Efficient Production of 5-Hydroxymethylfurfural Enhanced by Liquid

Jan 30, 2018 - slug flow microreactor, 8.76, 4, 3.9 × 10–4, 97.1, 88.5, 91.1, 45.3, 0.83, (36) .... Eng. 2014, 2 (6), 1461– 1473, DOI: 10.1021/sc...
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Research Article Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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Efficient Production of 5‑Hydroxymethylfurfural Enhanced by Liquid−Liquid Extraction in a Membrane Dispersion Microreactor Caijin Zhou,† Chun Shen,*,‡ Kaiyue Ji,‡ Jiabin Yin,‡ and Le Du*,† †

The State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Membrane Science and Technology, and Beijing Key Laboratory of Bioprocess, National Energy R&D Center for Biorefinery, College of Life Science and Technology, Beijing University of Chemical Technology, No. 15 of North Three-Ring East Road, Chaoyang District, Beijing, 100029, P.R. China

‡

S Supporting Information *

ABSTRACT: Aimed at efficient production of 5-hydroxymethylfurfural (HMF) in a green and sustainable way, dehydrogenation of fructose was enhanced by liquid−liquid extraction in a membrane dispersion microreactor. On account of the high mass-transfer rate resulted from dripping flow, the obtained HMF was readily extracted from the aqueous phase to the organic phase, effectively preventing the sequence side reaction and leading to high HMF selectivity. Enhanced by efficient extraction, the reaction duration decreased from 60 min in a traditional stirred reactor to 4 min in the microreactor, leading to an increase in the space-time yield by 3 orders of magnitude. The effects of total volume flow rate, droplet size, and phase ratio relating to extraction efficiency and HMF yield were systematically investigated. The highest extraction efficiency of nearly 100% coupled with the HMF yield of 93.0% was achieved at the phase ratio of 2 with volume flow rate of 600 mL/h. Overall, this work not only delineates an efficient strategy for synthesizing HMF but also opens a new avenue for reaction systems with subsequent side reaction, which suffer from low selectivity of the intermediates due to the in-line separation bottleneck under conditions of limited mass transfer. KEYWORDS: 5-Hydroxymethylfurfural production, Fructose dehydrogenation, Membrane dispersion microreactor, Extraction efficiency

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INTRODUCTION Utilization of biomass which represents abundant carbonneutral renewable resources for the production of biochemicals and biofuels is critical to address the climate change and global energy challenge.1−4 5-Hydroxymethylfurfural (HMF), which has been listed in the top 10 value-added biobased chemicals by the U.S. Department of Energy,5,6 plays a significant role in the connection of biomass and chemicals/liquid fuels.7−9 After selective oxidation of HMF, 2,5-furandicarboxylic acid, which serves as alternative to terephthalic acid for producing polyesters, could be synthesized.10,11 2,5-Dimethylfural, which is considered a promising biofuel to replace key petroleumbased building blocks, can be obtained from HMF through hydrogenolysis reactions.12,13 Recent years have witnessed rapid developments in catalytic systems for dehydration of monosaccharide into HMF.14−18 Considering that water is an ideal green solvent for chemical transformations, simple aqueous systems in which hydrochloric acid served as the catalyst were first evaluated for carbohydrate dehydration. However, HMF is readily converted into various by-products. For instance, levulinic acid and formic acid produced from HMF rehydration, which occurs on acidic sites with water molecules,19,20 resulted in a low HMF selectivity and limited the application of a simple aqueous system. © XXXX American Chemical Society

By virtue of the good stability of HMF in organic solvents, biphasic systems consisting of water and an organic solvent have been intensively investigated. The organic solvent continuously extracted HMF products from the aqueous solution, avoiding further conversion of HMF, leading to higher HMF yield and selectivity.21−23 In a batch reactor, Román-Leshkov et al. obtained a HMF selectivity of 60.0% in a methyl isobuthyl ketone (MIBK)−water system with HCl catalyst.1 Chan and Zhang reported that a 65.0% HMF yield was achieved by using THF−water solvent mixture in a continuous batch reactor.24 Organic−aqueous biphasic system in batch reactors still faced limited success despite their improvement in HMF selectivity compared with simple aqueous systems. The poor mass-transfer efficiency in batch reactors resulted in limited extraction efficiency and HMF selectivity and required a long time to complete the extraction process, which greatly reduced the space-time yield. In addition, large amounts of organic solvents were required due to the poor mass-transfer efficiency, causing difficulties in solvent recyclability and increase in energy consumption. Received: November 21, 2017 Revised: January 24, 2018 Published: January 30, 2018 A

DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

(Shanghai, China). 4-Methyl-2-pentanone (MIBK, 99.0%) was purchased from Aladdin (Shanghai, China). All other reagents were provided by Beijing Chemicals Co. (Beijing, China) and of analytical grade. Hastelloy alloy (type C276) tubes were obtained from Special Alloy Co., Ltd. (Shanghai, Beijing). Apparatus and Synthetic Process for HMF. Figure 1a shows the membrane dispersion microreactor setup employed

Nowadays, microreactors have been widely used in diverse fields, including nanomaterials preparation, drug delivery, and liquid−liquid biphasic extraction.25−27 Especially, because of high mass-transfer rate, it has shown to be a great prospect for application in an efficient extraction process. In our previous studies, microdispersion technologies have been widely applied in extraction processes, showing significant advantages in high mass-transfer efficiency and controllability. Through the microporous membrane, a large amount of droplets are formed and mixed with the other phase. In this case, the interfacial areas are increased and mass-transfer distances between liquid− liquid two phases are decreased, which greatly improved the extraction efficiency. For this reason, it is regarded as an ideal reactor to carry out an efficient extraction process. Luo and coworkers have reported that an efficient extraction process was realized with an extraction efficiency reaching as high as 100.0% in the short residence time.28−30 Jensen and co-workers also performed a rapid separation and efficient extraction process by using a porous membrane in a microreactor.31−33 These studies suggest that microreactors have great advantages in low-energy and efficient extraction. A continuous microreaction process was also developed for the production of HMF in the work of Tuercke et al., in which the highest HMF yield of 82.0% coupled with the HMF selectivity of 85.0% was obtained.34 Similarly, Shimanouchi et al. reported the continuous production of HMF in a slug flow microreactor.35−37 The highest yield was 88.5%, and the HMF yield in the organic phase (MIBK) was 41.0% with the R value (R value is the ratio of the HMF concentration in the organic phase to HMF concentration in the aqueous phase) of 0.83, indicating that an improved extraction performance was favorable for increasing HMF yield and selectivity. However, compared with the dripping flow, the extraction efficiency of this slug flow is usually poorer,29,38 and the throughput of HMF is also limited. Therefore, it is worth attempting to improve the HMF yield and selectivity by increasing the extraction efficiency based on the numerous droplets in the membrane dispersion microreactor. In this work, we explored the feasibility of producing HMF enhanced by in situ extraction in the membrane dispersion microreactor. From the standpoint of green and sustainable chemistry, there may be three possible advantages: first, microfiltration membranes with the pore size of 5 μm were used as the dispersion medium and divided the dispersed phase fluid into many small droplets, resulting in an increase in the interfacial area between organic and aqueous phases and a decrease in mass-transfer distance. The extraction performance was supposed to be greatly improved. Second, on account of the improved extraction performance of HMF, the HMF selectivity and yield would also be improved by preventing the subsequent side reactions. Besides, the dehydration was greatly enhanced by the efficient extraction, resulting in a significant decrease in reaction duration from 60 min in stirred tank to 4 min in the microreactor. Accordingly, the space-time yield was increased by 3 orders of magnitude. Third, the amount of organic solvent and energy expenditure for purifying HMF product would be reduced. The effects of total volume flow rate, droplet size, and phase ratio relating to extraction efficiency in the microreactor were systematically investigated.

