Download - Alkaline Transesterification of Waste Cooking Oil to Biodiesel

A presentation of Biodiesel Production From Non-Edible Vegetable Oil

1

Production of

Biodiesel from Non

Edible Vegetable Oil

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Why Biodiesel ….?

3

EconomicalRenewable

Depletion of Crude Oil

Environment

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Aim of this Work:

Achieve the maximum yield in parallel with standardproperties.

Prepare technical feasibility study and costeffectiveness of biodiesel production for a biodiesel plantusing alkaline transesterification of more than 100,000

ton of used cooking oil.

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First Part :

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Biodiesel Feedstock

Transesterification Methods

Materials & Experiment

Result and Discussion

Production Of Biodiesel From Used Cooking Oil


Biodiesel Feedstock

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Biodiesel FeedstockTwo main categories:

Edible vegetable oil:Soybean, Peanut, Sunflower, Palm and Coconut oil.

Non-edible vegetable oil: Rapeseed, Jatropha, Jojoba , Sea mango, Algae.Used cooking , Used motor vehicles oil.

Currently, more than 95% of the world biodiesel isproduced from edible oils such as sunflower oil (13%),palm oil (1%), soybean oil and others (2%)

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Biodiesel FeedstockFeedstock Productivity:

Oil Productivity (litre oil/litre

biodiesel

Palm oil 1.25

Rapeseed oil 1.1

Soya beans 1.3

Used cooking oil 1.03

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10

Biodiesel Feedstock







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Transesterification Process of exchanging the organic group of

an triglyceride with the organic group of an alcohol.These reactions are often catalyzed by the addition ofan acid or base catalyst. The reaction can also beaccomplished with the help of enzymes.

12Transesterification Reaction

TransesterificationTypes of Transesterification Process :-

Acid catalyst Transesterification.

Alkaline catalyst Transesterification.

Enzyme catalyst Transesterification.

Supercritical methanol Transesterification.

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Transesterification

I. Acid Catalyst Transesterification:

The homogeneous acid-catalyzed reaction is slowerthan the homogeneous base-catalyzed reaction .

Acid catalysts are insensitive to free fatty acids, andthey have better results for vegetable oil with FFAgreater than 1%.

The acid Transesterification process is catalyzedpreferably by sulfuric acids and hydrochloric acid.

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Transesterification

I. Acid Catalyst Transesterification …cont’d:

Advantages: Suitable for high FFA% Feedstock.

Disadvantages: Slow reaction, Severe condition ashigh temperature and long time, More corrosive,large amount of catalyst , more separation processesand high cost.

15

Transesterification II. Alkaline Catalyst Transesterification:

Alkali-catalyzed Transesterification is the most economical process requiring moderate temperatures and pressures to achieve a 98%conversion yield.

It is very sensitive to both water and free fatty acidscontent.

6 moles of alcohol are used for every mole oftriglyceride, which is more than the equationindicates. The reason is that the reaction is desiredto proceed in the direction of formation biodiesel.

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Transesterification II. Alkaline Catalyst Transesterification

…cont’d:

Advantages: Fastest reaction , Higher yield , Mildreaction condition, Low cost , Less corrosive , Lesstoxicity.

Disadvantages: Excessive Soap formation.

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TransesterificationMechanism of the Alkaline Catalyst Transesterification:

Eq.1: reaction of the base with alcohol to produce an alkoxide and protonated catalyst.

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TransesterificationMechanism of the Alkaline Catalyst Transesterification ….cont’d:

Eq.2: the nucleophilic attack of alkoxide at carbonyl group of triglyceride generates tetrahedral intermediate.

19

TransesterificationMechanism of the Alkaline Catalyst Transesterification ….cont’d:

Eq.3: alkyl ester and diglycerides anion are formed .

20

Transesterification Mechanism of the Alkaline Catalyst Transesterification ….cont’d:

Eq.4: the diglycerides deprotonate the catalyst so it will react with another molecule of alcohol starting another catalytic cycle. Diglycerides and monoglycerides are converted by the same mechanism to a mixture of alkyl esters and glycerol.

