Type of Manuscript : Review Paper

Title of Article : “Production Of Biofuel & Glycerin By Using Dairy Waste”

Name of Authors : Dr. P.V. Thorata*, Miss Priyanka Thombrea, Miss. Sandhya Warulkara ,Miss.Harshal Sathonea

Name of Department to which work should be attributed:

a Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road, Babhulgoan(JH),Akola-444104 ,Maharashtra State INDIA

Detail about the author and address:

Dr. P.V.Thorat : (HOD & Professor) Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road,Babhulgoan(JH),Akola-444104 Maharashtra State INDIA

Miss. Priyanka Thombre : (Assistant Professor) Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road, Babhulgoan(JH),Akola-444104 Maharashtra State INDIA

Miss. Sandhya Warulkar : (Assistant Professor) Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road, Babhulgoan(JH),Akola-444104 Maharashtra State INDIA

Miss. Harshal Sathone : (Assistant Professor) Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road, Babhulgoan(JH),Akola-444104 Maharashtra State INDIA

Author for Correspondence: +91-9960590202

Email : pvthorat@yahoo.com

Production of Biofuel & Glycerin by Using Dairy Waste

Dr. P.V. Thorata*, Miss.Priyanka Thombrea ,Miss. Sandhya Warulkara ,Miss.Harshal Sathonea ,a*Head of Department , a Assistant Professor

a Department of Polymer Technology, College of engineering and technology Akola, NH6, Murtizapur Road, Babhulgoan(JH),Akola-444104 ,Maharashtra State INDIA

Abstract: There are many Industries in India, The one is milk industry. The rate of milk production in India is about 150 million tonnes per year & accepted to increase in future, as per demand. A large dairy has processes 5 lakh litre of milk per day & produce approximately 200-350 kgs. Effluent scum per day. There solid waste is difficult to dispose. The present work investigates the feasibility of utilization of this dairy waste scum from milk industries for the production of Glycerine & biodiesel. The Transesterification reaction was carried out in presence of base catalyst (KOH) potassium hydroxide. The effects of methanol to oil ratio, temperature, reaction time, speed of agitation in rpm & amount of KOH were investigated. The fuel properties viz., specific gravity, viscosity, flash point, pour point, cloud point were studied. It was found that the properties were quite comparable and some even well than the properties of petroleum diesel. The analysis of some important fuel properties indicate that the biodiesel produced has the properties that meet the standard of biodiesel & diesel fuel. This work reduced the cost of production of biodiesel as it obtained from non-edible oil as well the problem of related to disposal of dairy waste.

KEYWORDS: dairy waste scum, biodiesel, glycerine, transesterification, non-edible oil.

INTRODUCTION

Biodiesel is a best option for an alternative fuel for conventional petroleum based diesel because it can produced by the use of simplest transesterification reaction of the organic feedstock such as vegetable oils or animal fats. The benefits of biodiesel over to petroleum diesel is its low production cost, include reduction of most exhaust gas emission, high flash point, high cetene nos. and superior lubricity. It is nontoxic and essentially free of sulphur, aromatic compounds, metals & crude oil residues.

Biodiesel is defined as a fuel comprised of monoalkyl ester of long chain fatty acids derived from vegetable oils or animals fats. The current feed stock for production of biodiesel or monoalkyl ester is vegetable oil, animal fats and micro algal oil. Out of more than 350 identified oil bearing crops only sunflower, safflower, soyabean, cotton seed, rapeseed and peanut oil are considered as potential feedstock. But due to diversion of this edible oil towards the feedstock for biodiesel production the world food crisis will occurs. This leads to search for excavation of biodiesel feedstock from unconventional non-edible oil & fats like, waste scum oil, waste grease, waste cooking oil, waste tallow, jetropha seed oil, tobacco seed oil, rubber seed oil, etc. While using edible oil as a feed stock the cost of raw materials accounts 75-85% of production cost of biodiesel. The higher prices of biodiesel made researchers to concentrate for newer way to reduced cost of biodiesel. The present analysis revels that, the using of dairy waste scum oil as a feed stock for biodiesel production is a suitable alternative for petroleum diesel.

Milk is the natural & complete food for all human as well as mammalian animals. It contains complete nutrients such as fats, proteins, vitamins & carbohydrate, especially fats was found in milk about 3-4%. There are number of milk industries producing drinking milk & milk associated products such as Cheese, Yogurt, Milk Powder, Ice-Cream, Ghee, Peda, Panner & Other Products. During these operation dairy has handling number of equipments for processing, handling, storing, packing & transportation of milk & its products. Large quantity of water are required

for housekeeping, sterilizing and washing equipments, during these processes residual butter & related fats that which are washed and get collected in effluent treatment plant as a dairy waste or scum. Scum is a less dense floating solid, white in texture & usually formed by the mixture of fats, lipids, proteins and some packing materials etc.

A large dairy which process 5 lakh litre of milk per day, will produce approximately 200-350 kgs of effluent scum per day, which also create disposal problem. Most of the dairies disposing this scum by incinerating. By doing so it economically waste fuel & generates pollutants. There are four different methods are used for production of biodiesel & Glycerin; these are blending, micro emulsification, Pyrolysis, and transesterification. Transesterification is the most commonly used & well established method, it also improve fuel property of oil due to this the method has choice for current study.NEED OF BIODIESEL PRODUCTION

The scarcity of conventional fossil fuels, growing emission of combustion-generated pollutants, it can create problem of global warming, and also increasing demand, cost of fossil fuels also increases, will make biomass sources more attractive .Petroleum –based fuels are limited reserve concentrated in certain regions of the world. The sources are on the verge of reaching their peak production. The fossil fuel resources are shortening day by day. This scarcity will make to search an alternative for it.TECHNICAL PROPERTIES OF

BIODIESEL

Common Name Biodiesel(bio-diesel)Common Chemical name

Fatty acid

Chemical Formula C15-C14 Methyl ester or C15 –C25H28-48O2

Kinematic Viscosity range(mm2/s,at 313 K)

3.3-5.2 (860-894)

Density range (kg/m3 , at 288K)

>475

Boiling point range(K) 420-450Distillation range(K) 470-600Vapour pressure (mm Hg, at 295K)

<5

Solubility in water Insoluble in waterPhysical appearance Light to dark yellow,

clear liquid

Odour Light musty /soapy odour

Biodegradability Reactivity

More biodegradable than petroleum diesel Stable, but avoid strong oxidizing agent

DIFFERENT PRODUCTION METHODS OF BIODIESEL Following methods have been considered to reduce the viscosity of vegetable oils such as dilution, micro emulsification, Pyrolysis catalytic cracking and transesterification.

Dilution of vegetable oils In dilution method solvent have used to reduce viscosity of vegetable oils. Some engine has performance problem such as injector coking and more carbon deposits. The viscosity of oil can reduce by blending with solvents. Twenty-five parts of sunflower and 75 parts of diesel were blended as diesel fuel. The viscosity was 4.88 cst at 313 K, while the maximum specified ASTM value is 4.0 cst at 313K. This mixture was not suitable for long term used in a direct injection engine. Another study was conducted by using the dilution technique on same freezing oil. The addition of 4% methanol. Diesel fuel increase the brake thermal efficiency, brake torque, and brake power, while decreasing the brake specific fuel consumption.

Micro emulsion of oilsShort chain alcohol such as methanol or ethanol was used for micro emulsion. To reduce the high viscosity of vegetable oil, micro emulsion with immiscible liquid such as methanol and ethanol and ionic and non ionic amphiphiles have been studied .The 2-octanol was found in effective amphiphiles in micelle solubilisation of methanol in triolein and soybean oil.Pyrolysis and catalytic crackingPyrolysis is the conversion of one substance into another by means of heat or by heat with the aid of catalyst. Pyrolysis and catalytic cracking of oil and fats result in production of alkanes, alkenes, alkadienes, cycloalkanes, carboxylic acids, aromatic and small amounts of gaseous products. It involves heating in

absence of air or oxygen and clevenge of chemical bonds to yield small molecules. The pyrolysed material can be vegetable oils, animal fats, and natural fatty acid and methyl esters of fatty acids.

