EXECUTIVE SUMMARY

Acetaldehyde is a colourless liquid with a pungent, fruity odour. It is primarily used as a chemical intermediate, mainly for production of acetic acid, pyridine and pyridine bases, peracetic acid, pentaeythritol, butylene glycol, and chloral. Acetaldehyde is a volatile and flammable liquid which is miscible in water, alcohol, ether, benzene, gasoline, and other common organic solvents. This report is about the production of acetaldehyde from oxidation of ethanol at its optimum residence time in a continuous stirred tank reactor. The objective functions of the process are developed in order to obtain the optimum residence time at which the optimum concentration of acetaldehyde is produced.

An algorithm based on Quasi-Newton optimization method is developed. By utilizing MATLAB 2007a software and setting the initial guess at 0.2, an optimum residence time of 0.69 hours is obtained. The concentration at this residence time is approximately 0.45 moles per litre which requires a reactor of 152 litres volume.

ACKNOWLEDGEMENT

First and foremost, we would like to express our gratitude to Allah S.W.T. for making the Process Optimization project successful and beneficial for us. To the rest of Group 10, the participation and dedication on performing each task is admirable.

An indication of appreciation also goes to Professor Dr. Saibal Ganguly for his guidance and advises throughout the project development. We express our gratitude in hearing and settling our doubts and problems on the course throughout the semester.

Of course, the team work spirit displayed by all the members of this group definitely played its part in making this design report such a remarkable success. All team members were dedicated to this project and sacrificed a lot of time and energy in order to complete this comprehensive report. Everyone was willing to help each other whenever one was facing any hardships.

Last but not least, we would also like to thank all our friends and course-mates in the school of chemical engineering in giving useful tips and suggestions to us whenever we require them. Their role was also crucial in helping us to complete this project.

Thank you.

TABLE OF CONTENTS EXECUTIVE SUMMARY............................................................................................ ACKNOWLEDGEMENT............................................................................................ TABLE OF CONTENTS............................................................................................ TABLE OF FIGURES..................................... ....................................................... CHAPTER 1 : BACKGROUND............................................................................................ CHAPTER 2 : PROBLEM STATEMENT AND OBJECTIVE FUNCTION.......................... CHAPTER 3 : FORMULATION OF THE SYSTEM MODEL............................................. CHAPTER 4 : ALGORITHM............................................................................................ CHAPTER 5 : MATLAB SIMULATION................................................................................ CHAPTER 6 : RESULT AND DISCUSSION........................................................................ CHAPTER 7 : CONCLUSION............................................... ............................................. REFERENCES............................................................................................

TABLE OF FIGURES Figure 1: World consumption of Acetaldehyde 2009 ........................................ ............ Figure 2: Concentration Profile Down a CSTR in term of Residence Time..........................

CHAPTER 1 BACKGROUND Although the demand of acetaldehyde has significantly declined due to the mature end-use markets and the effects of the economic downturn on these acetaldehyde-derived products, the overall global market for acetaldehyde is expected to grow 2-3% annually during 20092014. The following pie chart displays the world consumption of acetaldehyde.

Figure 1: World consumption of Acetaldehyde 2009

Source: Malveda M. & Funada C. (2010) Acetaldehyde from http://www.sriconsulting.com/CEH/Public/Reports/601.5000/

The economics of the various processes to produce acetaldehyde are strongly dependent on the price of the feedstock used. Since 1960, the liquid phase oxidation of ethylene has been the process of choice. Nevertheless, there is still commercial production by the partial oxidation of ethanol, dehydrogenation of ethanol and hydration of acetylene. Acetaldehyde is also formed as a co-product of reaction between ethanol and acetic acid. In the chemical process industry, it is often the case that one or more reactants are converted to one or more desired chemicals under conditions such that the desired chemicals can also react further to form undesired by-products. One example is in the cracking of crude oil, where high molecular weight non-volatile liquid reactants are converted to intermediate molecular weight volatile liquids suitable for gasoline, but these intermediate molecular weight liquids also react to form low molecular weight gases. Such gases, although sold, are worth less than the intermediate molecular weight volatile liquids. So the goal is to form the volatile liquids as much as possible, while avoiding the liquids to react further and produce unwanted gases.

For this project, the oxidation of ethanol to form acetaldehyde is carried out on a catalyst of Unfortunately, acetaldehyde is also oxidized on this catalyst to form carbon dioxide. CH3CH2 OH (g) CH3CHO 2CO2 (1)

The simplest representation of a system with the general features described above involves two reactions: A B C B C (2) (3) (4)

Reaction 1: A Reaction 2: B

Where B is the desired product (acetaldehyde) C is not desired (carbon dioxide) According to the ICIS pricing list, it is reported that the Asian hydrous ethanol; which is used as the feed material of the acetaldehyde production, was largely stable at record highs of the mid $900s/tonne CFR (cost and freight) northeast and southeast Asia. In addition, US market review stated that industrial ethanol contracts were steady in February, after rising by around 30 cents per gallon in January due to higher corn prices. The increase in January put 190proof ethanol contracts at $3.25-3.50/gal (RM9.80 RM10.56/gal) and 200-proof grade at $3.50-3.65/gal (RM10.56 RM11.01/gal). Meanwhile, SBIO Informatics had estimated the costs of 150 TPD acetaldehyde production plant in 2002, which are as follow: Fixed Capital Cost Direct Production Cost Total Production Cost Net Profit Rate of Return = Rs 2.13 billion (RM 144 million) = Rs 3.51 billion (RM 238 million) = Rs 5.67 billion (RM 385 million) = Rs 0.69 billion (RM 47 million) = 25%

CHAPTER 2 PROBLEM STATEMENT AND OBJECTIVE FUNCTION

Given the reaction described above, we wish to find the following quantities:
y

Maximum value of B that can be realized in well-mixed reactors operated in steadystate continuous mode

y y

The time or residence time at which this occurs, in continuous mode The reactor volume required to produce 100 moles B/hr, in continuous mode

The following information is given: CA,o = 1 mole/L; k1 = 3 hr-1; CB,o = CC,o = 0; k2 = 0.7 hr-1

Reaction time for the continuous reactor = mean liquid residence time = Where V = system volume Q = volumetric flow rate

= ,

Assume that the reactors are well-mixed and have constant volume, that the reactions occur in the liquid phase, as well as that the input and output liquid flow rates are the same for continuous reactor.

CHAPTER 3 FORMULATION OF THE SYSTEM MODEL

1. The rate laws. Based on the indicated mechanism, we can write the rate laws for each chemical species: rA = -k1CA (5)

rB = k1CA k2CB (6) rC = k2CB (7)

2. Material balance equations For a continuous reactor, the material balance equation is of the form (for A) (8)

We are only interested in the steady state response, so set the derivative to zero. CA,in CA + rA = 0 where = V/Q and Cout = C for a well-mixed reactor. (9)

We write an equation for each species, and substitute the rate laws to obtain three algebraic equations: CA,in CA + k1CA = 0 (10)

CB,in CB + (k1 CA k2CB) = 0 (11) CC,in CC + k2CB = 0 (12)

Only A is put into the reactor, at a concentration CA,in = CA,o, and CB,in = CC,in = 0. Solving the equations, (13) (14)

(15) Again, CA + CB + CC = CA,o, as they should. In this problem, the independent variables is the residence time, = V/Q.

3. Since the objective function is to maximize the concentration of B, equation (14) will be optimized in MATLAB Simulation. (16) where, x = (residence time, hr) k1 = 3 (rate constant for reaction 1, hr-1) k2 = 0.7 (rate constant for reaction 2, hr-1) CA,o = 1 (initial concentration of A, mole/L)

By substituting the above values, equation (16) becomes; (17) (18)

Since we want to maximize the value of objective function, the function becomes f(x) and thus equation (18) become; (19)

4. Choosing optimization method Since this is an unconstrained function with one dimensional search, we have decided to use the Quasi-Newton Method to solve the problem.