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TransesterificationEnzyme Catalyst Transesterification:

The Two most catalyst used : Candida Antarctica B lipase, Aero-genes lipase.

The reaction can be carried out at low temperature which ranges from 35 to 45 °C and pressure that reduces energy consumption and as such improves environmental performance .

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TransesterificationEnzyme Catalyst Transesterification ….cont’d:

Advantages: Enzyme catalysis proceeds without the generation of by-products or side reaction, mild reaction conditions, insensitive to high FFA in oil and water content, enzyme catalyst can be reused.

Disadvantages: Use of enzymes is limited because costs are high, the rate of reaction is slow, methanol that can cause enzyme deactivation, and the yields of methyl esters are typically less than those obtained by base catalyzed reaction.

23

TransesterificationSupercritical Methanol Transesterification:

It is not sensitive to high FFA or water contents. Itis a non-catalytic reaction, using alcohol (typicallymethanol) under supercritical conditions at hightemperatures and pressures (temperature 350–400

°C and pressure more than 80 bar) so FFAs aretrans-esterified simultaneously.

24

TransesterificationSupercritical Methanol Transesterification

….cont’d:

Advantages: The elimination of the pre-treatmentstep and soap, low reaction time ranges from 12 to50 minutes , High yield more than 96 % and variousresources of feedstocks.

Disadvantages: more power, require high alcohol ratio (42:1), high operating & capital cost

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Biodiesel Feedstock







27

Materials and ExperimentResearch methodology The present study was carried out under supervision of

the Cairo University and Egyptian petroleum research institute (EPRI) in order to identify an effective treatment of used cooking oil to get the ideal specification condition to obtain high yield of biodiesel, get the best conversion ratio of used cooking oil to biodiesel.

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Materials and ExperimentEquipment:

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Magnetic heat stirrer

Conical flask

Sensitive balance

Burette

Materials and ExperimentEquipment ….cont’d

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Thermometer

Beakers

Condenser

Separating funnel

Materials and ESxperimentEquipment ….cont’d

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Materials and ExperimentBiodiesel Production Steps:

1. Feedstock Treatment:

Measuring Free Fatty Acid.

Removal of Insoluble Impurities.

Water Removal.

Preparation of Alcohol and Catalyst. 32

Materials and ExperimentBiodiesel Production Steps ….cont’d:

2. Alkaline Transesterification Process

Addition of Alcohol and catalyst mixture to the oil at the specified temperature and mixing rate.

3. Biodiesel Treatment .

Biodiesel Purification.

Water Washing.

Drying Produced Biodiesel.33

Materials and ExperimentFeedstock specifications:

• It is necessary to get specification of feedstock beforereaction to decide pre-treatment if needed to reachthe specification of feedstock to satisfied conditions .

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Property Value

Density (gm/ cm3) 0.934

FFA % 0.522

Acid Value (mg /KOH) 1.04

Materials and ExperimentExperiment Setup:

In this Experiment Setup, the effect of Time,

temperature, catalyst concentration , methanol to oil

ratio and mixing rate on final yield and properties of

biodiesel produced were studied.

The experiments have been carried out by using the

rotatable central composite design (RCCD) as it

allows usage of few numbers of experiment to cover

wide range of variables.

Linear regression analysis was preformed to

investigate of the individual studied parameter.

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Materials and ExperimentExperiment Setup ….cont’d:

The multiple regression analysis was performed to

investigate and optimize the interactive effect of the

studied parameters.

The model used in this study to estimate the response

surface is the quadratic polynomial represented by the

following equation:

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Biodiesel Feedstock






Result & Discussion

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Result and Discussion1. Linear Regression Result:

Statistical analysis of the model was performed to evaluate the analysis of variance (ANOVA).

Minitab,Inc 16 software was used data analysis for linear regression analysis.

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Result and DiscussionThe linear regression equation is:

Biodiesel yield = 60.6 + 1.94 M:O + 11.3 Catalyst +0.171 Temperature - 1.42 Time - 0.0276 Mixing rate.

The value of R-seq is 0.467 (ensures moderate fitting).