Transesterification of oils and fatsIs a chemical reaction between triglycerides and alcohol in the presence of catalyst. It consist of a sequence of three consecutive reversible reactions where triglycerides are converted to diglycerides and then diglycerides are converted to Monoglycerides followed by conversion of Monoglycerides to glycerol. In each step ester is produced and thus three ester molecules are produced from one molecule of triglycerides. The transesterification reaction required a catalyst such as potassium hydroxide or sodium hydroxide to split the oil molecules and alcohol to combine with separate esters.

CH O - C - R2

CH O - C - R2

CH O2 - C - R

O

O

O

Glycride

+ CH OH3

CH

Alcohol

Catalyst

Ester Glycerol

3 CH O - C - R3

O

+ CH - OH

CH OH2

CH OH2

Among all these alternatives, transesterification seems to the best choice as the physical characteristics of fatty acid biodiesel are very close to those of diesel fuel and the process is relatively simple

BIODIESEL FROM TRIGLYCERIDES VIA TRANESTERIFICATION

The aim of this work was to study the application of those dairy wastes to be a raw material for production of biodiesel & Glycerin. The dairy waste had some residual fats with it; those fats will convert into the oil when it should heat. The extraction of oil from dairy waste was carried out by batch as well as continuous process. The transesterification reaction between glycerides & alcohol as shown in equation.

CH O - C - R2

CH O - C - R2

CH O2 - C - R

O

O

O

Glycride

+ CH OH3

CH

Alcohol

Catalyst

Ester Glycerol

3 CH O - C - R3

O

+ CH - OH

CH OH2

CH OH2

The transesterification reaction gives two products such as ester compounds which were known as biodiesel & glycerin. These are May reports on production of biodiesel & glycerin from different type of oil, but there was no report on production biodiesel & glycerin by using dairy waste scum oil. Transesterification reaction is widely used for reducing viscosity of Triglycerides which was derived from renewable sources such as vegetable oil or animal’s fats. The Catalyst is used to increase the reaction rate & as well as % yield of products. Excess alcohol must be used as per required by stiochometry to possible to complete the reversible reaction. Compared to other alcohol methanol is used because of its low cost & physical & chemical advantages. Alkali catalyst such as potassium hydroxide (KOH) is used due to easily dissolved in methanol. The rate of transesterification reaction occurs 4000 times faster in presence of alkali catalyst as compared to acid catalyst. For alkali catalyst transesterification reaction required must be anhydrous small droplet of water make reaction divert towards saponification reaction.

The transesterification reaction proceeds with or without catalyst .Among the alcohol that can be used in the transesterification reaction are methanol, ethanol, propanol, butanol and amyl alcohol. Methanol & ethanol are used frequently. Ethanol is a preferred alcohol in the transesterification reaction compared to methanol because it is derived from agriculture waste & it is renewable and biologically less objectionable in the environment. However methanol is preferred due to its low cost and also its physical and chemical advantages.

Fatty acid (RCOOH) + alcohol (ROH) ↔ ester (RCOOR) + water (H2O) (1)

Triglycerides + ROH ↔ diglycerides + RCOOR1 (2)

Diglycerides + ROH ↔ Monoglycerides + RCOOR2 (3)

Monoglycerides + ROH ↔ glycerol + RCOOR3 (4)Transesterification reaction consists of a number of consecutive, reversible reactions. The triglycerides are converted stepwise in diglycerides, Monoglycerides and finally, glycerol.Process Flow Schematic for Biodiesel Production

EXPERIMENTAL SETUP & PROCEDURE:This work has adopted following methods & procedure it was carried out into different steps, these are as follows.Step 1: Preparation of oil from dairy waste product:-

Dairy waste sample were collected from the sludge of waste water treatment plant. The sample was put from the plant & collected in PVC bottle.Extraction method of oil from dairy waste: Batch Extraction:-The sludge dairy waste 50 gm was put into 250 ml beaker, 25 ml of Hexane was added to the sludge. The sludge was heated at 40° C on hot plate for 10 minute. The extracted oil moved on the top layer of the sludge & removed out of the oil. The process was repeated further twice. The extracted oils were collected & weighed with record.Continuous Extraction:-The new sludge 50.00 gm was placed into thimble for soxhlet

apparatus set. The 25 ml of hexane was placed into a round bottom flask with equipped with heating mentle.The sludge dairy waste was continuous extracted at 40° C for 4 hrs. The extracted oil were collected & weighted with record.

Step 2: Preparation of biodiesel & glycerin by transesterification reaction:Analysis of residue free fatty acid (FFA) content in external dairy waste. The extracted oil 5040 gm was mixed with 20 ml phenolphthalein indicator & neutralized with 50 ml of neutral ethanol before titration with OH of NaOH solution. The volumes of sodium hydroxide were recorded & calculate the acid contents extracted oil by equation:

Where, V = Volume of sodium Hydroxide solution in titration (ml)N = concentration of sodium Hydroxide solution in normally.W = weight of oil sample (gm)

Transesterification Reaction:-The extracted oil 50.00 gm was mixed with 1 gm of KOH at 150 ml of methanol. The mixed solution was heated 60° C with stirring at 115 rpm to 1 hr. & left cool at room temperature for 30 minute. The layer of biodiesel & glycerin clearly separated into 2 layers. Those layers were removal out & weight to obtain the % yield of crude product.

Step 3: Purification of crude biodiesel & glycerinA 1. The purification of crude biodiesel:-The 100 ml of crude biodiesel from Step 2 was treated by this method. If washing with the warmed distilled water, until the color of biodiesel was brighter.

2. Evaporation & Removal of Reside methanol:-After washing the biodiesel was heated on water batch at 100° C for 15 minutes. The purified biodiesel was analyzed by using FTIR spectrophotometer & H-Nuclear Magnetic Resonance spectrophotometer for record the biodiesel spectrum & compare with the standard spectrum of methyl oleate,

methyl palmiate, and methyl stearate & methyl linoleate.B .Purification of crude glycerides:-The 100 gm of crude glycerin was heated on a hot plate at 100° C for 60 minute. The glycerin was weighted and analyzed glycerin contents by titration method.The 50 ml of distilled water was added to glycerin dropped 0.2 N Of bromothylmolblue for 7 drops. The glycerin solution was acidified with 0.2 N sulphuric acids then basified gain by 0.05 M of NaOH to control PH to 8.1 0.1. The 50 ml of sodium periodate was added to glycerin solution, warmed at 60° C for 30 minute. Then the glycerin sample was mixed with 10 ml of ethanediol & left at a room temperature for 20 minute & dilute again with 300 ml of distilled water. Then titrate with 0.1250 N of standard NaOH solution till the PH of solution charge to 6.5 0.1 the volume of standard NaOH solution was recorded. Calculate the % glycerin:

Where, = Volume of Std. NaOH solution used in

titration with Glycerin sample (ml) = Volume of Std. NaOH solution used in

titration with Blank solution (ml)M = Concentration factor of Std. NaOHW = Weight of glycerin sample (gm).

Neutralization Step:The purified glycerin was mixed with 25 ml of distilled water & neutralized with sulphuric acid. The PH of glycerin was controlled at 7

0.01. The glycerin was extracted with 25 ml of Hexane. The residue hexane & water evaporated out of glycerin large.

Decolorization and Deodorization Step:The activated carbon was added to

glycerin after neutralization in the proportion of activated carbon to glycerin was 1:1 by weight. The mixed component was left at room temperature for 24 hrs & activated carbon was filtered by vacuum filtration. The water was again evaporated out of glycerin. The pure glycerin was weighted & analysis glycerin content by titration method. In above

each step, the glycerin was checked the purity by FTIR & compared with standard glycerin.

Step 4: Quality check of biodiesel & Glycerine1. Purity check of biodiesel:-The content of biodiesel was analyzed by using GC to know the content of methyl oleate, methyl palmiate, methyl stearate, methyl linoleate in biodiesel which was prepared by waste product.2. Analysis of Impurity in glycerine :-The glycerine was analyzed for the residual free fatty acid by GC-MS & compared with standard pure glycerine.

Variable Affecting Reaction Amount of Catalyst

The amount of catalyst used affects the conversion efficiency of catalyst. In this process alkali KOH catalyst was used and its amount is varied in the range of 0.4-104 wt% for six different values (0.4, 0.6, 0.8, 1.0, 1.2 & 1.4 wt% of KOH). The effect of the catalyst amount on the yield is shown in graph 1. From the graph 1 it shows that, the excess addition of KOH increase the yield. The optimum was activated using 1.2 wt% of KOH, which produced 88.00% of yield of transport ester; KOH amounts greater than 1.2 wt% produced a smaller ester yield because of the presence of soap, which prevents ester layer separation. Optimum concentration of KOH was 1.2 wt% for 88% yield. It can be concluding that the concentration of KOH strongly dependent on the type of oil used.

Fig. 1. Percentage yield of ester vs. KOH wt%

Reaction TemperatureThe temperature increase the conversion rate also increase. The effect of temperature on the yield as shown in fig.2. The optimum temperature for the reaction is found to be in the range of 75°C and the Maximum yield at 75°C was found to be 95.5°C esters. This

shows that rate of conversion strongly influence by temperature. However there was a slight decrease in yield after 75°C, due to the enhancement of transesterification reaction & saponification reaction. The requirement of higher temperature in yield was due to different in raw feedstock oil.

Fig. 2 Percentage yield of ester vs. Temperature.

Reaction Time

The effect of time on the yield is shown on fig 3, it has been observed that the ester yield increase with increase in reaction time. The dependency of reaction time was studied under time intervals used “Between 20 to 60 minute”. Results obtained for 30 minute time was found to be sufficient for complication of the esterification reaction. The maximum yield of 95.9% occurs at 30 minute.

Fig. 3 Percentage yield of ester vs. Time.The increase in reaction temperature

speeds up the reaction time & shorter the time.

Methanol to oil RatioThe molar ratio of me: oil is one of the important factors that affect the conversion efficiency as well as production cost of biodiesel. The conversion efficiency is defined as the yield molar ratio is the ratio of numbers of moles of alcohol to the number of moles of oil. But theoretically transesterification required 3 mole of alcohol for each moles of oil, but in practice molar ratio should be higher than the stoichometric ratio in order to drive the reaction towards the completion.

The effect of molar ratio on ester yield as shown in fig.4. The maximum yield of ester was achieved at molar ratio of 6:1. The methanol of about 25-150% excess was studied [14]. The methyl ester yield achieved in 30 minute is 95.9%. When the methanol was 100% excess (6:1 me: oil).

LIST OF FIGURES:

Table 1 shows the content of extracted oil from dairy waste.

Table 2 shows the content of crude products.

Table 3 Shows the Fuel Specification of Dairy scum Biodiesel and biodiesel standards (ASTM).

Figure 1 shows the graph of % Yield of ester VS. KOH wt %.

Figure 2 shows the graph of % Yield of ester VS. Temperature.

Figure 3 shows the graph of % Yield of ester VS. Time.

Table no 1.

No of Ex

No. of Replication

% Extracted oil from dairy waste

Batch Method

Continuous Method

1 10 38.07

2.66

39.07

1.16

2 10 30.51

3.16

33.52

2.26

3 10 48.51

2.16

49.19

2.10

Avg. 10 39.08

2.66

40.82

1.84

Table no 2.Types of

catalyst

Crude biodiesel

(%)

Crude

Glycerine (%)

H2SO4 43.24+1.23 56.73+0.21

KOH 43.29+1.11 57.53+1.23

Table no 3.

Property UnitsScum

biodiesel

Biodiesel

Standard

Specific

Gravity_ 0.88

0.87-

0.90

Viscosity

@ 40 °Cmm2/sec. 3.75

1.9-

6.0

Pour

point°C 5-7

-15

to 10

Flash

point°C 157 130

Cloud

point°C 5

-3 to

12

CONCLUSIONS :From this work it’s conclude that dairy waste could be useful for value added product such as Biodiesel & Glycerin. The quality of Biodiesel was not quite good as compared to Glycerin because low content of methyl ester compound. Biodiesel has become best alternative due to its environmental benefits.& it’s made from renewable resources. The reaming factor was to reduce the cost of Biodiesel production. As using non-edible oil, raw material production cost was reduced up to 60-70% and by using continuous operation rather than Batch process it is possible to again reduce to same extent. Dairy industries can use these kinds of projects to solved there economical problem in scum disposal and to improve their economy. Blend of up to 20% biodiesel mixed with petroleum diesel fuels can be more effective as compare to 100% biodiesel. Now it can be used in nearly all diesel equipment and are compatible with more storage and distribution equipment.

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