with hexane from a

distillation flask until the solvent extend to over flow level, a siphon releases the solute from

the thimble holder moving the aliquot back into the distillation flask which then carries the

extracted oil into the bulk liquid. Extraction process continue until all the oil had been extracted

and the solvent is recycle through the sample in a continuous mode (Mohammad Azmin et al.,

2016). The extracts obtained from the process were being filtered and the solvent was removed

under reduced pressure and at defined temperature in a rotary evaporator.

Subcritical Water Technology

The use of water instead of organic solvent is an alternative recovery method of palm

oil from spent bleaching earth called Subcritical Water Technology(SWT) (Abdelmoez et al.,

2015). The extraction of vegetable oil from spent bleaching earth using subcritical water
technology method was performed in the laboratory whereby water was used as a solvent in a

reactor tube (Fattah et al., 2014). The reactor must be sealed and should not be filled up to

avert the hydraulics pressure of the liquid from fracturing the vessel. The operating

temperature of the extraction was between 180 to 280 °C and the pressure was obtained

from the steam table for the saturated steam. Water was cooled down after the required

reaction time and finally immersed in a cold-water bath. The extracted product obtained was

separated into the aqueous stage, solid and the oil phase. Simple centrifugation and

vacuum-filtration processes was used to separate the three different phases and then petroleum

ether was used to recover any oil traces from the aqueous phase. The recovered oil was weighed

after the petroleum ether was evaporated in a furnace at 80 °C.

Figure 1.2.4.b: Conventional method for recovery of oil from SBE (Cheryan, 2005)

Supercritical Fluid Extraction (SFE)

Supercritical fluid extraction (SFE) is one of the extraction methods used in the

recovery of oil from spent bleaching earth. Extraction of spent bleaching earth via supercritical

fluid technology is a clean and environmental friendly technology, utilising non-hazardous

carbon dioxide (SC-CO2) as solvent for extraction of oil (Herrero et al., 2010). Overall good

quality of oil can be recovered by this method (Kheang et al., 2006). Katiyar and Khanam

(2014) reveal that higher yields and better quality of oil can be achieved with supercritical fluid

extraction. Supercritical fluids (SCF) have been used in different fields such as the food,
pharmaceutical, chemical, and fuel industries due to the advantages of supercritical fluids, such

as the absence of toxic residue in the final product (Pereira and Meireles, 2009). In super critical

extraction process, the mobile phase is subjected to temperature and pressure near or above

critical point at the supercritical process for the purpose of improving the mobile phase

solvating power (Sovilj, 2010). Exclusion of organic solvent reduce the problem of their

storage in the lipidologist laboratory serves as major advantages of using supercritical

fluidextraction (Sairam et al., 2012). The critical temperature and pressure of carbon dioxide

at supercritical state are 31.1 °C and 73.8 bar. At this state, they have high diffusion coefficients

and low viscosities, and, possess 135 high solvating power properties with characteristics of

liquids. These account for supercritical CO2 as a good fluid solvent (Mohammad Azmin et al.,

2016). The penetration of carbon dioxide into the solid material was facilitated by the increased

diffusivity of solvent and decreased viscosities which lead to an increased mass transfer and

reduced extraction times in SFE (Mohammad Azmin et al., 2016). Another factor that

determine the effectiveness of the supercritical fluid extraction is the solvating power that

changes with temperature and pressure. The recovery of oil from SBE using supercritical fluid

extraction method can be achieved only by optimising the experimental conditions. The

extraction of oil from spent bleaching earth was conducted at 82.7 MPa and 80 °C in which the

solubility in SC-CO2 is maximised. Table 1 shows the SFE experiment on the recovery of

vegetable oil from spent bleaching clay. Such conditions have been shown to yield vegetable

oil at a slightly lower cost than oil obtained from the conventional liquid-extraction process

(King et al., 1992). Due to channelling of extraction fluid through the sorbent bed as well as

compaction of the clay bed under high pressure, the particle size of bleaching clays can also

inhibit complete extraction of the oil from the SBE.

This paper reviews the state-of-the art technologies for recovery of oil from spent

bleaching earth. It presents the development of the technologies chronologically and compares
their relative merits from aspects of capital requirements, resource utilisation, cleaner

production, sustainability and economy. The paper ends with a look at supercritical fluid

extraction (SFE) as a potentially promising alternative recovery technology that could offer

opportunities for process intensification; resulting in a simpler, cleaner and resource-efficient

system for oil recovery from bleaching earth.

1.2.4 Applications of Recovered Oil from SBE

The extracted oil recovered from Spent Bleaching Earth can be used as feedstock to a

refinery (Loh et al., 2006). Otherwise, it can be reused as a raw material for industrial

applications to save costs in the processing industry (Huang and Chang,2010). As the residual

oil has a very high FFA and Peroxide Value, it can only be used for non-food applications, as

feed stock for conversion to biodiesel, and as a lubricant base for bio-lubricants as a feedstock

to the oleo-chemical industry and animal feeds (Huang and Chang, 2010; Loh et al., 2007;

Chanrai and Burde, 2004; Damodaran, 2008). In addition, SBE utilization include regenerating

SBE as adsorbents (Cheah and Siew, 2004), fermenting oil-containing SBE to produce

riboflavin for use in medicine, food and fodder industries and recovering riboflavin-free SBE-

based (Park et al., 2004).

1.2.5 Applications for De-oiled SBE

The output de-oiled Spent Bleaching Earth is safe for disposal in land fill (Ng et al.,

2006). It can also be used as a fuel in the boilers. The anhydrous clay can be used in Cement

manufacturing, non-fired wall tiles and as briquette material (Sophonpong et al.,2007;

Wangrakdiskul et al., 2008; Chong Ann, 2010). It can also be used in manufacturing fertilizers

containing silica/silicates or can be used as a soil amendment, as it poses no harm to the soil

and acts as a soil conditioner (Wang et al., 2010).