CHAPTER 4 ALGORITHM

CHAPTER 5 MATLAB SIMULATION By using MATLAB 2007a, the following program is developed based on the algorithm in Chapter 4. For Optimization >> fun = inline('(-1)*((3*x)/(2.1*x^2+3.7*x+1))'); >> x0 = 0.2; %initial guess >> options = optimset('LargeScale','off','Display','iter'); >> [x, fval, exitflag, output] = fminunc(fun, x0, options);

Result First-order Iteration 0 1 2 3 4 5 6 7 Func-count 2 4 6 10 12 14 16 18 f(x) -0.328947 -0.439288 -0.444068 -0.454613 -0.454641 -0.454664 -0.454664 -0.454664 1 1 0.474323 1 1 1 1 Step-size optimality 0.826 0.074 0.0664 0.00672 0.00433 0.000149 3.44e-006 0

Optimization terminated: relative infinity-norm of gradient less than options.TolFun. >> x

x=

0.6901

>> fval

fval =

-0.4547

>> output

output =

iterations: 7 funcCount: 18 stepsize: 1 firstorderopt: 0 algorithm: 'medium-scale: Quasi-Newton line search'

message: 'Optimization terminated: relative infinity-norm of gradient less than options.TolFun.'

Plotting the graph >> CA0 = 1; % Moles/L >> k1 = 3; % 1/hr >> k2 = 0.7; % 1/hr >> theta = linspace(0,4); >> CA = CA0 ./(1 + k1*theta); >> CB = theta.*k1.*CA./( 1 + theta*k2); >> CC = theta.*k2.*CB; >> plot(theta,CA, theta,CB,':', theta,CC,'--'), grid >> xlabel('Residence time, \theta [hours]'), ylabel('C [moles/L]') >> legend('C_A','C_B','C_C')

CHAPTE 6 E Result B it t ti ti M i t
1 C 0.9 0.8 0.7 C [m oles /L] 0.6 0.5 0.4 0.3 0.2 0.1 0 C C
A B C

LT AND DISCUSSION

B t

i l t i

l ti l

t it i

ti i it t ti

l ti B t

t ti l

t t l

0.5
opt

1.5 2 2.5 R es idenc e tim e, U [hours ]

3.5

Fi Discussion i i ti

:C

t ti

il

Ri t

R i

t ti

B i l ti

t l ti it i :

l /lit

it

(20)

(21)

To produce 100 moles/ r wit t is process, we would need a reactor volume of: (22) (23)

CHAPTER 7 CONCLUSION Acetaldehyde is produced via the oxidation of ethanol by using a catalyst of 4 wt% Cu-2 wt% Cr on Al2 O3 in a continuous stirred tank reactor (CSTR). However, the process also forms an undesired by-product which is carbon dioxide. After simulating the process using MATLAB 2007a software with Quasi-Newton Optimization Method, a residence time of 0.69 hours is obtained with a total of seven (7) iterations and a function count of 18. From the graph, the optimum concentration of acetaldehyde which is about 0.45 moles per litre is obtained at the optimum residence time. Finally, a CSTR of 152 L or 0.152 m3 is required to produce 100 moles per hour of acetaldehyde.

REFERENCES 1. H. Scott Fogler, Elements of Chemical Reaction Engineering 2. ICIS. Ethanol Prices and Pricing Information obtained from

http://www.icis.com/V2/chemicals/9075312/ethanol/pricing.html 3. MathWorks from www.mathworks.com 4. Reacting System Examples Engineering Sciences 22 from www.darthmouth.edu 5. SBIO Informatics (2002). Acetaldehyde Cost: Estimation & Economics. Obtained from http://www.sbioinformatics.com/design_thesis/Acetaldehyde/Acetaldehyde_Cost2520Estimation&Economics.pdf 6. Malveda M. & Funada C. (2010). Acetaldehyde obtained from http://www.sriconsulting.com/CEH/Public/Reports/601.5000/ 7. Currency converter obtained from http://coinmill.com