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Ind. Eng. Chem. Res.

2011, 50, 1003–1011

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Reactive Extraction of Itaconic Acid Using Quaternary Amine Aliquat 336 in Ethyl Acetate, Toluene, Hexane, and Kerosene
Kailas L. Wasewar,*,† Diwakar Shende,† and Amit Keshav‡
Department of Chemical Engineering, VisVesVaraya National Institute of Technology, Nagpur 440010, India, and Department of Chemical Engineering, National Institute of Technology (NIT) Raipur, Chhattisgarh 492010, India

The synthesis method of producing itaconic acid by catalytic condensation of succinic acid and formalin is unsustainable and expensive because it requires huge chemicals, consumes more energy, and discharges harmful chemicals. Production of this acid by fermentation is a relatively clean and less expensive process. The highest cost factor for the acid is the recovery of acid present in dilute form. Reactive extraction is one of the cleaner and more energy-efficient technologies for the recovery of carboxylic acids from dilute streams. Reactive extraction of itaconic acid from aqueous solution using Aliquat 336 (quaternary amine) as the extractant in various diluents was studied. The study highlighted the effects of ester (ethyl acetate), inert (kerosene), aromatic (toluene), and alkane (hexane) on the degree of solvation/ion exchange of the extractants. A comparison among the different categories of diluents was made. The results were presented in the form of distribution coefficient, loading ratio, and equilibrium complexation constant. In most cases, a 1:1 acid-amine complex was observed. Also, attempts were made to relate the distribution coefficient with the various physicochemical properties of the diluent.
1. Introduction Itaconic acid is a dicarboxylic acid that is soluble in water, acetone, and ethanol, moderately soluble in acetic acid, slightly soluble in organic solvents, and very slightly soluble in benzene, chloroform, ether, carbon disulfide, and petroleum ether. Itaconic acid is a functionalized analogue of acrylic acid, the simplest conjugated alkenoic acid.1 Itaconic acid finds its place in various industrial applications. It is used in paints to improve the quality and as a fiber carpet sizing agent to make carpet more durable. Itaconic acid can react with acrylic and methacrylic acid or their esters to prepare resins that can be widely used in emulsion coating, leather coating, and coatings for cars, refrigerators, and other electrical appliances to improve adhesion, color, and weather resistance. With (chloroalkyl)dimethylbenzylammonium chloride added, they can be used to prepare a water-soluble coating for food packaging to reduce bacteria contamination. Esters of itaconic acid can be used in paint, ion-exchange resin, lubricant, binder, plasticizer, and sealant and molding plastics. Itaconic acid polymer has a special luster and transparency; it is fit for making synthetic cut stone and special lens. Itaconic acid can be manufactured by the catalytic condensation of succinic acid derivatives with formaldehyde.2 Although the synthesis process is simple, it still suffers from a number of disadvantages: consumption of lot of chemicals, high energy utilization, and harmful byproduct generation. Fermentation is a relatively clean method to manufacture itaconic acid. Aspergilluss terreus species, grown under phosphate-limited conditions, are known to produce itaconic acid by fermentation.3 Fermentation is an important replacement in the petrochemical route for the production of a wide range of carboxylic acids like propionic acid, lactic acid, acetic acid, citric acid, etc. A stumbling block in the use of fermentation to produce these
* To whom correspondence should be addressed. Phone: +91-7122801561. Fax: +91-712-2223230 or -2223969. E-mail: k_wasewar@ rediffmail.com. † Visvesvaraya National Institute of Technology. ‡ National Institute of Technology (NIT) Raipur.

acids is the difficulty in recovery from dilute solutions, in which they are produced. The main problem with fermentation technology is that, as the acid is generated, the pH of the system falls. Lowering of the pH destroys the bacterial species responsible for growth. This leads to low acid product yield and concentration. A number of recovery methods are available like precipitation, distillation, membrane bioreactor, liquid surfactant membrane extraction, adsorption, direct distillation, electrodialysis, reactive extraction, reverse osmosis, anionexchange distillation, supported membranes, etc.4 Calcium hydroxide precipitation is the industrially used recovery method. However, it has a few shortcomings: consumption of large quantities of reagents (H2SO4 and lime); a huge amount of waste generation per ton of acid produced; waste disposal problem, and very poor sustainability. Dialysis has good potential but has drawbacks of the need for frequent cleaning, membrane fouling, and the requirement of a large dialysis unit compared to the fermenter. Electrodialysis allows the simultaneous separation and concentration of the acid but requires higher power consumption. Ion exchange is a reliable technology but requires a large amount of chemicals and has huge waste generation. The distillation method is a well-established technology. Its drawbacks are the formation of high-boiling internal esters and dimers and consumption of more power.4 Reactive extraction with the proper selection of diluents and extractants can provide high selectivity and extraction but suffers from toxicity problems of the solvents toward microbial strains. Recovery of solute species can be achieved by solvent extraction, and reactive extraction has received increasing attention.5-10 Each of the above separation methods has their advantages and disadvantages, yet reactive extraction is one of the sustainable technologies, widely used for carboxylic acid extraction. With proper selection of the extractant and diluents, reactive extraction can be proven to be an efficient and reliable process with higher concentration and recovery of the acid. Generally, the acid content in fermentation broth/waste stream sources is less than 10% w/w. The separation, purification, and preconcentration of itaconic acid is rather difficult due to its