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Item Coefficient Significant

M:O 1.94 High significant

Catalyst 11.3 Statistically Significant

Temperature 0.171 Non statistically Significant

Time -1.42 Non statistically Significant

Mixing rate -0.037 Non statistically significant

Significance of regression parameters

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10090807060

12

10

8

6

4

2

0

Biodiesel yield

M:O

Scatterplot of M:O vs Biodiesel yield

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10090807060

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Biodiesel yield

Ca

ta

lyst

Scatterplot of Catalyst vs Biodiesel yield

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10090807060

80

70

60

50

40

Biodiesel yield

Te

mp

era

tu

re

Scatterplot of Temperature vs Biodiesel yield

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10090807060

4

3

2

1

0

Biodiesel yield

Tim

eScatterplot of Time vs Biodiesel yield

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10090807060

500

400

300

200

100

Biodiesel yield

Mix

ing

ra

te

Scatterplot of Mixing rate vs Biodiesel yield

Result and Discussion2. Quadratic Regression Results:

The statistical software Design Expert 6.0.7 (Stat-Ease Inc., Minneapolis, USA) was used for designof experiments, regression and graphical analysesof the data obtained, doing the statistical analysesof the model and determine the significance levelsof different parameters by evaluation of theanalysis of variance (ANOVA), and it was also usedfor the optimization of the transesterificationprocess .

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Result and Discussion2. Quadratic Regression Results ….cont’d:

Determination coefficients, which measure themodel fitting reliability, were calculated and foundto be 0.990, respectively. This indicates the highsignificance of the model.

The standard deviation SD and the coefficient ofvariance were low, recording; 1.98 and 2.53 formodel, respectively.

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The experimental plan was able to describe thefollowing second order quadratic model equationby applying the multiple regression analysis :

After exclusion the non-significant factors:

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The M:O molar ratio and catalyst concentrationwt% had a highly positive statistical significanteffect on the biodiesel yield.

The process temperature had a positive statistical significant effect.

The process time had a non statistical significantnegative effect on the biodiesel yield and themixing rate had a highly negative statisticalsignificant effect.

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Result and Discussion Effect of M:O and Catalyst concentration on yield:

The negative interactive effect of M:O and catalyst loading, at constant reaction temperature, time and mixing rate.

High biodiesel conversions were obtained at high M:O molar ratio and catalyst.

Excessive methanol would make the recovery of glycerol difficult, as it prevent the separation of the glycerol.

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Result and Discussion Effect of M:O and Mixing rate on yield

The positive interactive effect of M:O and mixing rate is very obvious in the Figure, where there was an overall increase in the biodiesel yield with the increment of M:O molar ratio and the mixing rate.

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Result and Discussion Effect of Temperature and Catalyst concentration on yield: The negative interactive factor of

process temperature and initial catalyst concentration at constant M:O, process time and mixing rate is shown in fig.

Low conversion occurred at low temperature and catalyst concentration.

The biodiesel yield was progressively decreased at high level of temperature and low level of catalyst concentration and also at higher level of KOH and temperature.

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Result and Discussion Effect of Time and Catalyst concentration on yield :

The biodiesel yield was low at low catalyst and reaction time, at lower catalyst concentrations, the biodiesel conversion at a given time increased sharply with increasing of catalyst concentration.

Using less time and more catalyst is the possibility of obtaining lower production cost.

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Result and Discussion Effect of Temperature & Mixing rate on yield :

The positive interactive effect of mixing rate and process temperature at constant M:O, catalyst concentration and reaction time is shown in below Fig.

The biodiesel yield was low at low temperature and mixing rate, but increased with the increment of both factors.

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Result and DiscussionEffect of Time & Mixing rate on yield :

The positive interactive effect of mixing rate and time on the biodiesel yield is shown below.

The low mixing rate and short process time would produce low biodiesel yield.