Figure 1. Schematic diagram of the microreaction system. (a) Experimental setup for continuous production of HMF; (b) microreactor used in this experiment.

in the experiment, which is used for continuous production of HMF. The microreactor shown in Figure 1b has a mixing chamber, a sintering membrane made of stainless steel, and a cross-flow channel. The microfiltration membrane (3 × 1 × 0.3 mm) with an average pore size of 5 μm is placed between the mixing chamber and the cross-flow channel (10 × 1 × 0.6 mm). The diameter of the Hastelloy alloy tube is 3 mm. In the process of synthesizing HMF, the MIBK organic solution and the saturated sodium chloride aqueous solution containing 10 wt % fructose and 25 mol/m3 HCl served as the dispersed phase and the continuous phase pumped into the microreactor, respectively. As shown in Figure 1a, the dispersed phase fluid was pumped through the membrane into the continuous phase and divided into droplets. Then the two phases were mixed in the microreactor. In the heating bath, the well-mixed fructose solution was catalyzed by hydrochloric acid to synthesize HMF at 453 K, 3 MPa. The pressure in the setup was controlled by the back pressure valve. When the length of Hastelloy alloy tube was changed, the residence time of reactants in the heating bath was tuned. Analytical Methods. A high-performance liquid chromatograph (HPLC, Agilent 1260 Infinity) equipped with a variable wavelength detector (320 nm) was used to determine the concentration of HMF. The concentration of fructose after reaction was analyzed using a refractive index detector. The details of the experiment are shown in the Supporting Information. A microscope with a CCD video camera (PLA742, PixeLink, Canada) was used to measure the drop size. The conversion of fructose (X), HMF yield (Y), and selectivity (S) are defined by the following equations:

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EXPERIMENTAL SECTION Materials. 5-Hydroxymethylfurfural (HMF, 99.5+%) and fructose (99.0+%) were purchased from Sigma-Aldrich B

DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering Conversion rate of fructose: mol of initial fructose − mol of final fructose × 100 mol of initial fructose

X(%) =

(1)

HMF yield: Y(%) =

mol of HMF production × 100 mol of initial fructose

(2)

HMF selectivity: Y S(%) = X =

mol of HMF production × 100 mol of initial fructose − mol of final fructose (3) Figure 2. Effect of volume flow rate on extraction efficiency E.

The extraction efficiency E defined as follows was introduced to assess the extraction performance of the microreactor:

E=

where dd is the droplet size, di is the diameter of the pore or junction connecting dispersed and continuous phases, Ca is the capillary number, uc and μc are the volume flow rate and viscosity of continuous phase, and γ is the interfacial tension between the two phases. From the equation, it is clear that the droplet size decreases with the increase of total volume flow rate. Because of the decreased droplet size, the total interfacial area between organic phase and aqueous phase was significantly increased, leading to an efficient extraction process in the microreactor. In Figure 2, it also shows the variation of extraction efficiency E with volume flow rate. As the volume flow rate increased, extraction efficiency E also increased, which allowed the HMF product to be rapidly extracted into the organic phase and effectively prevented side reactions of HMF. Therefore, as extraction efficiency E was increased, the HMF yield and selectivity were also increased. However, at higher volume flow rates, the residence time in the mixing chamber of the microreactor was shorter. However, the extraction efficiency E was close to 100% because, in this range of volume flow rate, the effect of interfacial area on extraction efficiency E is dominant. In the same microextraction process, Xu et al. had also found that with the increase of volume flow rate, the extraction efficiency E was also greatly increased and reached nearly 100%.41 However, when the flow rate increased to a certain value, extraction efficiency was slightly decreased. Before reaching the maximum value, the total interfacial area was greatly increased with the increase of the volume flow rate. After maximum value, the total interfacial area was not further increased, as shown in Figure 2. After the flow rate increased to around 480 mL/h, the droplet size was slightly decreased. The result indicates that the total interfacial area has a significant impact on the extraction efficiency E, and HMF yield and selectivity. Relationship between Droplet Size and Mass-Transfer Performance. For further study of the relationship between droplet size and extraction efficiency E, the microfiltration membrane sizes of 5 and 10 μm were used to obtain two different droplet sizes. Droplet size was determined using a high-speed CCD video camera, and the micrographs with corresponding droplet size distributions at different experimental conditions are shown in Figure 3. Obviously, the diameter of the droplets obtained by the 5 μm membrane is significantly less than those by the 10 μm membrane. Figure 4 shows the extraction efficiencies E for two different membranes. As can be seen from Figure 4, at the same extraction time, a

y′ − y0 y* − y0

(4)

y′ represents the final concentration of HMF production in organic phase, y0 is the initial concentration of HMF in organic phase, and y* is the equilibrium HMF concentration of organic phase with aqueous phase.