10.1021/ie1011883  2011 American Chemical Society Published on Web 12/15/2010

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Ind. Eng. Chem. Res., Vol. 50, No. 2, 2011

chemical behavior because it has a strong affinity to water. The high solubility in water causes traditional solvents such as alcohols, ethers, esters, and inert diluents (hexane, n-heptane), etc., to give low distribution coefficients. Thus, physical extraction with conventional solvents is not an efficient method for the recovery of itaconic acid. In order to increase the selectivity and yield of acid, a combination of diluent with an extractant, which can chemically complex with acid, was tried.4-9 The improved results laid down the establishment of technology of reactive extraction for the recovery of carboxylic acids. The advantages for extractive fermentation include high reactor productivity, ease in reactor pH control without requiring base addition, and use of a high-concentration substrate as the process feed to reduce process wastes and production costs. Extractive fermentation also allows the process to produce and recover the fermentation product in one continuous step and to reduce the downstream processing load and recovery costs. Reactive extraction involves the use of an extractant-diluent system to extract the acid. Extractants are usually classified as (i) anion-exchange extractants (e.g., aliphatic primary, secondary, and tertiary amines), which form ion pairs (salts) in an acidic medium, (ii) cation-exchange extractants (e.g., phosphine and phosphoric acid), which exchange proton with the cation, (iii) solvating extractants (e.g., phosphoric and phosphinic acid, esters, and phosphinoxides), which are Lewis bases and form nonstoichiometric compounds with neutral solutes, and (iv) chelate-forming extractants (e.g., aliphatic and aromatic hydroxyines), which exchange the cation and form coordinate binding.7 Extractants are generally viscous or solid, so they are dissolved in diluents, which improve their physical properties like the surface tension and viscosity. Diluents provide the solution of the extractants and also general and specific solvation to the acid-extractant complexes formed. Polar diluents are more favorable than zero-polarity, low-dielectric-constant, aliphatic or aromatic hydrocarbons. Solvation of the whole extractant-acid complex is based on dipole-dipole interaction and was found to play an important role in the neutralization reaction between acid and extractant, which is promoted by increasing the polarity of the diluent. Wide literature is available on reactive extraction of different carboxylic acids from aqueous streams, but very few can be found for extraction of itaconic acid from dilute streams. The extraction of dicarboxylic acids (itaconic, maleic, malic, oxalic, tartaric, and succinic acid) from aqueous solutions with tributylphosphate dissolved in dodecane was studied at different volume-phase ratios.10 Hano et al.11 (1990) studied the extraction equilibria of different organic acids using tri-n-octylphosphine oxide (TOPO) in hexane. TOPO + hexane, a relatively nontoxic extractant-diluent combination, was used, and an equilibrium complexation constant value of 80.8 was obtained for itaconic acid. The selective separation of itaconic acids by amine extractants was studied by Bressler and Braun.12 Loading and distribution curves as well as Fourier transform IR and fluorescence spectra were recorded. Acid-base-coupled extractants composed of di-2-ethylhexylphosphoric acid and a methyltriocylammonium cation in dichloromethane were found to be selective for the more hydrophobic itaconate, which is located in the apolar envelope of the reverse micelle.13 In the present paper, reactive extraction of itaconic acid using Aliquat 336 in various diluents was studied. The study highlighted the effects of ester (ethyl acetate), inert (kerosene), aromatic (toluene), and alkane (hexane) on the degree of solvation/ion exchange of the extractant. Physical and chemical

Figure 1. Physical extraction of itaconic acid in various diluents at 305 K.

extraction experiments were conducted. Values of the distribution coefficient and degree of extraction using physical and chemical extraction were compared. Also, attempts were made to relate the equilibrium complexation constant with the diluent properties. 2. Experimental Section 2.1. Chemicals. Aliquat 336 (trioctylmethylammonium chloride, Himedia, India), a quaternary amine, is a mixture of C8-C10 with a minimum assay of 80%, a molecular weight of 404.17, and a density of 0.888 g/cm3. Itaconic acid was purchased from Himedia, India. Diluents ethyl acetate, toluene, hexane, and kerosene of analytical grade were purchased from Ranbaxy, India, and were used without further purification. For titration, NaOH was used and obtained from S.d. Fine-Chem Ltd., India. A phenolphthalein solution (pH range 8.2-10.0) was used as an indicator. A low initial aqueous concentration of acid (0.05-0.2 kmol/ m3) was used with the goal of finding the effectiveness reactive extraction for the recovery of acid present in dilute form, and the concentration is not expected to be greater than 0.2 kmol/m3 in waste streams and in fermentation broths. 2.2. Extraction Method. The experiments were carried out in conical flasks (100 mL). Extraction experiments involved the shaking of equal volumes (20 cm3) of aqueous and organic phases for 12 h in a constant-temperature (305 K) water bath (Remi, India), followed by settling of the mixture for at least 2 h at the same temperature (305 K). The aqueous-phase pH was measured by an Orion 3 star pH benchtop (Thermo Electron Corp., Marietta, OH). The aqueous-phase acid concentration was determined by titration with NaOH. The results of the above methods were noted when NaOH was prepared fresh every time before titration was to be carried out. The acid content in the organic phase was determined by mass balance. The few experiments were repeated to check the consistency and found to be within the limit of (2%. 3. Results and Discussion 3.1. Physical Extraction. Physical extraction of itaconic acid using ethyl acetate, kerosene, toluene, and hexane was performed and is shown in Figure 1. Extraction of itaconic acid by diluent alone was accounted for by three phenomena: (i) ionization of acid in the aqueous phase (KHA); (ii) partition of the undissociated acid in the organic phase (P); (iii) dimerization of acid in the organic phase (D).7 These have been described as follows:

