Biodiesel vs. Diesel: Combustion Analysis and Comparison

Categories: Chemistry

1. Abstract

The aim of this experiment was to analyze an alternative energy supply, biodiesel, as a substitute for traditional diesel fuel. Biodiesel offers an eco-friendly alternative to conventional diesel, making it crucial for both present and future energy needs. In this study, biodiesel was prepared using canola oil, a vegetable-based oil, and its energy content was compared to that of regular diesel fuel using an oxygen bomb calorimeter to measure temperature changes resulting from combustion reactions.

The experiment involved the combustion of benzoic acid as a reference, followed by three separate runs for biodiesel samples and three runs for regular diesel samples.

The heat of combustion values were calculated and compared between biodiesel and diesel. According to the literature, the heat of combustion value for canola oil biodiesel is 43.96 MJ/kg [5], whereas diesel has a value of 44.8 MJ/kg [15]. The experimental results yielded values of 40.71 ± 9.5 MJ/kg for biodiesel and 50.82 ± 9.9 MJ/kg for regular diesel.

These results indicate that biodiesel is a viable energy source, although its energy content is lower than that of regular diesel fuel.

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This underscores the importance of exploring additional biodiesel sources when higher energy output is required. Furthermore, the p-values obtained from the t-test were 0.58 for biodiesel and 0.35 for regular diesel, respectively. Diesel's p-value is smaller than the chosen significance level (α), indicating repeatability, whereas biodiesel's p-value is larger than α, suggesting that the experiment is not easily repeatable for biodiesel.

2. Introduction

2.1. Background

Energy supply stands as one of the most critical global issues today, with petroleum being the most prevalent and in-demand energy source.

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As of November 2018, the production volume of petroleum reached 159 million gallons [12]. Biodiesel, on the other hand, is derived from oils through transesterification, a process that converts oils into biodiesel and glycerin [10]. The feedstock volume presents a challenge, with a total of 1,218 million pounds of feedstocks used for biodiesel production in November 2018. Soybean oil remained the primary biodiesel feedstock during that period, with 704 million pounds being consumed [12]. Other raw materials for biodiesel include corn and canola oil.

However, biodiesel offers several advantages over petroleum-based diesel, particularly in terms of environmental impact. Biodiesel emits fewer greenhouse gases, produces biodegradable byproducts, and releases fewer air pollutants [9]. This experiment aims to compare the heating values of biodiesel and regular diesel, demonstrating which fuel has a more effective heating value. In the literature, the heating value of biodiesel produced from canola oil is reported as 43.96 MJ/kg [5], while diesel has a value of 44.8 MJ/kg [15]. Diesel's heating value surpasses that of biodiesel, with a negligible 10% energy loss.

2.2. Objective

The primary objective of this experiment was to determine the heating values of biodiesel produced from canola oil and regular petroleum diesel using bomb calorimetry. To collect data, calorific values of three different biodiesel samples from canola oil and three different samples of regular diesel were measured using the bomb calorimeter. Subsequently, an equal variance t-test was employed to assess whether the experimental values significantly differed from the theoretical values.

3. Theory

There are several feedstock options for producing biodiesel, including vegetable oil, animal fat, cooking oil, and yellow grease [1]. Various techniques are available for biodiesel production, such as base-catalyzed transesterification of oils, direct acid-catalyzed transesterification, or conversion of oils to fatty acids and then to biodiesel. In this experiment, biodiesel was produced from canola oil using the base-catalyzed transesterification process. Canola oil is a vegetable oil containing triglycerides, which undergo a reaction with alcohol to produce esters and glycerol through the transesterification process [2]. This reaction occurs in the presence of methanol () and sodium hydroxide (NaOH) as the alcohol and catalyst, respectively.

The reactants in this process are triglycerides (canola oil) and methanol. Upon their reaction, glycerol and methyl esters, which constitute biodiesel, are formed. To separate biodiesel from glycerol, their density difference is utilized. Glycerol has a density of 1.26 g/cm³ [4], while biodiesel has a density of 0.84 g/cm³ [5]. When the product solution, which includes petrodiesel, is allowed to stand for 24-48 hours, glycerol with higher density precipitates, and biodiesel can be collected from the top of the heterogeneous mixture.

