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Kinetics of Condensation Reaction of Crude Glycerol with Acetaldehyde in a Reactive Extraction Process

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Abstract Glycerol is formed as a byproduct in biodiesel production from vegetable oils and animal fats. Today more than 20 Mt / annum of fats and oils are processed chemically, yielding large amounts of glycerol. One ton of biodiesel yields about 200 kg of crude glycerol stream or about 100 kg of pure glycerol. As per 2008 scenario, bio-diesel process is the 2nd largest producer of glycerol. Due to the setting up of number of bio-diesel plants the average demand for the glycerine (3.5 %) has become much less than the supply (5.2 %). There by the price of glycerol has come down. To increase its demand the glycerol has to be obtained in its purest form for further applications to get value added products. The crude glycerol driven from biodiesel is of poor quality and requires expensive refining before it is suitable for use as a food or pharma grade product. Conventional processes for glycerol purification comprises of the following steps: Pretreatment, concentration, purification and refining. The pretreatment step is used to remove colour and odor matters as well as any remaining fat components from crude glycerol. The purification step will remove inorganic salts, fat and soap components, colour and odor causing matters. The final concentration of glycerol to 99.5% is carried out in vacuum (0.5-1 Kpa) in forced circulation evaporators. The above purification steps increase the total production cost and moreover the process is energy intensive. The heat required per kg of recovered material is high and the purification steps increase with increase in impurity levels. Research on different methodologies for achieving pure glycerol other than the conventional approach is the need of the hour. An alternate easier recovery of pure glycerol is by reactive extraction. In this area the work presented in the paper suggests recovery of glycerol by reversible reactions. Compared to evaporation and distillation, extraction process is advantageous as the energy requirement is lower. The reactive extraction route includes acetalization reaction followed by hydrolysis reaction. The process utilizes an acid catalyst for condensation reaction of glycerol with aldehyde to form acetals. These acetals were extracted using toluene, and the extracted acetal is hydrolyzed to recover the glycerol. As both the reactions are equilibrium limited, the reactions are forced to completion by extracting the reaction product continuously. The present work involves the kinetic study of this acetalization reaction using acetaldehyde. This study is a part of ongoing research on recovery of glycerol by reactive extraction technique. Thermo chemistry of the reaction indicated that the reaction is highly reversible and equilibrium limited reaction. The reaction is pushed forward by continuous extraction of the product formed. Process optimization by studying the parameters like

temperature, mole ratio of the reactants, and agitation was carried out to get for maximum conversion & high yield of glycerol. The experimental results were found to fit a 2nd order rate equation for the forward reaction. The influence of temperature on the kinetic constants was determined & the activation energy was obtained. Introduction Glycerol is produced as a side product in the transesterification of vegetable oils during biodiesel production. The crude glycerol contains methanol, water, alkali, soap and organic matter. It is conventionally refined through filtration, chemical additions and distillation to yield an industrial grade glycerol with purity close to 90%. When glycerin is used in food, cosmetics, and drugs, further purifications such as bleaching, de-odorizing, and ion exchange treatment are needed to remove all trace impurities and get purity close to 99.9% [1]. With increased production of biodiesel market more and more crude glycerol is continuously generated. Research is therefore needed to explore effective ways of the glycerol utilization. Moreover separation and recovery of glycerin through processes that are less energy intensive as compared to the existing technologies need to be developed. Presently biodiesel production using crude vegetable oils involves two stages. An acid catalyzed esterification step followed by a base catalyzed transesterification step [2-5]. The esterification is carried out to convert the high concentration of free fatty acids present in the oil to alkyl ester and the transesterification is carried out to convert the triglycerides to the corresponding alkyl ester. The commonly used catalysts being sulfuric acid for esterification, potassium hydroxide and sodium hydroxide for transesterification reaction and the most preferred alcohol methanol [6]. After the final processing is completed the product is obtained in two layers: the methyl ester layer and the glycerol layer. The product layers are separated, weighed and analyzed after which the biodiesel layer is washed with water and dried to get methyl ester with high purity and yield [7]. The purification steps involved in the treatment of the biodiesel glycerol is largely based on the requirement of the final purity of glycerol. The crude glycerol contains glycerol 33%, methanol 49.6%, fatty matter 0.07% and free fatty acids. In some biodiesel processes the transesterification reaction is done in two stages wherein the first stage the glycerol layer is obtained. In the second stage the glycerol formed during the reaction is present in the biodiesel layer and no separate layer is formed. This glycerol lost during the washing of the biodiesel layer ranges from 4-6% by weight. In the present work, the washed water effluent layer from biodiesel washing stage is combined with the crude glycerol stream as a result the methanol and the glycerol from the biodiesel layer are recovered during glycerol recovery. Due to the addition of the water effluent layer the concentration of glycerol in the stream is reduced greatly. Conventionally recovery of glycerol from aqueous solutions is usually achieved in multiple effect evaporators or distillation. The heat required per kg of recovered material is high and the purification steps increase with increase in impurity levels. Different methodologies for achieving pure glycerol other than the conventional approach may prove to be more energy efficient. An alternate easier recovery approach is by reactive extraction. The present study is therefore focused mainly on recovery of glycerol from aqueous streams by reversible reactions.