Ind. Eng. Chem. Res., Vol. 50, No. 2, 2011
Table 1. Partition Coefficient, Dimerization Constant, Distribution Coefficient, and Degree of Extraction for Itaconic Acid Extracted from Water into Organic Solvents at 305 K ([HA]org ) P[HA]aq + D[HA]aq2) diluent ethyl acetate kerosene toluene hexane partition coefficient (P) 0.457 0.009 0.13 0.15 dimerization coefficient (D) 3.578 0.389 2.374 0.345 range of KD 0.5-0.83 0.005-0.06 0.01-0.2 0.04-0.24 avg. KD 0.72 0.047 0.08 0.14 range of E % 36-47 2-6.2 1.3-17.3 4-19

1005

avg. E % 41.6 4.4 8.55 11.97

1. Ionization of the acid in an aqueous solution HAaq T H+ + AKHA ) [H+][A-]/[HA] ) 1.41 × 10-4 kmol/m3

(1) (2)

2. Partition of the undissociated molecular acid between the two phases, aqueous (aq) and organic (org) HAaq T HAorg (3) P ) [HA]org /[HA]aq 3. Dimerization of the acid in the organic phase: 2HAorg T HA2,org D ) [HA]2,org /[HA]org2

(4) (5) (6)

The overall distribution coefficient for physical extraction diluent (KD ) can be written in terms of these parameters as
diluent KD

are offered by the reactive extraction technique by employing organophosphorous compounds and amines, which have proven to be effective in the recovery of carboxylic acids.7 3.2. Chemical Extraction. Aliquat 336, a quaternary amine, was used in the concentration range of 10-30% (0.19-0.59 kmol/m3) for extraction of itaconic acid. Quaternary ammonium chloride (Aliquat 336) extracts both the dissociated and undissociated forms of the acids.14 A higher concentration of Aliquat 336 was not taken because it was highly viscous and would lead to the problem of third-phase formation during extraction. Because Aliquat 336 is highly viscous, a diluent was used in association with it to improve its physical properties, thus allowing easier handling. The diluent lowered the viscosity of Aliquat 336 and decreased the surface tension at the interface. For extraction of itaconic acid by Aliquat 336 with chemical interaction, the distribution coefficient and degree of extraction (E%) were defined as
overall KD )

P + 2P2D[HA]aq [HA]org,total [HA]org + 2[HA]2 ) ) ) [HA]aq,total [HA]aq + [A-] 1 + KHA /[H+]aq

[HA]org [HA]aq + [A-]aq

(11)

(7)
For the dilute concentration of acid (used in the study), it can be fairly assumed that the second term in the denominator of the above equation can be neglected
diluent KD ) P + 2P2D[HA]aq

and E% )
overall 100 × KD overall 1 + KD

(12)

(8)

Extraction involves a chemical reaction between the quaternary amine and acid. Figures 2-5 show the chemical equilibria of

or it can be written in another form as [HA]org ) P[HA]aq + 2P2D[HA]2 aq

(9)

The degree of extraction (E %) of itaconic acid in respective diluents is expressed as
diluent diluent E % ) KD × 100/(1 + KD )

(10)

Equation 9 was fitted to the experimental value (Figure 1) to yield the values of P and D. The values of the partition coefficient, dimerization constant, distribution coefficient, and degree of extraction are given in Table 1. The values of P and D are found as 0.457 and 3.578 for ethyl acetate, 0.009 and 0.389 for kerosene, 0.15 and 0.345 for hexane, and 0.13 and 2.374 for toluene. The trend of the P and KD values is observed as ethyl acetate (ester) > hexane (alkane) > toluene diluent values for all diluents (aromatic) > kerosene (inert). The KD lie between 0.005 and 0.83, which is not sufficiently high. Also, the degree of extraction is very low. The values of the distribution coefficients were found to be higher in ethyl acetate than in other diluents. Itaconic acid has a high affinity to water and a low relative volatility, which renders it difficult to separate. The low activity of itaconic acid toward these diluents, i.e., its higher solubility in water than in organic solvents, is the cause of the low distribution coefficient (<1). Further, because these solvents are relatively soluble in water, their back-recovery proves to be costly. The conventional extraction techniques are thus unprofitable. Better possibilities

Figure 2. Chemical equilibria for extraction of itaconic acid using various percentages of Aliquat 336 in ethyl acetate.

Figure 3. Chemical equilibria for extraction of itaconic acid using various percentages of Aliquat 336 in kerosene.

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Figure 4. Chemical equilibria for extraction of itaconic acid using various percentages of Aliquat 336 in toluene.

Figure 5. Chemical equilibria for extraction of itaconic acid using various percentages of Aliquat 336 in hexane.

extraction of itaconic acid using Aliquat 336 in ethyl acetate, kerosene, toluene, and hexane, respectively. Tables 2-5 show the values of various parameters for reactive extraction of itaconic acid using Aliquat 336 [0.19-0.59 kmol/m3 (10-30%)] in ethyl acetate, kerosene, toluene, and hexane, respectively. Extraction involving Aliquat 336 with ethyl acetate, toluene, hexane, and kerosene clearly shows an enhanced extraction compared to physical extraction. It can be found that the addition of Aliquat has brought about up to 100% improvement in the degree of extraction (E %). This increase in E % clearly suggests that chemical extraction is far better than physical extraction. 3.2.1. Effect of the Acid Concentration on the Distribution Coefficient. Chemical extraction by Aliquat 336 in diluents for various acid concentrations (0.05-0.4 kmol/m3) is shown in Tables 2-5. The distribution coefficients obtained