The heat of combustion is calculated to compare biodiesel and regular diesel. However, prior to conducting experiments with biofuels, the bomb calorimeter is standardized using 1 g of benzoic acid. Benzoic acid is chosen for standardization as it completely dissolves in oxygen and is therefore ideal for this purpose [9]. The energy equivalent or heat capacity of the calorimeter is determined through this standardization test, using Equation 1. In this experiment, the correction factor e1 is neglected, as titration to obtain nitric acid data is not the goal.

Equation 1: \( W = \frac{H \cdot m}{t - e1 - e3} \)

Where:

  • \( W \) = energy equivalent of the calorimeter in calories per °C
  • \( H \) = heat of combustion of the standard benzoic acid sample in calories per gram
  • \( m \) = mass of the standard benzoic acid sample in grams
  • \( t \) = net corrected temperature rise in °C
  • \( e1 \) = correction for heat of formation of nitric acid in calories
  • \( e3 \) = correction for heat of combustion of the firing wire in calories

After standardization, Equation 2 is employed for calculating the net corrected temperature rise:

Equation 2: \( t = \frac{(a - b) + (c - b)}{2} \)

Where:

  • \( a \) = time of firing
  • \( b \) = time (to nearest 0.1 min.) when the temperature reaches 60 percent of the total rise
  • \( c \) = time at the beginning of the period (after the temperature rise) in which the rate of temperature change has become constant
  • \( t \) = net corrected temperature rise in °C
  • \( Ta \) = temperature at the time of firing
  • \( Tc = temperature at time \( c \)
  • \( Rbefore \) = rate (temperature units per minute) at which the temperature was rising during the 5 min. period before firing
  • \( Rafter \) = rate (temperature units per minute) at which the temperature was rising during the 5 min. period after time \( b \)

Once \( t \) and \( W \) values are determined, the gross heat of combustion (\( Q \)) can be calculated using Equation 3, utilizing data obtained from the bomb calorimeter. For this experiment, the corrections for \( e1 \) and \( e3 \) are neglected, as titration is not the focus.

Equation 3: \( Q = \frac{W}{t} \)

Where:

  • \( Q \) = gross heat of combustion
  • \( t \) = net corrected temperature rise in °C
  • \( W \) = energy equivalent of the calorimeter in calories per °C
  • \( e1 \) = correction for heat of formation of nitric acid in calories
  • \( e3 \) = correction for heat of combustion of the firing wire in calories

The correction factor for the fuse wire can be calculated using Equation 4. The factor for the fuse wire is typically provided on its packaging. Additionally, the weight of the wire is measured after it is removed from the bomb calorimeter.

Equation 4: \( Cwire = \frac{Winit - Wfinal}{mwire} \)

Where:

  • \( Cwire \) = correction factor for the fuse wire in calories per degree Celsius
  • \( Winit \) = initial weight of the wire in grams
  • \( Wfinal \) = final weight of the wire in grams
  • \( mwire \) = mass of the wire used in the calorimeter in grams

Finally, the gross heat of combustion value includes the heat of vaporization. To determine the net combustion value, the hydrogen content involved in vaporization needs to be subtracted, as shown in Equation 5. However, in this experiment, \( \text{H} \) was not calculated because the hydrogen content was not known.

Equation 5: \( Qnet = Qgross - \left(\frac{\text{H}}{100}\right) \cdot Qgross \)

Where:

  • \( Qnet \) = net heating value (Btu/lb)
  • \( Qgross \) = gross heating value (Btu/lb)
  • \( \text{H} \) = percentage of hydrogen in the sample

4. Methods

4.1. Equipment

This experiment was conducted in two parts. In the first part, biodiesel was synthesized from canola oil, and in the second part, bomb calorimetry was performed to determine the calorific values of the samples.

For the biodiesel synthesis:

  • Potholders
  • Mason jar
  • Methanol
  • Selected oil (canola oil)
  • Hot plate
  • Stir bar
  • 2000 mL beaker
  • 250 mL Erlenmeyer flask
  • 500 mL graduated cylinder
  • Sodium hydroxide pellets (NaOH)

For bomb calorimetry:

  • Oxygen combustion bomb
  • Digital thermometer
  • Oxygen bomb calorimeter

4.1.1 Oxygen Combustion Bomb

The oxygen combustion bomb is a crucial component of the oxygen bomb calorimeter. It is a robust, thick-walled metal vessel that can be opened for various actions, such as inserting samples and removing combusted products. In this experiment, fuel samples weighing 1 g were measured and placed inside the oxygen combustion bomb [13].