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Result and DiscussionOptimum Run :

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Item Unit Optimum

run (1)

Optimum

run (2)

Optimum

run (3)

M:O 8.76 8.56 7.54

Catalyst % 0.362 0.654 0.875

Temperature C 65.7 62.4 52.7

Time Hr 2.51 2.9 1.17

Mixing rate Rpm 384 391 266

Yield gm 98.5 98.8 99.2

Comparison Between Linear & Multiple Yield

Item Unit Linear Multiple Diff

M:O 6 7.54 1.54

Catalyst % 0.6 0.875 0.275

Temperature C 60 52.7 - 7.3

Time Hr 2 1.17 - 0.83

Mixing rate Rpm 300 266 - 34

Yield gm 85.5 99.2 13.7

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Biodiesel Yield Specifications

Density

Viscosity

Cetane number

Acid number

Flash point

Aniline point

Pour point & cloud point

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Biodiesel Yield Specifications …cont’d

Cetane number :High Cetane number improves high quality ,less NOx,

less noise .

Acid number : Amount of KOH to neutralize 1 gram of substance.It is a measure of FFA & water in biodiesel .

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Biodiesel Yield Specifications …cont’d

Flash point : Higher flash point better storage, more safer

Aniline point :Measure of aromatics and saturated HydrocarbonsLower aniline point indication of higher aromatics and

lower paraffins.

Pour point & cloud point : Fuel flow in cold weather, storage and transportation.

Comparison between Biodiesel Standard & Yield Specs:

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Property Units Limits Yield

Density g/cm3 0.88 0.8953

Cetane number --- 48 - 65 48.57

Kinematic

Viscosity Cst 1.9-6 4.4

Free fatty acid % 0.42 max 0.014

Acid number mg KOH/g 0.8 max 0.028

Flash point ºC 120-191 127

Aniline point ºC 96-97 95

Cloud point ºC -3 to 12 -3

Pour point ºC -15 to 10 -7

Calorific value MJ/kg 37.3 39.6

Result and DiscussionPhysico-Chemical Characterization of theProduced Biodiesel:

The purified product obtained from thetransesterification of WCO using the selectedoptimum conditions was tested for estimating andevaluating its fuel properties, using the standardmethods of analysis for petroleum products (ASTM,1991).

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FAME wt%

Saturated FAME 12.06

Unsaturated FAME 77.68

Polyunsaturated FAME (PUFA)

10.26

Biodiesel Composition

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Second Part:

Types of cost estimation

Analogous Estimating

Estimating uses the values such as scope, cost,budget, and duration or measures of scale such assize, weight, and complexity from a previous, similarproject as the basis for estimating the sameparameter or measurement for a current project.

Parametric Estimating

Parametric estimating uses a statistical relationshipbetween relevant historical data and other variables(e.g., square footage in construction) to calculate acost estimate for project work.

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Design of Cost Estimation

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Design of Cost Estimation Criteria

This study is concerning with evaluation theeconomic costs of transforming crude usedcooking oil into a methyl ester product viacommercial plant scale with capacity 100,000 tonper year.

The cost analysis is designed according to theoptimum conditions of feedstock, temperature,catalyst concentration, and methanol to oil ratio,obtained from experimental design.

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Design of Cost Estimation Criteria

Capital Expenditure: It is fixed, one-timeexpenses incurred on the purchase of land,buildings, construction and equipment used inthe production.

Operating Cost: It is the expenses which arerelated to the operation of plant. Operating costsare divided into fixed and variable costs.

E-1

E-2

E-4

E-5

P-1

E-6 E-7 E-8E-9

P-3

P-6

E-11

P-8E-12

E-13

P-10

P-11

P-12

E-14

P-13

E-15

P-14

Catalyst

KOH Methanol

Main reactor

Used

Cooking oil

Filtration Tank

E-16

P-16

Condenser

Methanol

separator

P-17

E-17

P-18

E-18

Distilled

water

P-21

Glycerin

Washing Units

Biodiesel

Glycerin

Separator

E-19 E-20

P-22 P-23

P-24

P-25

P-26 P-28

P-26

P-29

E-21

Sewage

water

P-28P-26

P-32

E-22

Biodiesel

Methanol

vapors

P-35

P-19

P-36

P-19

P-37

P-40

E-23E-24

P-4

E-26

P-7P-15 P-20

E-27

E-28

P-31

E-29

P-39P-41

Condenser

Cooler

Heat

exchanger

P-42

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Flow Diagram

Biodiesel Plant

Capital Expenditure (CAPEX)