were found to be higher than those of the pure diluents, thus signifying the advantage of chemical extraction over physical extraction. It was found that for extraction involving Aliquat 336 in different diluents and unit Vorg to Vaq ratios, KD is either slightly effected by the acid concentration or higher at lower acid concentration (0.05 kmol/m3). At higher initial itaconic acid concentrations, the amount of Aliquat 336 may be the limiting factor for the amine-acid reaction. The results were completely in well agreement with that obtained for the lactic acid recovery using a tertiary amine.14 Kahya et al.15 have studied extraction of lactic acid with Alamine 336 and reported a large KD decrease from 10.5 to 0.5 and from 13 to 4 upon an increase of the initial lactic acid concentration from 10 to 100 g/L with 15% and 50% Alamine 336 in oleyl alcohol, respectively. Thus, it can be concluded that, in contrast to tertiary amine, quaternary amine could successfully extract acid at all acid concentrations prevailing in the fermentation broth or aqueous phase. 3.2.2. Effect of the Diluent and Extractant Concentrations on the Distribution Coefficient. Diluent is added to improve the physical properties of the extractant and the solvation efficiency of the acid-extractant complex. The distribution coefficient also depends on the type of diluent and the resulting concentration of the extractant in the solvent phase.7 In general, a polar solvent should improve the extracting power of the nonpolar amine by providing solvation of acid-amine complexes. For an inactive diluent, KD would be expected to be proportional to the concentration of the extractant. Aliquat 336 is highly viscous; therefore, diluent is used with it to reduce its viscosity and to improve its physical properties. As can be seen from Tables 2-5, when the Aliquat 336 volume fraction was increased from 0 to 30% in the diluents, average KD values of acid were found to increase from 0.66, 0.031, 0.098, and 0.14 to 1.93, 0.832, 1.26, and 1.3 in the case of ethyl acetate, kerosene, toluene, and hexane, respectively, using 30% Aliquat 336 in these diluents. 3.2.3. Extraction Mechanism and Equilibrium Complexation Constant. The quaternary ammonium chloride extracts both dissociated and undissociated forms of acid. Kyuchoukov et al.14 experimented with the lactic acid extraction with quaternary ammonium chloride (Aliquat 336) and found that, at a low pH value and low acid concentration (5 g/L), the part of the whole molecule removed by the extractant is bigger than the part of the extracted anions, but with an increase in the pH, the ratio turns. Thus, the concentration of undissociated acid is a function of the pH of the aqueous phase. Because the present study is at pHs of 3.4-3.7, it can be assumed that only undissociated acid is involved in the extraction. Extraction of

Table 2. Chemical Extraction of Itaconic Acid Using Aliquat 336 in Ethyl Acetate at 305 K [B]0 (kmol/m3) 0 [HA]0 (kmol/m3) 0.05 0.1 0.15 0.2 0.05 0.1 0.15 0.2 0.05 0.1 0.15 0.2 0.05 0.1 0.15 0.2 [HA]aq (kmol/m3) 0.032 0.062 0.082 0.120 0.021 0.046 0.054 0.069 0.019 0.044 0.047 0.057 0.021 0.042 0.045 0.054 [HA]org (kmol/m3) 0.018 0.038 0.068 0.080 0.029 0.053 0.096 0.130 0.030 0.056 0.102 0.142 0.029 0.058 0.104 0.145 KD 0.56 0.61 0.82 0.66 1.38 1.14 1.77 1.88 1.58 1.27 2.16 2.48 1.38 1.38 2.30 2.65 avg. KD 0.66 E% 36 38 45.33 40 58 53.33 64 65.33 61.33 56 68.44 71.33 58 58 69.77 72.66 avg. E % 39.83 pHaq 3.65 3.60 3.57 3.52 3.67 3.63 3.62 3.59 3.67 3.63 3.63 3.61 3.67 3.63 3.63 3.61 z 0 0 0 0 0.152 0.280 0.505 0.687 0.0786 0.143 0.263 0.365 0.049 0.098 0.177 0.246

0.19

1.54

60.16

0.39

1.87

64.27

0.59

1.93

64.61

Ind. Eng. Chem. Res., Vol. 50, No. 2, 2011
Table 3. Chemical Extraction of Itaconic Acid Using Aliquat 336 in Kerosene at 305 K [B]0 (kmol/m3) 0 [HA]0 (kmol/m3) 0.05 0.075 0.1 0.125 0.14 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 [HA]aq (kmol/m3) 0.0491 0.0735 0.0995 0.1185 0.132 0.035 0.072 0.15 0.32 0.028 0.065 0.1 0.26 0.020 0.068 0.134 0.205 [HA]org (kmol/m3) 0.0008 0.0015 0.0005 0.0065 0.008 0.015 0.028 0.05 0.08 0.022 0.035 0.1 0.14 0.0293 0.032 0.066 0.1946 KD 0.017 0.020 0.005 0.054 0.060 0.428 0.388 0.333 0.25 0.785 0.538 1 0.538 1.419 0.470 0.492 0.948 avg. KD 0.031 E% 1.73 2 0.5 5.2 5.71 30 28 25 20 44 35 50 35 58.66 32 33 48.66 avg. E % 3.03 pHaq 3.62 3.59 3.55 3.52 3.51 3.65 3.59 3.48 3.32 3.66 3.60 3.55 3.37 3.67 3.59 3.50 3.42

1007
z 0 0 0 0 0 0.078 0.142 0.264 0.421 0.056 0.089 0.256 0.358 0.049 0.054 0.111 0.329

0.19

0.350

25.75

0.39

0.715

41

0.59

0.832

43.08

Table 4. Chemical Extraction of Itaconic Acid Using Aliquat 336 in Toluene at 305 K [B]0 (kmol/m3) 0 [HA]0 (kmol/m3) 0.05 0.1 0.15 0.2 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 [HA]aq (kmol/m3) 0.046 0.0986 0.1386 0.1653 0.0333 0.068 0.134 0.232 0.0246 0.05 0.098 0.216 0.0206 0.0413 0.0886 0.2053 [HA]org (kmol/m3) 0.004 0.0013 0.0113 0.0346 0.0166 0.032 0.066 0.168 0.0253 0.05 0.102 0.184 0.0293 0.0586 0.1113 0.1946 KD 0.086 0.013 0.081 0.209 0.5 0.470 0.492 0.724 1.027 1 1.040 0.851 1.419 1.419 1.255 0.948 avg. KD 0.098 E% 8 1.33 7.55 17.33 33.33 32 33 42 50.66 50 51 46 58.66 58.66 55.66 48.66 avg. E % 8.55 pHaq 3.63 3.55 3.50 3.47 3.65 3.59 3.50 3.39 3.66 3.62 3.55 3.41 3.67 3.64 3.56 3.42 z 0 0 0 0 0.087 0.168 0.347 0.884 0.064 0.128 0.261 0.471 0.049 0.099 0.188 0.329

0.19

0.547

35.08

0.39

0.98

49.41

0.59

1.26

55.41

Table 5. Chemical Extraction of Itaconic Acid Using Aliquat 336 in Hexane at 305 K [B]0 (kmol/m3) 0 [HA]0 (kmol/m3) 0.05 0.1 0.15 0.2 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 0.05 0.1 0.2 0.4 [HA]aq (kmol/m3) 0.0426 0.096 0.1346 0.162 0.0313 0.0633 0.1186 0.232 0.0246 0.0493 0.098 0.1973 0.0206 0.0413 0.0886 0.1906 [HA]org (kmol/m3) 0.0073 0.004 0.0153 0.038 0.0186 0.0366 0.0813 0.168 0.0253 0.0506 0.102 0.2026 0.0293 0.0586 0.1113 0.2093 KD 0.172 0.041 0.114 0.234 0.595 0.578 0.685 0.724 1.027 1.027 1.041 1.027 1.419 1.419 1.255 1.098 avg. KD 0.14 E% 14.66 4 10.22 19 37.33 36.66 40.66 42 50.66 50.66 51 50.66 58.66 58.66 55.66 52.33 avg. E % 11.97 pHaq 3.63 3.55 3.50 3.47 3.65 3.60 3.52 3.39 3.66 3.62 3.55 3.43 3.67 3.64 3.56 3.44 z 0 0 0 0 0.098 0.193 0.428 0.884 0.065 0.13 0.262 0.519 0.05 0.099 0.189 0.355

0.19

0.646

39.16

0.39

1.03

50.75

0.59

1.298

56.33

the undissociated molecules of itaconic acid by chemical interaction thus can be represented as eq 13, (R4N+CI-)org + (HA)aq T (R4N+CI-:HA)org with the equilibrium complexation constant
KE ) [R4N Cl :HA]org [HA][R4N+Cl-]org
+ -

KD )

[R4N+Cl-:HA]org {[HA] + [A-]}

) KE(HA)(1 - R)[R4N+Cl-]org

(15) (13)
or KD [R4N+Cl-:HA]org ) ) KE[R4N+Cl-]org 1-R (1 - R)CHA

)

[R4N Cl :HA]org(KHA + [H ]) [H+]{[HA] + A-}[R4N+Cl-]org KD(HA) [R4N+Cl-]org(1 - R)

+

-

+

(16)

)

(14)

KHA in eq 14 is the dissociation constant of the acid, and R ) KHA/(KHA + [H+]) represents the part of the dissociated form of acid. Rearranging eq 14, we get eqs 15 and 16 as

The distribution coefficient and equilibrium extraction coefficient of undissociated molecules can be determined under the condition that R ) 0, i.e., mineral acid must be added, but in this way, the extraction system changes and KD will not be the same as that in the absence of mineral acid. Taking the logarithm of eq 16 and considering the above assumption, we get eq 17:

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log KD ) log KE + log [R4N+Cl-]org

(17)

The plot of log KD versus log [R4N+Cl-]org would provide a straight line with the intercept of log KE. From the above equation, it can be seen that the distribution coefficient of itaconic acid depends on the free extractant concentration in the organic phase. The equilibrium concentration of free extractant can be represented as eq 18:
0 [R4N+Cl-]org ) [R4N+Cl-]org - [R4N+HA]org

(18)

Figures 6-9 show the plot of eq 17 for itaconic acid extraction using Aliquat 336 in ethyl acetate, kerosene, toluene, and hexane, respectively. As shown in Figures 6-9, the slope is far less than unity; this implies that the extraction mechanism is different from the assumed form. Keeping in mind that the exact chemistry involved in the uptake of extra acid is unknown, the distribution coefficient can be interpreted by the following set of equations (eqs 19-21): [HA]aq + [R4N+Cl-]org 7 8 [R4N+Cl-:HA]org 9 [HA]aq + [R4N+Cl-:HA]org 7 8 [R4N+Cl-:(HA)2]org 9
K2:1 K1:1

Figure 6. Distribution coefficient of itaconic acid in Aliquat 336 in ethyl acetate as a function of the free amine concentration in the organic phase.

(19)

(20)
[HA]aq + [R4N+Cl-:(HA)n-1]org 7 8 [R4N+Cl-:(HA)n]org 9
Kn:1

(21)
The equilibrium complexation constant for the reaction represented by the above equations is (eq 14) KE(n:1) ) [R4N+Cl-:(HA)n]org [R4N+Cl-]org[HA]n aq
Figure 7. Distribution coefficient of itaconic acid in Aliquat 336 in kerosene as a function of the free amine concentration in the organic phase.

(22)

The extent to which the organic phase (amine + diluent) can be loaded with carboxylic acid is expressed as the loading ratio7 z. z) [HA]org [R4N+Cl-]i,org

(23)

The value of z in eq 23 depends on the extractability of the acid (strength of the acid-base interaction) and its aqueous concentration. The stoichiometry of the overall extraction reaction depends on the loading ratio in the organic phase, z. Because in the extraction of itaconic acid using Aliquat 336 in various diluents the organic phase is not highly concentrated, i.e., loading ratios are less than 0.5, the 1:1 complex is formed and the following eq 24 holds: z ) KE1[HA]aq 1-z

Figure 8. Distribution coefficient of itaconic acid in Aliquat 336 in toluene as a function of the free amine concentration in the organic phase.

(24)

Figure 10 shows the plot of z/1 - z versus [HA]aq for the extraction of itaconic acid using Aliquat 336 in ethyl acetate and kerosene, respectively. A straight line passing through the origin was obtained. Similarly, the values of KE1 were obtained for toluene and hexane and are summarized in Table 6. The value of KE1 is more for Aliquat 336 + ethyl acetate compared to the other diluents. Thus, the highest value of KE1 was obtained for Aliquat 336 in ethyl acetate.

The difference among KE1 values for the same acid in different diluents indicates that solvation by the diluent is a critical factor in the extraction of acid. Inert diluents alkanes (hexane), inerts (kerosene), and aromatic (toluene) give a very low distribution of the acid in the solvent phase. Kerosene, toluene, and hexane being nonpolar provide for very little solvation of polar complexes. Esters (ethyl acetate), on the other hand, have greater abilities to solvate the acid-amine complex. In the case of extraction using esters as diluents, the specific hydrogen bonding between the proton of the diluent and the acid-amine complex is the reason of the extra solvation and thus high equilibrium constants. For low acid concentrations of the acid, a 1:1 itaconic acid-Aliquat 336 complex is common, and its structure is

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Figure 9. Distribution coefficient of itaconic acid in Aliquat 336 in hexane as a function of the free amine concentration in the organic phase.

Figure 11. n:1 itaconic acid-Aliquat 336 complex structures: (i) 1:1; (ii) 2:1; (iii) 3:1.

Figure 10. Plot of z/1 - z versus [HA]aq for estimation of the 1:1 itaconic acid-amine equilibrium complexation constant in ethyl acetate and kerosene. Table 6. Equilibrium Complexation Constant for Extraction of Itaconic Acid Using Aliquat 336 (0.22-0.66 kmol/m3) in Various Diluents. diluent ethyl acetate kerosene toluene hexane KE1 (m3/kmol) 6.456 3.022 3.345 3.615 KE2 (m3/kmol)2 110.8 11.24 11.015 14.358

shown in Figure 11i. The formation of 2:1 and 3:1 complexes depends on the itaconic acid concentration in the aqueous phase, and the ratio of 1:1 to 2:1 complex formation is diluentdependent.14 At higher concentrations of itaconic acid, the 2:1 and 3:1 complexes may be formed. This overloading phenomenon results from a second itaconic acid molecule hydrogen bonding to the itaconic acid that is already involved in the 1:1 complex (Figure 11ii). At still higher loading, 3:1 complexes are formed in which a third itaconic acid is hydrogen bonded to the second itaconic acid of the 2:1 complex, as shown in Figure 11iii. In most cases, only the 1:1 complex was observed. In the present case, slight overloading was observed and KE2 values were evaluated in ethyl acetate, kerosene, toluene, and hexane and are given in Table 6. 3.2.4. Effect of the Physical Properties of the Diluents on Extraction. Different approaches have been used to quantify the effect of the diluents on 1:1 complexation. Both partition and self-association constants are strongly dependent on the nature of the diluents; i.e., the thermodynamic activity of the species taking part in the organic-phase equilibria is changed when one diluent is replaced by another. The effect of the diluent on the partition and self-association constants was explained

by specific interactions only between Aliquat 336 and the diluents. King et al.16 have suggested the use of the Hilderbrand solubility parameter as a measure of solvation of the complex by the diluent. In some of the work, a relationship was found between the distribution coefficient and other physiochemical diluent parameters such as the dielectric constant, dipole moment, refractive index, boiling point, etc.17 The extraction constant has been correlated with the solvation energy: the more inert the solvent, the smaller is the extraction constant, which frequently occurs in the solvent extraction practice. The effect of the diluents is determined by the ratio of contributions of solvation of the extractant and the extracted complex to the free energy of extraction. Solvation, in turn, depends on the different kinds of intermolecular forces, which cannot be determined merely from the above-mentioned physical parameters. However, in some cases, the solvation energy is represented in terms of the empirical parameters of the solvent polarity. The parameters most frequently used are the Z parameter (proposed by Kosower18), which accounts for the influence of the solvent on the position of the charge-transfer band in the spectrum of alkylpyridine iodide, and the ET parameter, which is based on the absorption spectrum of pyridinium N-phenolbetaine. The greater the ET and Z values, the greater is the solvating power of the solvent. Attempts have been made to correlate the extraction efficiency in terms of the KE values with solvent properties like the molecular mass, boiling point, density, refractive index, dielectric constant, and dipole moment. A few properties of the various solvents used are given in Table 7. Ethyl acetate has a lower molecular mass in comparison to kerosene and toluene. Thus, it can be suggested that, because Aliquat 336 is itself relatively viscous, employing a lower molecular weight diluent can significantly improve the complexation ability of Aliquat 336 with the acid. However, it can be stated here that it is not obvious that a lower molecular weight of the solvent would result in a better Aliquat 336-diluent system because the lower the molecular weight, the higher will be the miscibility of the solvent with water. Thus, optimization should be done during selection of the diluent for Aliquat 336. Hexane has a slightly lower molecular weight than ethyl acetate but has a lower solvation of the complex because of the inert nature of the diluent. Similarly, it can seen that the higher extraction in ethyl acetate can be explained by its higher solvent dipole moment µ value

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Table 7. Physical Properties of Various Diluents properties density (kg/m3) at 25 °C 894 800 862 655 dielectric constant at 25 °C 6.02 1.8 2.38 1.88 dipole moment µ (D) at 20 °C 1.88 ∼0 0.31 0.08 viscosity (cP) at 20 °C 0.45 0.78-0.82 0.59 0.31 refractive index at 20 °C 1.3724 1.448 1.4969 1.3749 boiling point (°C) 77.11 150-300 110.62 68.7 surface tension (dyn/cm) at 20 °C 23.75 23-32 28.53 17.91 solubility of water (%) at 20 °C 3.3 ∼0 0.033 0.01 solubility in water (%) at 20 °C 0.7 ∼0 0.052 0.014

solvent ethyl acetate kerosene toluene hexane

mol wt 88.104 120 92.14 86.18

polarity index 4.4 ∼0 2.4 0.1

(µ for ethyl acetate ) 1.78 D) than kerosene (∼0), toluene (0.31 D), and hexane (0.0 D). Because extraction probably occurs via solvation of the complex based on dipole-dipole interaction, a higher µ value of ethyl acetate provides it with a higher ability to solvate the amine-acid complexes. 3.2.5. Water Coextraction. Water coextraction is the term used to describe the water that enters the organic phase with the solute. This may affect the process economics because this entered water would have to be removed during the regeneration phases and would lead to extra expenditure on power and cost. Tamada and King19 had stated that water coextraction decreases in the same trend as the solubility of the the diluents in water. The mutual solubility between an aqueous solution and a given solvent at a fixed temperature is affected by the nature of the acid and its concentration. With weak acids like itaconic acid, mutual solubilities cause substantial volume changes, which can be related to the coextraction of water along with the acid. Volume changes depend on the type of diluent and the type and concentration of the extractant as well as the temperature. In the present case, it was found that, for extraction involving 10% Aliquat 336 in various diluents, the ratio of the organicphase volume to the aqueous-phase volume increases with an increase in the acid concentration. For 20% and 30% Aliquat 336 concentrations, with an increase in the acid concentration, the value of the phases first increases and then decreases. The explanation of the phenomenon can be explained on the basis of the diluent and equilibrium characteristics. Because the diluent is mainly responsible for water coextraction, at higher diluent concentration, the water coextraction is higher. Further, as water is extracted along with the complexes, at high diluent concentrations, more water will be extracted if more acid is present. This leads to more acid-Aliquat 336 complexes and a better solvation provided to them by the diluent, which is in excess. On the contrary, at low diluent concentrations, extraction would increase only to the point when the diluent concentration becomes the limiting factor because this limits solvation of the complexes from the interface to the organic phase. Tamada and King19 found in the extraction of lactic acid that the amounts of coextracted water and extracted lactic acid increase with an increase in the number of moles of tertiary amine; however, the type and concentration of the active diluent are more important factors than the number of moles of extractant for the extraction of lactic acid. Similar results can be seen here in the extraction of itaconic acid by quaternary amine (Aliquat 336). It was observed that, at a higher concentration of itaconic acid (0.4 kmol/m3), the increase in the Aliquat 336 concentration or the decrease in the diluent concentration decreases water coextraction. However, in general, the selectivity of acid over water in the extraction by amine extractant is high relative to the results with a conventional solvent, and in all cases, the water coextraction is not above 5-8%, which has little effect upon the process viability.

3.2.6. Back-extraction/Regeneration. Back-extraction of acid is another important point in the context to the choice of extractant. The overall degree of concentration relative to the feed that can be achieved by reactive extraction is limited by the extent to which the distribution equilibrium for carboxylic acid can be exchanged between forward extraction and backextraction. There are numerous methods found in the literature for back-extraction, like back-extraction with water at higher temperature (temperature swing) and back-extraction with caustic, diluent swing, and distillation and using a volatile amine.4 In order to avoid the consumption of chemicals and the creation of a salt byproduct, the method of using a volatile amine for back-extraction in a countercurrent back-extractor, thereby enabling thermal decomposition of the acid-base complex in the aqueous countercurrent back-extractor, can be proposed as the regeneration method. With a countercurrent back-extractor, the existing acid-depleted organic phase would have last contacted an entering aqueous base containing little if no acid, and there would therefore be substantial partitioning of the base into that existing organic stream. This would, however, require a subsequent base-removal step. Decomposition of the base-acid complex formed will form itaconic acid as the product and the free volatile base as a vapor, which can be reabsorbed in water and recycled for reuse in the backextraction. In order to achieve a high degree of back-extraction into the volatile base, it is proposed to keep the base/acid ratio in the back-extractor close to or higher than the stoichiometric ratio. 4. Conclusion Physical and reactive extraction of itaconic acid was studied using Aliquat 336 in various diluents: ester (ethyl acetate), inert (kerosene), aromatic (toluene), and alkane (hexane). Very low extraction was observed by physical extraction. Physical extraction was represented in terms of the partition coefficient, dimerization constant, distribution coefficient, and degree of extraction. The values of P and D are found as 0.457 and 3.578 for ethyl acetate, 0.009 and 0.389 for kerosene, 0.15 and 0.345 for hexane, and 0.13 and 2.374 for toluene. The trend of the P and KD values is observed as ethyl acetate (ester) > hexane diluent (alkane) > toluene (aromatic) > kerosene (inert). The KD values for all diluents lies between 0.005 and 0.83, which is not sufficiently high. Also, the degree of extraction is very low. Reactive extraction enhanced significantly the extraction of itaconic acid in the organic phase. Reactive extraction was represented in terms of equilibrium complexation constants, loading ratios, and distribution coefficients. 1:1 and 2:1 acid-amine complexes were formed in the present case. The results obtained are useful for the design of the reactive extraction process for the recovery of itaconic acid.

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Nomenclature
[A ] ) concentration of dissociated acid in the aqueous phase (kmol/m3) [B] ) concentration of extractant in the organic phase (kmol/m3) [H+] ) H+ ion concentration in the aqueous phase (kmol/m3) [HA] ) acid concentration (kmol/m3) [R4N+Cl-:(HA)2] ) concentration of the 2:1 acid-extractant complex (kmol/m3) [R4N+Cl-:(HA)n] ) concentration of the n:1 acid-extractant complex (kmol/m3) [R4N+Cl-:HA] ) concentration of the 1:1 acid-extractant complex (kmol/m3) D ) dimerization constant (m3/kmol) E % ) degree of extraction KD ) distribution coefficient of acid in the organic phase KE(1:1) ) extraction equilibrium constant for the 1:1 acid-extractant complex (m3/kmol) KE(2;1) ) extraction equilibrium constant for the 2:1 acid-extractant complex (m3/kmol)2 KE(n:1) ) extraction equilibrium constant for the n:1 acid-extractant complex (m3/kmol)n KHA ) ionization constant of itaconic acid ) 1.41 × 10-4 kmol/ m3 P ) partition coefficient z ) loading ratio Subscripts aq ) aqueous phase org ) organic phase 0 ) initial Superscripts diluent ) for diluent only overall ) for extractant + diluent
-

Literature Cited
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(4) Wasewar, K. L.; Yawalkar, A. A.; Moulijn, J. A.; Pangarkar, V. G. Fermentation of Glucose to Lactic Acid Coupled with Reactive Extraction: A Review. Ind. Eng. Chem. Res. 2004, 43, 5969. (5) Tamada, J. A.; King, C. J. Extraction of Carboxylic Acids with Amine Extractants, (3) Effect of Temperature, Water Co-extraction, and Process Considerations. Ind. Eng. Chem. Res. 1990, 29, 1333. (6) Wasewar, K. L.; Heesink, A. B.; Versteeg, G. F.; Pangarkar, V. G. Equilibria and Kinetics for Reactive Extraction of Lactic Acid Using Alamine 336 in Decanol. J. Chem. Technol. Biotechnol. 2002, 77, 1068. (7) Kertes, A. S.; King, C. J. Extraction Chemistry of Fermentation Product Carboxylic Acids. Biotechnol. Bioeng. 1986, 28, 269. (8) Ricker, N. L.; Pittman, E. F.; King, C. J. Solvent Extraction with Amines for Recovery of Acetic Acid from Dilute Aqueous Industrial Streams. J. Sep. Process Technol. 1980, 1 (2), 23. (9) Jung, M.; Schierbaum, B.; Vogel, H. Extraction of Carboxylic Acids from Aqueous Solutions with the Extractant System Alcohol /Tri-nalkylamines. Chem. Eng. Technol. 2000, 23, 70. (10) Kyuchoukov, G.; Morales, A. F.; Albet, J.; Malmary, G.; Molinier, J. On the Possibility of Predicting the Extraction of Dicarboxylic Acids with Tributylphosphate Dissolved in a Diluent. J. Chem. Eng. Data 2008, 53 (3), 639. (11) Hano, T.; Matsumoto, M.; Ohtake, T.; Sasaki, K.; Hori, F.; Kawano, Y. Extraction Equilibria of Organic acid with Tri-n-octylphosphine Oxide. J. Chem. Eng. Jpn. 1990, 6, 734. (12) Bressler, E.; Braun, S. Separation Mechanisms of Citric and Itaconic Acids by Water-Immiscible Amines. J. Chem. Technol. Biotechnol. 1999, 74 (9), 891. (13) Matsumoto, M.; Otono, T.; Kondo, K. Synergistic Extraction of Organic Acids with Tri-n-octylamine and Tri-n-butylphosphate. Sep. Purif. Technol. 2001, 24, 337. (14) Kyuchoukov, G.; Yankov, D.; Molinier, J.; Albet, J. Mechanism of Lactic Acid Extraction with Quaternary Ammonium Chloride (Aliquat 336). Ind. Eng. Chem. Res. 2005, 44, 5733. (15) Kahya, E.; Bayraktar, E.; Mehmetoglu, U. Optimization of Process Parameters for Reactive Lactic Acid Extraction. Turk. J. Chem. 2001, 25, 223. (16) Tamada, J. A.; Kertes, A. S.; King, C. J. Extraction of Carboxylic Acids with Amine Extractants, (1) Equilibria and Law of Mass Action Modeling. Ind. Eng. Chem. Res. 1990, 29, 1319. (17) Bora, M. M. Study of Reactive Extraction of Certain Beta-lactum Antibiotics: Equilibrium and Kinetics. Ph.D. Dissertation, Gauhati University, Gauhati, India, 2000. (18) Kosower, M. The Effect of Solvent on Spectra. I. A New Empirical Measure of Solvent Polarity: Z values. J. Am. Chem. Soc. 1958, 80, 3253. (19) Tamada, J. A.; King, C. J. Extraction of Carboxylic Acids with Amine Extractants. 2. Chemical Interaction and Interpretation of Data. Ind. Eng. Chem. Res. 1990, 29, 1327.

ReceiVed for reView May 30, 2010 ReVised manuscript receiVed October 29, 2010 Accepted November 26, 2010 IE1011883