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RESULTS AND DISCUSSION Effect of Volume Flow Rate. Production of HMF in the membrane dispersion microreactor was carried out at different volume flow rates. As shown in Table 1, when the total volume Table 1. Conversion, Yield, and Selectivity of HMF Production at Different Volume Flow Ratesa no.

V (mL/h)

X (%)

Y (%)

S (%)

yield of HMF in MIBK phase (%)

1 2 3 4 5

120 240 360 480 600

98.9 99.2 99.9 99.7 99.9

68.5 73.7 78.1 84.8 92.2

69.2 74.3 78.1 85.1 92.2

66.7 68.9 70.3 75.8 81.5

a

Phase ratio of the organic phase to the aqueous phase was kept at 2.

flow rates increased from 120 to 600 mL/h, HMF selectivity was increased from 69.2% to 92.2% and HMF yield was increased from 68.5% to 92.2%. In addition, the yield of HMF in MIBK phase also increased. Since the total volume flow rate increases, the droplet size decreases and the total interfacial area of the two phases greatly increases, which effectively decreased the mass-transfer distance between the two phases. Droplet size is mainly dependent on the total volume flow rate. The effect of total volume flow rate on droplet size is shown in Figure 2. With the increase of total volume flow rate, the droplet size decreases. The experimental results are identical with Cristini’s theoretical model, which is used to evaluate the droplet size in the microdispersion process. The relationship between drop size and volume flow rate can be described by the equations39,40

dd /d i ∼ 1/Ca

(5)

Ca = μc uc /γ

(6) C

DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

Figure 3. Microphotographs of droplets obtained through different experimental conditions: (a, c, d) correspond to the operation with the membrane size of 5 μm, Va = 360 mL/h, Vc = 120 mL/h, and Vd = 600 mL/h; (b) corresponds to the operation with the membrane size of 10 μm, Vb = 360 mL/h. Other conditions: phase ratio = 2, reaction temperature = 180 °C.

The ratio of c/c0 as an index is used to evaluate the extraction performance, and r, VE/VR, and t represent drop size, phase ratio, and residence time, respectively. The πr2 is the interfacial area of a drop. In the equation, when the droplet size r decreases linearly, the interfacial area of a drop decreases; however, the extraction efficiency E is greatly increased. Besides, the equation also distinctly shows residence time and phase ratio have effects on extraction efficiency E. Effect of Phase Ratio on Extraction Efficiency E. For more effectively improving extraction performance to increase HMF yield and selectivity by changing the operating conditions, the effects of phase ratio and residence time on extraction efficiency E were studied. Figure 5 shows the change in extraction efficiency E and HMF yield in organic phase at different phase ratios. In the Figure 5, with the increase of phase ratio, the extraction efficiency E and HMF yield in organic phase are also increased. The effect of phase ratio on extraction efficiency E of a microreactor is mainly caused by the effect of HMF product concentration on mass-transfer rate. At a low phase ratio, the HMF concentration in organic phase was too high, which reduced the mass-transfer rate from aqueous phase to organic phase and caused HMF product to have a longer residence time in the aqueous phase. The HMF in aqueous phase tended to be converted into other by-products. Therefore, the amount of HMF that was extracted into organic phase decreased, leading to a low extraction efficiency and yield of HMF. With the increase of phase ratio, the effect of HMF concentration in organic phase on mass-transfer rate was reduced. The HMF was extracted immediately from the aqueous phase to organic phase, which effectively prevented the side reaction of HMF and reduced the HMF concentration in the aqueous phase.

