A PROJECT REPORT OF PLANT DESIGNING TOPIC CATALYTIC PRODUCTION OF CALCIUM PROPIONATE GROUP MEMBERS H. M. Absar Raza (H-1601040) H.M. Owais (H-1601042) Hasna Salman Ahmed (H-1601047) Iqra Wasi (H-1601052) Jabeen Fatima (H-1601055) 1 INDEX Chapter 1 ……………...………………………………….INTRODUCTION Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 2 Calcium Propionate Calcium propionate (also known as E282) is an organic salt formed by the reaction of calcium hydroxide with propionic acid (also known as propanoic acid). Its chemical formula is Ca(OOCCH2CH3)2 . The compound occurs in either crystalline or powder form. It is soluble in water and only very slightly soluble in alcohol . INTRODUCTION Bakery products are an important source of nutrients, energy, protein, iron,calcium and several vitamins. Physical spoilage of bakery products usually involves moisture loss or gain leading to a loss of texture or mold growth. Microbiological spoilage is often the main factor limiting the time period of bakery products. Spoilage from microbial growth causes economic loss for both manufacturers and consumers. This problem usually occurs in the summer season when the climate is warm and humid. Physical factors are the important factors governing mold free time period of bakery products. It plays a decisive role when molds compete with bacteria to spoil high moisture foods . Preservatives are most commonly used to control mold growth in baked goods Propionic acid, an aminocarboxylic acid (CH3CH2-COOH), is a naturally occurring organic acid and is an oily liquid with a slightly pungent, disagreeable rancid odor. Its salts are white, free-flowing powders with a slight cheese-like flavor Propionates were selected on the basis that higher MW fatty acids had a higher antimicrobial effect. This acid or its salt are often wont to prevent the bacterial spoilage of bread known as rope caused by certain Bacillus sp . Several studies have also reported the effects of propionic acid and its salt on mold growth. Concentrations of propionate starting from 8 to 12 per cent have been reported effective in controlling mold growth on the surface of bakery products Studies indicate that calcium propionate is one of the safest food additives used by the food industry. Rats fed a diet containing nearly 4% calcium propionate for a year showed no ill effects. As a result, the U.S. Food and Drug Administration has placed no limitations on its use in foods. In addition to baked goods, it is commonly used as a preservative in chocolate products, processed cheeses, and fruit preserves. The tobacco industry has also used calcium propionate as a preservative in some of its products. Properties of Calcium Propionate Physical and Chemical Characteristics of Calcium Propionate Calcium propionate is an organic salt obtained from the reaction between calcium hydroxide and propionic acid and has the molecular formula (CH3CH2COO)2Ca. The compound exists in either crystalline or powder form. Calcium propionate is soluble in water and can be hydrolyzed into Ca2+ and propionic acid. The solution is alkaline, but exerts bacteriostatic effects in acidic media. Antibacterial Properties of Calcium Propionate The antimicrobial effect of calcium propionate depends on the pH value of the product because the undissociated acid has a better antimicrobial effect than the dissociated acid. Compared to 71% undissociated propionic acid at pH 4.5, only 7% of the propionic acid can be un dissociated at pH 6. An enhanced inhibitory effect of calcium propionate at a lower pH 3 is expected, and the maximum pH at which calcium propionate exerts measurable antimicrobial activity is approximately 5.0–5.5 . Therefore, a lower pH is beneficial to the improvement of the antibacterial properties of calcium propionate under appropriate conditions.Because of its antimicrobial properties, calcium propionate can also reduce mold and act as a preservative in many industries Nutritive Properties of Calcium Propionate Calcium and propionic acid in solution are indispensable sources of nutrients for ruminants.Calcium is essential for the formation of skeletal tissue, transmission of nervous tissue, muscle contractility, and essential minerals for blood and milk.The role of calcium with respect to the immune function and intermediary metabolism explains the contribution of subclinical hypocalcemia to the development of several diseases observed in early lactation and underlines its importance in high-performing dairy cows. Oral calcium supplementation with