Purchased Equipment cost 69

Equipment Numbers Price US ($) Total price

Carbon steel Tank 10000 m3 10 30,000 300,000

Tank with capacity 1000 m3 2 20,000 40000

Condenser 3 100,000 300000

Heat exchanger 4 15,000 60000

Carbon steel Vessels 3 30,000 90000

Pumps with flow rate 10

m3/h8 20,000 160000

Filters 4 15,000 60000

Batched stirred reactor 3 50,000 150000

Vapour–liquid separator 2 50,000 100000

Mixer 2 20000 40000

Total price ($) 1,300,000

Capital Expenditure (CAPEX)

Total Capital Cost 70

Item Percentage Price $

Equipment Installation 35% 455000

Instrumentation 20% 260000

Piping 66% 858000

Electrical 11% 143000

Building 45% 585000

Transportation 15% 195000

Purchased equipment cost 1,300,000

Total CAPEX 3,796,000

Contingency 25% 325,000

Total CAPEX with

contingency reserves4,121,000

Operating Costs (OPEX)

Fixed Costs:

Fixed costs considered in the study are depreciation,local taxes, insurance, plant overhead, interest anddirect labors.

Maintenance and insurance will be 2% of total directmaterial or purchased equipment cost so the both ofmaintenance and insurance cost will be 280

thousands $ per year.

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Fixed Costs ….cont’d:

Taxes will be 25 % of difference between total revenue& total OPEX.

Direct labor is estimated to be 150 employeesincluding engineers, technician, accountants, HRrepresentatives ...etc. Expected average salaries will bearound 1800 US $ /month for each employee, so totalannual salaries will be nearly 3.3 million US $.

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Variable Costs:

Variable costs considered in study are: Raw material,Utilities, and Chemicals.

Raw materials such as methanol and biodiesel priceswas obtained from ICIS weekly pricing report whileprice of potassium hydroxide price obtained frominternet and price of used cooking obtained by localsurvey.

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Variable Costs ….cont’d:

The prices of feedstock waste cooking oil is 400 US$/ton and this prices is average prices from localmarket.

Utilities include steam, utility water, process water,cooling water, electricity ...etc. The prices of utilitiesare obtained from other projects executed in Egyptespecially petrochemical projects.

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Variable Costs …cont’d:

Chemicals used in biodiesel production are dedicatedfor treatment of cooling water. Chemicals used suchas sodium bisulfate for removing free chlorine andorganic compound, ion exchange resin (strong acid )for removing water scaling ,caustic soda or sulphuricacid for PH neutralization, corrosion inhibitors. Theexpected price of these chemicals estimated as threemillion $ per year.

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Technical Assumption

Construction Period (year) 2

Project Life Cycle (year) 20

Startup Date 1/01/2018

working hours per year 8,000

Operating Capacity

Year 1 80%

Year 2 90%

Year 3+ 100%

Economic Assumptions

Inflation Rate 3%

Labour Inflation Rate 8%

Equity 49%

Debt 51%

Loan Interest 9%

Debt Repayment Period (years) 7 76

Biodiesel Project Technical & Economic Assumptions

Products (thousand Tons per year)

Biodiesel 100

Feedstock (thousand tons per year)

Methanol 26.8

Potassium hydroxide 0.875

Used Cooking Oil 101

Utilities

Cooling and process Water Consumption

without recirculation m3/yr1,000,000

Steam Consumptions (tons per year) 300,000

Electricity Consumption (MWH) 15,000

Chemicals and Catalyst Cost

(MMUSD/Year)3

Land Requirement (m2) 42,000

Labor Requirement (number) 150 77

Biodiesel Operating Assumptions

0

20

40

60

80

100

120

140

160

2015 2020 2025 2030 2035 2040

TotalRevenues MM$

Total OpexMMUSD

Year

MMUSD

Total revenue versus Total Revenue versus Total OPEX

78

Biodiesel Production Cost & Price

79

0

0.2

0.4

0.6

0.8

1

1.2

1.4

2015 2020 2025 2030 2035 2040

Biodiesel production cost

Petro-diesel price

Year

USD / Litre

80

0

1

2

3

4

5

6

2018 2019 2020 2021 2022 2023 2024 2025 2026 2027 2028 2029 2030 2031 2032 2033 2034 2035 2036 2037