Compared to evaporation and distillation, extraction process is advantageous as the energy requirement is lower [8, 9]. The recovery of pure glycerol from aqueous effluent streams via reversible reactions is studied in the present work. The reactive extraction route followed by hydrolysis is adopted for the present process. The process utilizes an acid catalyzed condensation reaction of glycerol with acetaldehyde to form glycerol acetal. The acetal is hydrolyzed to recover the glycerol. As both the reactions are equilibrium limited, the reactions are forced to completion by removing the reaction product continuously. Research on extraction of poly hydroxyl compounds was carried out by Tink et al [10]. The authors had applied the technique to extract sugars and sugar alcohols from dilute solutions by cyclic acetal formation. Robert et.al [11] studied the recovery of 1, 2-propanediol and 1,3propanediol from a dilute aqueous solution through cyclic acetalization with formaldehyde and acetaldehyde. The acetals obtained in the reaction were separated from the solution by distillation or extraction. Atul et al [12] and Chopade et al [13] reported the recovery of 1,2propanediol and ethylene glycol from an aqueous solution via reactive distillation; the acetalization reaction was also carried out with formaldehyde or acetaldehyde. Malinowski et al [14] reported the recovery of PDO by cyclic acetalization with acetaldehyde to form 2-methyl-1, 3-dioxane; the acetal was recovered by o-xylene, toluene, or ethylbenzene extraction, but the hydrolyzation of the acetal was not studied. Broekhuiset et al [15] compared reactive distillation and reactive extraction via acetalization with formaldehyde or acetaldehyde to conventional separations for the recovery of PG from dilute solution. Chopade et al [16] studied the recovery of EG from aqueous solution via acetalization with formaldehyde using ion exchange resins as catalysts in batch and continuous reactive distillation. Chopade et al [17] have also generated the vapor pressures of the acetals and vaporliquid equilibrium data for 24DMDwater and 2MDwater. Reaction equilibrium constants for acetalization were measured via simple batch experiments. Moreover the same authors [18] have developed a method for recovery of EG or PG from aqueous glycol streams produced via epoxide hydration. The present work is a part of the work related to the process development for biodiesel production using crude vegetable oils. In the present work the recovery of glycerol is carried via reversible reactions. The condensation reaction of glycerol with acetaldehyde to form glycerol acetal, followed by hydrolysis of acetal to recover the glycerol. The glycerol acetal formed during the condensation reaction is continuously extracted using toluene as the solvent. Present work is focused on the kinetics of this reactive extraction process. The new route for recovery of pure glycerol from crude glycerol stream is less energy intensive than the existing conventional purification processes.

Experimental

The crude glycerol stream after the addition of the effluent water streams is alkaline in nature because of the alkali catalyst. The pretreatment step involves acidification with sulfuric acid to pH 3-4. The soap and alkali present in the mixture is converted to FFA in this stage. The FFA being insoluble separates out at the top as a layer and is filtered out. The salt remains dissolved in the mixture. The remaining mixture is subjected to distillation to recover the alcohol present in the system. The crude glycerol then contains glycerol 42%, water 46 %, fatty matter 6% and dissolved salts 6%. The reversible reactions are carried out after the pretreatment step to recover glycerol in pure form. Chemicals Acetaldehyde (28 %), toluene (99.8 %), and catalysts sulphuric acid and amberlyst-15 were purchased from SD fine chemicals, India. The chemicals were used without further purification and amberlyst -15 was used in acidic form. Experimental procedure Preparation of the glycerol acetal from crude glycerol was carried out in a 500 ml four necked jacketed glass reactor equipped with a condenser, overhead stirrer, provision for temperature measurement and sample withdrawal. The temperature in the reactor was maintained by circulating hot fluid through a thermostat. The condenser temperature was maintained by circulating chilled water. A typical run was started by charging the reactants and extracting solvent into the reactor. The reaction was initiated with the addition of the catalyst after the desired temperature was attained. Samples were drawn periodically and analyzed. The acetal formed was continuously extracted from the aqueous layer by the addition of a solvent like toluene. Water formed in the reaction is retained in the aqueous layer. After completion of the reaction the two product layers were separated, weighed and analyzed. The final reaction mixture was also analyzed to get values for the equilibrium constant at various temperatures. Analysis The layers obtained were analyzed for the distribution of the acetal in both the phases. The analysis was carried out on a Gas Chromatograph GC-17A, FID detector. An FID detector was utilized for analysis of organic layer. The column used was 5% SE-30, initial temperature 130 oC, final temperature 210 oC, rate 10 oC/min, injector temperature was 220 oC and detector temperature 230 oC. Nitrogen was used as carrier gas. After equilibrium was attained also the analysis was carried out. The aqueous layer was analyzed for glycerol concentration by, sodium periodate method. Experimental details Experiments were carried out at four different temperatures (5, 10, 15, 20 & 25 oC respectively), with 1:1 mole ration of glycerol to acetaldehyde. The effect of temperature on the conversion of glycerol and the extraction of glycerol acetal was determined. Based on the conversion time data the kinetics were established. Results and Discussion

Thermo chemistry The feasibility of the condensation reaction with acetaldehyde is checked by calculating the free energy. The standard heat of reaction at 25 oC was calculated to be 91.6 kJ/mol, Gibbs free energy of reaction at 25 oC was 125 kJ/mol. The estimated values indicate that the conversion of glycerol to glycerol acetal using acetaldehyde is an endothermic in nature and therefore the conversions are expected to increase with increase in temperature. However as the boiling point of acetaldehyde is 21 oC and it is volatile in nature all the reactions are conducted at temperatures lower than 25 oC. The equilibrium constant K was calculated from the experimental data at different temperatures using the expression given below.
K= [ glycerolac etal ][ water ] . (1) [ glycerol ][ acetaldehy de ]

Effect of Temperature The conversion of glycerol to glycerol acetal increased with increase in temperature and the trend is depicted in Figure 2. As is evident from the plot the maximum conversion attained is 88%.
100 90 80

% Conversion of glycerol

70 60 50 40 30 20 10 0 0 5 10 15 20
0

25

30

Temperature C

Figure: 2 Effect of temperature on conversion of glycerol for the condensation reaction of glycerol with acetaldehyde.

The effect of temperature on the distribution ratio of toluene is given in Figure 3.

10

KD
4 2 0 5 10 15 20
0

25

30

Temperature, C

Figure: 3 Effect of temperature on the distribution ratio for acetaldehyde-glycerol reaction

The extraction efficiency calculated based on the weight fraction of the product in extractant layer to that of the raffinate layer when obtained at different temperatures showed marked increase in the efficiency with increase in temperature as is shown in Figure 4.
100

90

80

70

60

50

40

30 5 10 15 20
0

25

30

Temperature C

Figure: 4 Effect of temperature on extraction efficiency for acetaldehyde-glycerol reaction.

Kinetic Interpretation The following reaction takes place during the condensation reaction of glycerol with acetaldehyde
Glycerol + Acetaldehy de Glucerolac etal +Water

All the reactions were carried out at 1:1 molar ratio of glycerol to acetaldehyde hence a second order elementary kinetic expression was assumed.
rA = k1C AC B k 2C R C S . (2)

Where CA, CB, CR & CS represents the concentrations of glycerol, acetaldehyde, glycerolacetal and water respectively. The equilibrium constant K is defined as:
k1 . (3) k2 Solving the above rate equation gives K=
ln K ( X A 1) X A = 2 K k 2 C AO t .. (4) K ( X A 1) + X A

Where XA represents the conversion of glycerol and CAO represents the initial concentration. The value of K is obtained from equation (1). The experimental data of XA vs. t is confronted with the above equation to get the value of k2 while the rate constant k1 is calculated form the equation (3). A plot of equation (4) at a tmeperature of 10 oC is shown below

2.25

Y = 0.5899*t 2 R = 0.92

1.50

Y
0.75 0.00 0 1 2 3 4

Time, t

Figure: 5 Plot of Y vs. t, where Y is defined as ln

K ( X A 1) X A in the equation (4) K ( X A 1) + X A

The slope obtained from the above graph gives the value of k 2. The rate constant k1 is calculated by the equation (3). Similar calculations were done at other temperatures and the corresponding rate constants are shown below Temperature (oK) 278 283 288 293 k1 (lit/mol.hr) 0.0244 0.0445 0.09 0.147 k2 (lit/mol.hr) 0.0385 0.0531 0.0686 0.0951

The Arrhenius plot for the forward reaction is shown below

-2.0

ln k1= -9917.6*(1/T) + 31.964

-2.4

ln k 1

-2.8

-3.2

-3.6

0.00340

0.00344

0.00348

0.00352
o

0.00356

0.00360

1/T, (/ K)

Figure: 6 Arrhenius plot for the reaction

From the above graph the slope (-Ea/R) = -9917.6. Activation energy (Ea) = 9917.6*1.984 = 19676.52 cal/mol Conclusions The recovery of glycerol in its purest form from aqueous solutions containing impurities such as salts and solvents is achieved in this paper. The glycerol in the aqueous solution is converted to glycerol acetal by reaction with acetaldehyde, extracted into an organic layer and hydrolyzed back to glycerol. Chemical equilibrium limitations do not allow the reaction to proceed to an appreciable extent therefore simultaneous extraction of the product acetal into the toluene pushes the reaction forward. The kinetics of the reaction showed that the activation energy is 19.67 kcal/mol, which indidates that the reaction proceeds well in the low temperature region. The reactive extraction approach is an attractive alternate route for attaining pure glycerol.

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