calcium propionate, which is a calcium source in solution, can be greatly absorbed by the rumen and increase the ionized calcium concentration in the blood. APPLICATIONS Its utilization restricts the growth of mold and reproduction of mold and other microorganisms and increases the shelf life of the product. Commonly Calcium Propionate is used as food additive or preservative for many food products including bakery items, dairy products, pharmaceutical industry, beverages & meat processing, cosmetics items, fruits processing. Majorly bread and other bakery goods such as pastries, pizza doughs were kept fresh or preserved by calcium propionate during processing. Calcium Propionate also acts as an antimicrobial agent in pharmaceutical products for killing microorganisms such as bacteria, algae, viruses and fungi.. It is used and as a feed supplement & to prevent milk fever in cows in agricultural fields. Beyond food preservative, calcium propionate also utilizes as the paints and coating additive, also finding some application in the butyl rubber production. SYNTHESIS ROUTE Screening Calcium propionate is produced by the neutralization of propionic acid with calcium hydroxide. C2H5COOH + Ca(OH)2 → Ca(OOCC2H5)2 + 2H2O 4 But for the production of propionic acid, there are 4 different routes on the basis of chemical or biological methods. Chemical Methods 1. Reppe’s Process (Oxo Process) In this process, propionic acid is produced by the hydroformylation of ethylene which gives propionaldehyde with n-propanol as a major product. Both have different industrial applications. Reaction of ethylene and syngas takes place in the presence of Rhodium at the temperature of 100 O C and pressure of 15 atm. Ethylene + Syngas ➝ Propionaldehyde Now, propionaldehyde undergoes the oxidation process to give propionic acid at 60 90OC and 2 atm.. Propionaldehyde + Oxygen ➝ Propionic acid 2. Larsons’s Process Major product of this process is propionic acid along with ester. Operating conditions for this reaction are, temperature 125 - 1600 O C, pressure 16 - 25 atm and boron trifluoride used as a catalyst. Ethanol + Carbon Monoxide ➝ Propionic acid 3. Fischer-Tropsch Process In this chemical method, a mixture of carbon monoxide and hydrogen converts into many liquid hydrocarbons. Now, separation of propionaldehyde occurs then it proceeds with the oxidation to give propionic acid. Relatively extreme operating conditions apply during reaction. High temperature and pressure are favorable for high conversion rate. Carbon Monoxide + Hydrogen ➝ Liquid Hydrocarbons ➝ Oxidation ➝ Propionic acid Biological Method 4. Fermentation Process Propionic acid is also produced by the fermentation process using renewable sugars such as glucose, sucrose etc. Propionibacterium shermanii (Propionic acid bacteria) produces acid as a product of their anaerobic metabolism of sugars. Selection: Reppe’s Process for the catalytic production of Propionic Acid. 5 SELECTION CRITERIA ● ● ● ● ● ● The main objective of this project is to produce propionic acid catalytically. Reppe’s process generally proceeds with relatively lower operating conditions (i.e. temperature and pressure). No separation required for propionaldehyde as required in Fischer Tropsch Process. High yield with high selectivity is obtained by the oxidation of propionaldehyde that means less undesirable material. Lower operating conditions lowers the energy consumption and leads to economical production of acid. Less explosion risk due to the low process temperature. INPUT OUTPUT DIAGRAM Stage 1: Input output diagram for the production of propionic acid. 6 Stage 2: Input output diagram for the production of calcium propionate.. MATERIAL BALANCE Balanced equation for Reppe’s Process: C2H4 (28.05 g/mol) + CO (28 g/mol) + H2 (2 g/mol) → CH3CH2CHO (58.08 g/mol) ---- Eq 1 2 CH3CH2CHO (58.08 g/mol) + O2 (32 g/mol) → 2 C2H5COOH (74.08 g/mol) ---- Eq 2 Balanced equation for Neutralization of propionic acid to calcium propionate.: 2 CH₃CH₂COOH (74.08 g/mol) + Ca(OH)2 (74.09 g/mol) → Ca(C2H5COO)2 (186.22 g/mol) + 2 H2O (18 g/mol) ---- Eq 3 FOR 100 gm PRODUCTION OF CP Using Eq 3 148x100/186 + 74x100/186 → 186x100/186 + 36x100/186 79.56 g + 39.78 g → 100 g + 19.35 g Using Eq 2 For 100 gm production of CP we need 79.56 gm of propionic acid 116x79.56/148 + 32x79.56/148 → 148x 79.56/148 62.35 g + → 17.2 g 79.56 g Using Eq 1 For 79.56 gm production of propionic acid we need 62.35 gm of propionaldehyde 28x62.35/58 + 30x62.35/58 → 58x 62.35/58 30.1 g 7 + 32.25 g → 58 g