Income After

Tax

MMUSD

Year

Net Income after taxes versus Depreciation

Item Price

Methanol cost ($/litre biodiesel) 0.072

KOH cost ($/litre biodiesel) 0.02

Waste cooking oil cost ($/litre biodiesel) 0.333

Utilities cost ($/litre biodiesel) 0.036

Other chemicals costs ($/litre biodiesel) 0.027

Fixed cost (maintenance, salaries and insurance) ($/litre

biodiesel)0.027

Biodiesel production cost ($/litre) 0.515

Biodiesel production cost ($/gallon) 1.949

Current market price biodiesel ($/gallon) 3.77

Current market price petro-diesel in USA ($/gallon) 2.561

Current market price petro-diesel in Egypt ($/gallon) 0.871

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Estimation for the cost of One litre Biodiesel

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CONCLUSION

CONCLUSION

The first part of work investigates the optimum conditions to produce high yield of biodiesel in addition the best fuel quality by using factorial design method.

The experiments were carried out in the following conditions: reaction temperature from 40 to 78 C, reaction time from 1 hr to 3 hrs; catalyst concentration from 0.05% to 1.15% by weight of used cooking oil; methanol to oil molar ratio from 3:1 to 11:1, mixing rate from 200 to 400 rpm.

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CONCLUSION ….cont’d

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Multiple regression analysis conclude that methanol to oil ratio, catalyst concentration have high positive statistical significant effect.

Temperature has a positive statistical significant effect.

The process time had a non statistical significant negative effect on the biodiesel yield and the mixing rate had a highly negative statistical significant effect.


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The best methyl ester conversion obtained was 99.2 wt.% based on the following conditions : methanol to oil molar ratio of 7.54:1, catalyst concentration of 0.875% , 1.17 hr of reaction time, temperature of 52 °C, mixing rate 266 rpm.

The produced biodiesel can be used in compression ignition engine as its quality is agreeing the American standard testing method (ASTM) and all properties such as Cetane number, acid number, flash point, pour point, cloud point, aniline point, pour point are in the standard range.


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The calorific value of produced biodiesel is 39.6

MJ/kg higher than the standard biodiesel calorific value by 6 %. The properties of produced biodiesel ensure the successful utilization of biodiesel in vehicles instead of fossil fuel and replace fossil fuels by biofuels.

The physic-chemical characterization of produced biodiesel concludes that the percentage of saturated FAME is 12.06%, unsaturated FAME is 77.68% and polyunsaturated FAME is 10.26%.


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The second part of work related to technical feasibility and cost effectiveness of biodiesel production for a biodiesel plant using alkaline transesterification of more than 100,000 ton of used cooking oil.

Biodiesel project is very profitable and the economic indicators for the project is very high and execution of such a project will strength the national economic and provide about 150 direct job opportunity and 1000 non direct labors.


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The total CAPEX needed to build up the biodiesel plant is 4.121 million $ as the purchased equipment cost is 1.3 million $ while other CAPEX is 2.8 million $.

The total OPEX will be 58 million US $ in 2018

reaches up to 132 million US $ in 2037 while the revenue in 2018 will be 50 million US $ increasing gradually every year reaching to 136 million US $ in 2037.


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The net income or profit is the difference between the revenue and the total OPEX.

There will be a variation in net income during all 20 years of the project.

The project will not achieve any profit during the first two years in contrast while from 2020 the project will achieve a net income about 5.03

million US $ verifying in the next years up and down achieving a total net income during the life cycle of project about 72.5 million US


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Cost analysis concluded that the current price of biodiesel 3.77 $ /gallon or 1 $/litre and for petro-diesel is 2.56 $/gallon or 0.677 $/litre while the cost of production one litre of biodiesel is 0.515$.

Accelerate in Changing to utilization of biodiesel from waste cooking oil will have a great profit especially that Egypt consumption of petro-diesel is very high as it consumed 12 million ton of petro-diesel in 2011.

Download - Alkaline Transesterification of Waste Cooking Oil to Biodiesel

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