Figure 4. Variation of extraction efficiency E with extraction time using membranes with different pore sizes.

better extraction performance could be achieved in the smaller membrane. It is mainly attributed to the fact that, with the decrease of droplet size, the mass-transfer length 2r decreases and the total interfacial area between the two phase increases, which remarkably enhances the extraction efficiency. Benz and others have proposed a mass-transfer model describing the diffusion from a sphere of radius r into a well-stirred volume during time t, for assessing the relationship between interfacial area and extraction efficiency E. It can be described as the following equation:41,42 ⎡ Dt kV ⎤ c = f⎢ 2 , E⎥ c0 VR ⎦ ⎣r

(7) D

DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering

Figure 6. Effect of residence time T on extraction efficiency E and HMF yield. Other operation conditions: V = 600 mL/h, Vorg/Vaq = 2, the pore size of membrane is 5 μm.

Figure 5. Effect of phase ratio on extraction efficiency E and HMF yield in organic phase. Experimental conditions: V = 600 mL/h, reaction temperature = 453 K, pressure = 3 MPa.

Because of the decrease in HMF concentration, the reaction rate of fructose converted to HMF increased, and the HMF selectivity was also increased. As shown in Table 2, the fructose Table 2. Effect of Phase Ratio on HMF Yield in MIBK Phasea no.

Vorg/ Vaq

residence time in heating bath (min)

X (%)

Y (%)

S (%)

yield of HMF in MIBK phase (%)

6 7 8 9

1 1.5 2 4

4 4 4 4

68.0 79.0 98.8 99.0

36.0 55.0 88.0 90.0

52.0 69.0 89.0 90.0

30.0 48.0 70.0 75.0

a

Yield of HMF in MIBK phase is the percentage of total HMF yield.

conversion rate and HMF selectivity were increased with the increase of phase ratio. Therefore, the results confirm that the mass-transfer rate has a great influence on HMF selectivity and fructose conversion rate. Effect of Residence Time T on Extraction Efficiency E and HMF Yield in the Heating Bath. When the length of the tube was changed, the residence time of HMF product in the heating bath was tuned. Figure 6 shows the effect of residence time on extraction efficiency E and yield of HMF product. With the increase of residence time, the extraction efficiency E and yield are also increased. However, after the residence time reached 4 min, the extraction efficiency E and yield are slightly decreased with the increase of residence time. The reason should be attributed to the fact that extraction equilibrium between two phases plays an important part in extraction efficiency E. After a certain period of residence time, extraction equilibrium can be achieved. During this time period, as the residence time increased, the HMF product could be completely extracted into the organic phase, leading to the increase of extraction efficiency E. Figure 7 shows the variation of HMF concentration in the organic phase with the increase of residence time T. In Figure 7, with the increase of residence time T, the HMF concentration in the organic phases is also increased. However, after the residence time reached 4 min, the HMF concentration is slightly decreased. At first, as the residence time T increased, a large amount of fructose reacted to produce HMF, and the synthesized HMF was instantly extracted into the organic phase. The HMF concentration in

Figure 7. Effect of residence time T on HMF concentration C in organic phase.

the organic phase also increased. As a result, the extraction efficiency E and yield were increased. When the residence time was 4 min, the extraction efficiency E reached the maximum value and phase equilibrium was achieved. After that, with the increase of residence time, the HMF in the aqueous phase was converted into other by-products, and the HMF concentration in the aqueous phase was decreased. As the HMF concentration decreased, the HMF product had been extracted into the organic phase, and then transferred back to the aqueous phase to reach a new equilibrium. In this case, the HMF concentration in organic phase was decreased, and thus the HMF yield and selectivity were also decreased. Comparison with Other Extraction Processes. The method for synthesizing HMF product in stirred tanks has been widely used. To compare the extraction process in the microreactor with stirred tanks, HMF was obtained using two different extraction processes at the same operation condition. Table 3 shows the HMF yield and selectivity from different extraction processes. The R value is the ratio of the HMF concentration in the organic phase to HMF concentration in the aqueous phase, which is regarded as another parameter to evaluate extraction efficiency. As can be seen from Table 3, with the membrane dispersion microreactor, the HMF yield and selectivity reached 93% in the reaction duration of 4 min, which was approximately 88−93% shorter than that in the stirred E

DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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ACS Sustainable Chemistry & Engineering Table 3. Comparison with Other Extraction Processesa type microreactor stirred tank batch reactor (add phase modifiers) microchannel reactor slug flow microreactor a

