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CHAPTER 2

LITERATURE REVIEW

2.0 Introduction
This chapter discusses an overview about agricultural waste based catalyst as the main
topic. The subtopic contains of biodiesel, heterogeneous catalyst, and catalyst support.
All the reviewed topic related with previous studies which are relevant to this study.
2.1 Biodiesel
Biodiesel is a non-petroleum based diesel fuel which consists of the mono alkyl esters
of long chain fatty acids derived from renewable lipid sources. Biodiesel is typically
produced through the reaction of a vegetable oil or animal fat with methanol in the
presence of a catalyst to yield glycerin and biodiesel (chemically called methylesters).
(John, 2006)

Nowadays, the method of producing biodisel have been known quiet a while.
However, there has been interest significant in the production of biodisel. Biodiesel, a
methyl ester, is an alternative to diesel that is made from a triglyceride (like vegetable
oil) and either ethanol or methanol. The oil used in the process can come from many
sources including soybeans, corn, canola, and used frying oil. Because it comes from
renewable resource, it is referred to as a biofuel (John, 2006). The process involves
taking the oil, a triglyceride, combining it with an alcohol, to form biodiesel, which is
either an ethyl ester or a methyl ester.

2.1.2 Transestrification

from diglyceride monoglyceride is produced and in the last step. The stecheometric relation between alcohol and the oil is 3:1. which are reversible reactions. 2.1 Transesterification of Oil and methanol to produce FAME(Sharif. from triglycerides diglyceride is obtained. to produce esters and glycerin. heterogeneous catalysts have the advantage of easy separation and . triglycerides react with an alcohol. Being in a different phase. an excess of alcohol is usually more appropriate to improve the reaction towards the desired product. Homogeneous catalysts act in the same phase as the reaction mixture. a catalyst is added to the reaction The reaction is shown below: Figure 2. 2010) Marchetti et. To make it possible.In the transesterification of different types of oils. from monoglycerides glycerin is obtained. whereas heterogeneous catalysts act in a different phase from the reaction mixture. al (2007) mention that the overall process is normally a sequence of three consecutive steps. In all these reactions esters are produced. generally methanol or ethanol. However.2 Heterogeneous catalyst Catalysts mainly belong to the categories of homogeneous or heterogeneous. In the first step.

while . For a catalyst to be truly heterogeneous in nature. it should not leach into the reaction medium and should be reused. 2007). The mechanism of reaction for heterogeneous catalysts is similar to that of homogeneous catalysts. However.M. The major drawback of heterogeneous catalysts in general lies their preparation and reaction conditions which is energy intensive which will escalate their production cost and their leaching aspect. 2. In addition. The widely used alkaline catalysts NaOH and KOH are easily soluble in methanol. Heterogeneous catalysts (acid and base) have been classified as Brønsted or Lewis catalysts. Marchetti.1 Acid Catalyst This way of production is the second conventional way of making the biodiesel. The most commonly used is sulfuric acid (J. the catalyst should have high selectivity for the desired product formation and should give high yield and conversion to biodiesel. 2007) and some authors prefer sulfonic acid (J. forming sodium and potassium methoxide and augmenting the reaction to completion. The combustion characteristics of the fuel are independent of the catalyst used for transesterification. Marchetti. The idea is to use the triglycerides with alcohol and instead of a base to use an acid. Di Serio et al. the characteristics of the fuel depend on the feedstock used in synthesis of biodiesel.M. The solid catalysts can be categorized as solid base and solid acid catalyst.reuse. requiring almost always more than one day to finish. A catalyst may possess one or both of the sites and the relative importance of these two sites is not known so far. This type of catalyst gives very high yield in esters but the reaction is very slow. have discussed the mechanism of various heterogeneous catalysts. Freedman and Pryde (2001) get the desirable product with 1 mol% of sulfuric acid with a molar ratio of 30:1 at 65⁰C and they get 99% of conversion in 50 h.2.

The type of alcohol. a 1 mol% of sulfuric acid is a good amount for a final conversion of 99% in a time around 50 h. refine. The alcohol–oil molar ratio that should be used varies from N=1:1–6:1. A kinetics modeling for soybean oil has been made by Freedman (J. either sodium hydroxide (NaOH) or potassium hydroxide (KOH) should be used with methanol or ethanol as well as any kind of oils. 2007). The types of alcohol are usually methanol and ethanol.. 2007) 2.2. molar ratio 30:1.M.5 mol% (J.the butanolysis will need 117⁰C and the ethanolysis 78⁰C but the times should be 3 and 18 h. canola.g. In general. respectively. However N=6:1 is the most used ratio giving an important conversion for the alkali catalyst without using a great amount of alcohol.5 to 1 mol%. The typical value is 1%. In this process it is better to produce the Alcoxy before the reaction to obtain a better global efficiency. Marchetti. usually. . is the same as the one that can be used in alkali catalyst reaction. but recovering glycerol becomes more difficult and that is why optimal relation between alcohol and raw material has should be determined experimentally considering each process as a new problem. but some authors have used 3. As in the alkali reaction. Marchetti. The possible operation condition is. The acid transesterification is a great way to make biodiesel if the sample has relatively high free fatty acid content. crude or frying. The temperature range varies from 55 to 80⁰C. corn. peanut. if an excess of alcohol is used in the experiment then better conversion of triglycerides is obtained. as well as the oils. The last one has fewer safety problems because it is less toxic. The oils used could come from any vegetable.M. e.2 Alkali Catalyst For a basic catalyst. The amount of catalyst supposed to be added to the reactor varies from 0.

In multiphase catalysts.2005). the surface science of catalysis. improved selectivities. The standard value for the reaction to take place is 60⁰C. to which a catalyst is affixed (Johnny J. The support may be catalytically inert but it may contribute to the overall catalytic activity. The amount of catalyst that should be added to the reactor varies from 0. The support may be inert or participate in the catalytic reactions. palm kernel. alumina. Most catalytic processes are heterogeneous in nature. and silica (Zaera. 2006). in particular those associated with the designing and characterization of novel catalytic materials. In this study case. several promising new research directions related to the future development of heterogeneous metal catalysis are highlighted.2002). and green chemistry (Zhen Ma. The reactivity of heterogeneous catalysts and nanomaterial-based catalysts occurs at the surface atoms. the active catalytic material is often present as the minor component dispersed upon a support sometimes called a carrier. usually a solid with a high surface area. high throughput catalyst testing. olive.3 Catalyst Support Catalyst support is the material.5% to 1% w/w (Barnwal and Sharma. but depending on the type of catalyst different temperatures will give different degrees of conversion. making it a preferred catalyst to be used in industries. soybean. Typical supports include various kinds of carbon.1 Palm kernel shell . 2006). Finally.35% w/w (Hanna. the heterogeneous catalyst as a NaOH supported on agricultural waste that has been chosen to be studied and the effectiveness of the catalyst will be tested in transesterification. and often rely on the use of transition metal particles dispersed on high surface area supports. The last but not least important variable is the reaction temperature. 2. 1999) should be used. The reason there is a great interest in the alkali process is it is more efficient and less corrosive than the acid process. Consequently great effort is made to maximize the surface area of a catalyst by distributing it over the support.sunflower. 2. palm. and for that reason the temperature range should be from 25 to 120⁰C (Barnwal and Sharma.005% and 0.2005) and more preferred advice are any values between 0.3.

2010). One of the most favorable used of palm kernel shell is to process become charcoal. due to its high grade solid. Furthermore. 2009).2 Activated Carbon Activated Carbon (AC) also called activated charcoal. Oil palm tree native of west africa also known as Elaeis guineensis and nowadays widely spread throughout the tropic. 2009). Mazzoni (2013) the carbon-based material is changed over to activated carbon by thermal decomposition deterioration in a furnace utilizing a controlled atmosphere and heat. 2006). mesocarp fibre and oil palm nut will be separated. after the cyclone separation process. the burned palm kernel shell charcoal has other economy value too. Activated carbon has been clarified in different method of definition from authors this will provide basis understanding of activated carbon as solid carbon material (Ain. palm kernel shell can be considered as pellet form because of it nature form.3. Palm kernel shell charcoal has also been used as activated carbon for water purification. Based on T. low-volume pores that increase the surface area available for adsorption or chemical reactions. At crude palm oil process. low ash and low sulphur content.2007). 2. palm kernel shell has been used as a burner for power plant. The oil palm nut will be drying to remove moisture at nut drying process and then cracking at nut cracking process. Kernel will be separated for kernel oil process and the nut shell will place in the waste section (Hoong.Palm kernel shell are a hard endocarp of palm kernel fruit that surround palm kernel seed of oil palm tree (abiola. is a form of carbon processed to be riddled with small. activated coal. In palm oil industry. or carbo activatus. The resultant product has an amazingly . The palm kernel shell are obtain after threshing or crushing the palm kernel into crushed pieces (Yusuf. Otherwise. and also and active agent for soil improvement (Hoong. the crash shell without nut is referring to palm kernel shell. promote organic farming. Deithorn and F.

because their relatively high density.3. particularly the final activation temperature. potential extent of activation. Recently.have large surface area per unit volume.3. 2010). and a system of submicroscopic pores where adsorption happens. but relatively high volatile content is also needed for the control of the manufacturing process. several factors are taken into consideration. hardness and volatile content are ideal for production of hard granular activated carbon (Guo and Lua. The dividers of the pores give the surface layer particles crucial for adsorption.3. 2001) 2. the researches have been working out on optimizing the final activation . affects the characteristic of the activated carbon produced. Low content in organic materials is important to produce activated carbon with low ash content. inexpensive material.1 Raw material Most organic materials rich in carbon that do not fuse upon carbonization can be used as raw material for the manufacture of activated carbon. the stability of supply in the countries. 2007) . There are a severel factor that affect AC production which is high carbon content. Generally.3 Factors Affecting Activated Carbon Production 2. and low degradation upon storage. low in inorganic content.3. Raw materials such as palm kernel shell are very popular for many types of activated carbon. for commercial activated carbon usually conducted at temperature above 800⁰C in a mixture of steam and CO 2 (Ain. The selection of raw material for preparation of porous carbon.3. 2. AC can be prepared from a large number of raw materials. high density and sufficient volatile content. especially agro-industrial by-products like palm kernel shells by one of the following process which is physical reactivation and chemical activation (Zafirah.2 Temperature Temperature.

As the time increased. 2010). . Activation temperature significantly affects the production yield of activated carbon and also the surface area of activated carbon (Zafirah 2010).3 Activation time Besides activation temperature. Previously.3. 2001) 2. It is also unsuitable to prepare activated carbon when carbonization temperature was more than 800°C since the successive decreased in volatile matter is minimal above this range (Guo and Lua. From previous study. the activation times normally used were from 1 hour to 3 hour for palm shell (Ibrahim T. The decreasing trend in yield is paralleled by the increasing activation temperature due to the activation reaction. the percentage of yield decreased gradually and the surface area also increased.temperature to economize the cost of production and time. According to Guo and Lua (2001). it is suggested that the percentage of volatile matter decreased with an increased of carbonization temperature and the variation of this parameter was maximum between 200°C and 800°C due to rapid carbonization occurring in this region. These phenomena are also manifested in the decreasing volatile content and increasing fixed carbon for increasing activation temperature. The increasing of activation temperature reduces the yield of the activated carbon continuously (Zafirah. this is expected since an increasing amount of volatiles is released at increasing temperature from 500°C to 900°C. 2010). the activation time also affects the carbonization process and properties of activated carbon. The optimum temperatures have been reported to be between 400°C to 500°C by most the earlier researchers irrespective of the time of activation and impregnation ratio for different raw material.3.