4.1.2 Digital Thermometer

The digital thermometer is another essential part of the oxygen bomb calorimeter equipment. It was utilized to measure the temperature change during the experiment runs.

4.1.3 Oxygen Bomb Calorimeter

The oxygen bomb calorimeter is a constant-volume calorimeter, which serves as a standard instrument for estimating the calorific value of liquid and solid combustible samples. In this calorimeter, electrical energy is employed to ignite the fuel. As the fuel burns in pressurized oxygen, heat is generated. This heat causes the air inside the calorimeter to expand, and the expanded air escapes through tubes. As the air escapes, it heats the water surrounding the tubes. The temperature difference in the water is then used to calculate the calorific value of the fuel. The oxygen bomb calorimeter essentially comprises three main components: the oxygen combustion bomb, digital thermometer, and insulating jacket.

4.2. Experimental Design

For the production of biodiesel from canola oil, the following steps were followed:

  1. Weighed 0.875 g of NaOH and mixed it with 50 mL of methanol in a 250 mL Erlenmeyer flask. The mixture was stirred at 700 rpm with a magnetic stirrer until the NaOH dissolved.
  2. Heated 250 mL of canola oil on a hotplate, setting the temperature to 46°C. This step was repeated three times.
  3. When the oil temperature reached 55°C, the NaOH and methanol mixture was added to the oil, and the mixture was stirred at 700 rpm for 20 minutes.
  4. After 20 minutes, the mixture was transferred to a Mason jar and allowed to sit for 24 hours until glycerin in the mixture formed a distinct layer.
  5. After 24 hours, the top layer of the mixture, which is biodiesel, was extracted from the jar and placed in the bomb calorimeter for heat value determination.

For bomb calorimetry:

  1. The bomb calorimeter was standardized using benzoic acid.
  2. After standardization, a fuse wire was attached to the A38A stand, and a fuel capsule was arranged [7].
  3. Next, the thermistor was placed, and the nut was tightened adequately.
  4. After confirming the calorimeter bucket's condition, the ignition unit was connected. A 23-volt power source was used to ignite the fuse inside the oxygen bomb.
  5. The final step involved attaching the oxygen filling connection for assembly.
  6. Approximately 1.0 g of each sample was taken, and the calorimeter tank was filled with approximately 2 L of water.
  7. The bomb's pressure was adjusted to 30 psig.
  8. After setup, the stirrer was operated for 5 minutes to establish thermal equilibrium, and the temperature was recorded every minute.
  9. Subsequently, ignition was initiated, and the temperature was recorded every 30 seconds. Temperature measurements continued until a sudden increase in temperature was observed, after which the temperature changes were recorded every 30 seconds.
  10. Each sample was run three times for t-test comparison.

4.3. Safety Concerns/Plans

Prior to conducting the experiment, safety considerations are paramount. This experiment involves the use of chemicals such as methanol, sodium hydroxide, and benzoic acid, which present specific safety concerns:

  • Methanol: Methanol is toxic and highly flammable. Minimize skin contact, and if contact occurs, rinse skin or eyes with water. Exercise extreme caution when working with methanol.
  • Sodium Hydroxide: Sodium hydroxide is corrosive, causing severe eye damage and skin burns. In the event of skin contact, remove contaminated clothing and shoes immediately.
  • Benzoic Acid: Benzoic acid can irritate the skin and eyes. In case of contact, rinse eyes or skin with water for at least 15 minutes.

Additionally, it is essential to wear safety glasses and gloves throughout the experiment, considering the volatility of methanol and the irritability of other chemicals.

The equipment used in this experiment also requires careful handling:

  • The bomb calorimeter is utilized to conduct reactions under high pressure. Ensure the calorimeter lid is securely tightened to prevent potential explosions.
  • Charge the bomb with oxygen cautiously, avoiding overloading.
  • After firing the calorimeter, maintain a safe distance of at least 15 seconds.
  • Do not fire the bomb if there is a gas bubble leakage [6].
  • Avoid contact between equipment and electrical lines [8] since electricity is used for measurements.

Furthermore, it is crucial to clean the laboratory thoroughly after the experiment, as methanol is volatile, and other chemicals can be irritating. Ensure that all equipment is turned off upon completing the experiment.

4.4. Experimental Protocol

4.4.1 Preparation of Biodiesel

  1. Weigh out 0.875 g of NaOH and place it into a 250 mL Erlenmeyer flask.
  2. Measure 50 mL of methanol and pour it into the same 250 mL Erlenmeyer flask.
  3. Stir the mixture at 700 rpm until most of the NaOH has dissolved.
  4. Set the mixture aside.
  5. Measure out 250 ml of Canola oil.
  6. Heat the canola oil on the hotplate at 45-48°C while monitoring the temperature using a thermocouple.
  7. Introduce the prepared methanol/NaOH mixture into the canola oil when the canola oil temperature reaches 55°C.
  8. Stir the solution quickly with a stirrer for 20 minutes using a stir bar.
  9. Pour the resulting biodiesel into a Mason jar and allow the mixture to sit for 24 hours, allowing it to separate into two layers, with biodiesel on top.

4.4.2 Oxygen Bomb Calorimeter

  1. Weigh out a 10 cm nickel wire and record its weight.
  2. Secure a 10 cm length of wire between the electrodes in the bomb canister.
  3. Remove the crucible from the bomb canister and zero the scale.
  4. Place 1 tablet of benzoic acid in the crucible, weigh it, and record the weight. (Note: This step will change with different substances.)
  5. Put the crucible back into the bomb head and adjust the wire to touch the surface of the pellets.
  6. Reassemble the bomb canister.
  7. Connect the canister's outlet valve to the oxygen tank using a hose.
  8. Turn on the tank valve a quarter turn after ensuring the cap is sealed completely.
  9. Fill the bomb canister with oxygen until it reaches 30 atm gauge.
  10. Close the oxygen tank valve and empty the oxygen from the hose by pushing down the attached lever.
  11. Remove the hose from the bomb.
  12. Pour 2L of distilled water into a container.
  13. Using the lift handle, place the bomb canister halfway into the water.
  14. Connect one of the lead wires to the ignition unit.
  15. Connect the second wire to the middle terminal.
  16. Submerge the bomb completely and close the calorimeter cover.
  17. Connect the stirrer to the drive motor and run for five minutes.
  18. Insert the thermometer into the calorimeter bomb.
  19. Monitor the temperature every minute and record values for five minutes.
  20. Press the firing button for five seconds.
  21. Monitor the temperature difference each minute.
  22. Remove the thermometer, thermocouples, and calorimeter cover once the temperature difference stabilizes.
  23. Remove the canister from the calorimeter.
  24. Release the pressure in the canister using the pressure release valve for one minute.
  25. Seal the cap and remove the bomb head.
  26. Remove the crucible and record its final weight.
  27. Remove the fuse wire and record its final weight.
  28. Thoroughly wash the bomb and crucible with distilled water.
  29. Repeat all steps for three samples of biodiesel and three samples of regular diesel by weighing 2-3 g of samples at the fourth step in each case.

5. Results and Discussion

Measurements were conducted on three biodiesel samples prepared using canola oil and three regular diesel samples during the experiment. Prior to these measurements, the oxygen bomb calorimeter was standardized using a benzoic acid sample.

The firing moment temperatures for the samples and their respective temperature changes were as follows:

  • Sample 1: From 31°C to 35.1°C
  • Sample 2: From 33°C to 37.1°C
  • Sample 3: From 35°C to 37.4°C

The combustion reactions inside the oxygen calorimeter bomb caused temperature increases over time, resulting in different firing temperatures for each sample. The consistent temperature change difference across all samples suggests a stable experimental setup.

For the regular diesel samples, the firing moment temperatures and temperature changes were:

  • Sample 1: From 19.2°C to 23.8°C
  • Sample 2: From 23.8°C to 28.4°C
  • Sample 3: From 26.8°C to 32.6°C

After recording all data, the net corrected temperature rise (t) was calculated using Equation 2, and the values were determined from the slopes of the graphs (as shown in 9.2 Sample Calculations and Graphs section). Subsequently, the heat of combustion value for each sample was calculated using Equation 3.

Table 5.1: Gross Heat of Combustion Values for Each Sample
Sample Type Heat of Combustion (MJ/kg)
Biodiesel Sample 1 47.02
Diesel Sample 1 46.65
Biodiesel Sample 2 45.33
Diesel Sample 2 43.65
Biodiesel Sample 3 29.79
Diesel Sample 3 62.18
Average 40.71 ± 9.5
Average 50.82 ± 9.9

Table 6.1 displays the calculated heat of combustion values for each sample. Comparing sample 1 and 2, we observe slight variations in values, while sample 3 values for both biodiesel and diesel samples significantly differ. This suggests the possibility of temperature change observation or diesel weight errors during the third trial.

A two-sample assuming equal variances t-test was conducted to assess the differences between biodiesel and diesel values. The results are presented in Excel tables (as shown in 9.5 Completed Excel Analysis Tables section). The significance level (α) was set at 0.05, and two-tailed p-values were obtained. The t-test results for temperature change comparison revealed that all two-tailed p-values were smaller than 0.05, leading to the rejection of the null hypothesis. Specifically, the p-values for sample 1, sample 2, and sample 3 were , , and 8.83, respectively.

Additionally, the heat of combustion values were compared using the t-test, assuming equal variances. For biodiesel, the p-value was found to be 0.58, which is higher than α=0.05, indicating that the null hypothesis cannot be rejected, and the experiment is repeatable. Conversely, for diesel, the p-value was found to be 0.35, which is smaller than α, leading to the rejection of the null hypothesis for regular diesel and indicating that the experiment is not repeatable.

6. Conclusions

Heat of combustion values were calculated for biodiesel and regular diesel samples in this experiment, with biodiesel prepared using canola oil. Three samples of each were tested, and data were recorded. The aim was to obtain more accurate results by collecting data from three separate samples. The average heat of combustion was found to be 9740.76 ± 2279.8 Cal/gr for biodiesel and 12140.16 ± 2376.6 Cal/gr for regular diesel. This experiment showed that the heat of combustion value for biodiesel was less than expected.

7. Appendices

Time (min) Sample 1 Temperature (°C) Sample 2 Temperature (°C) Sample 3 Temperature (°C)
0 31.3 31.3 35.0
1 31.2 33.2 35.2
2 31.2 33.1 35.2
3 31.1 33.0 35.1
4 31.0 33.0 35.0
5 31.0 33.0 35.0
5.5 32.2 34.1 36.0
6 33.0 35.4 36.4
6.5 33.9 36.2 36.8
7 34.4 36.6 37.1
7.5 34.8 36.9 37.2
8 34.9 37.0 37.3
8.5 35.0 37.1 37.3
9 35.0 37.1 37.4
9.5 35.1 37.1 37.4
10 35.1 37.1 37.4
10.5 35.1 37.1 37.4
11 35.1 37.1 37.4
11.5 35.1 37.1 37.4

 

Time (min) Sample 1 Temperature (°C) Sample 2 Temperature (°C) Sample 3 Temperature (°C)
0 18.9 23.7 26.2
1 19.1 23.8 26.8
2 19.1 23.7 26.8
3 19.2 23.8 26.8
4 19.2 23.8 26.8
5 19.2 23.8 26.8
5.5 19.4 24.0 27.4
6 21.1 24.2 29.6
6.5 22.1 25.9 30.6
7 22.7 26.6 31.5
7.5 23.3 27.5 32.0
8 23.4 27.8 32.2
8.5 23.5 28.1 32.3
9 23.7 28.3 32.5
9.5 23.7 28.3 32.5
10 23.8 28.4 32.6
10.5 23.8 28.4 32.6
11 23.8 28.4 32.6
11.5 23.8 28.4 32.6
Updated: Jan 12, 2024
Cite this page

Biodiesel vs. Diesel: Combustion Analysis and Comparison. (2024, Jan 12). Retrieved from https://studymoose.com/document/biodiesel-vs-diesel-combustion-analysis-and-comparison

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