V (mL/h) 600

30 8.76

T (min)

space-time yield (mol·mL−1· min−1)

X (%)

Y (%)

S (%)

HMF yield in organic phase (%)

R

ref

4 60 35

6.13 × 10−3 1.7 × 10−6 8.7 × 10−5

99.9 94.5 83.0

93.0 68.5 68.0

93.0 72.5 82.0

81.5 28.7 71.9

4.42 0.41 2.7

this work this work 21

3 4

2.1 × 10−4 3.9 × 10−4

71.0 97.1

54.0 88.5

75.0 91.1

45.3

0.83

38 36

R = [HMF]org/[HMF]aq. The space-time yield was obtained from the total effective amount of HMF product in unit volume per unit reaction time.

and selectivity were increased. In addition, the amount of extraction solvent and energy consumption for purification were significantly decreased. For efficiently increasing extraction efficiency to increase HMF yield and selectivity, the operating conditions relating to extraction efficiency E were experimentally investigated, indicating that the volume flow rate, phase ratio, and residence time T had a great influence on extraction performance. Under the optimal condition, the extraction efficiency E reached nearly 100% and the HMF yield was 93.0% with the reaction duration of 4 min. Compared with stirred tank, the reaction duration of 88.0−93.0% shorter was achieved with a higher HMF selectivity, while the space-time yield was 103 times higher. Given the excellent performance of microextraction and microreaction, the work provides a more economical and green process to continuously synthesize the HMF product.

tank. However, the extraction performance of the microreactor is much better than the stirred tank. In the stirred tank, synthesized HMF product was not extracted immediately into the organic phase, and thus converted into other by-products, resulting in low HMF yield and selectivity. In contrast, in the membrane dispersion microreactor, the dispersed phase droplets were uniformly distributed in the continuous phase within the mixing time less than 1 s. Figure 8 shows the two

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ASSOCIATED CONTENT

S Supporting Information *

Figure 8. Schematic diagram of HMF production in stirred tank and microreactor.

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b04368. Related experimental details (PDF)

different extraction processes. Because of the presence of large amounts of droplets, the total interfacial area between two phases was increased and the mass-transfer distance was also decreased. Therefore, the mass-transfer rate was significantly increased, which allowed the HMF to be extracted into the organic phase in a short time and avoided the side reaction of HMF product. In addition, by virtue of the higher selectivity and shorter reaction time, the space-time yield of the microreactor was 103 times higher than that of the stirred tank. The membrane dispersion microreactor shows enormous advantages in the production process. Compared with other microextraction processes, despite throughput and space-time yield of membrane dispersion microreactor increasing more than 20 times, the HMF yield and selectivity increased. On account of improving the extraction performance, the continuous production throughput and space-time yield also notably increased in the membrane dispersion microreactor, which provides a green and efficient process to obtain HMF product.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (C.S.). *E-mail: [email protected] (L.D.). ORCID

Chun Shen: 0000-0001-6993-4336 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the support of the National Nature Science Foundation of China (21606008, U1663227), State Key Laboratory of Chemical Engineering (No. SKL-ChE16A01, SKL-ChE-17A02), and the Fundamental Research Funds for the Central Universities (buctrc201616).

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CONCLUSIONS In this work, a novel efficient extraction process has been proposed using the membrane dispersion microreactor. In the microreactor, the dispersed phase fluid was formed into a large number of droplets, and mixed evenly with the continuous phase fluid in no more than 1 s. The generated droplets greatly increased the total interfacial area between the organic phase and the aqueous phase and decreased mass-transfer distance, leading to significant improvement in extraction performance. With improvement in extraction performance, the HMF yield

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DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

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DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX

Research Article

ACS Sustainable Chemistry & Engineering (42) Benz, K.; Jackel, K. P.; Regenauer, K. J.; Schiewe, J.; Drese, K.; Ehrfeld, W.; Hessel, V.; Lowe, H. Utilization of micromixers for extraction processes. Chem. Eng. Technol. 2001, 24 (1), 11−17.

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DOI: 10.1021/acssuschemeng.7b04368 ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX