Organic Solvent NF (OSN)

Chapter

10

Organic Solvent NF (OSN) ACRONYM A APDEMS API APTMS

Aminopropyldiethoxymethylsilane Active pharmaceutical ingredients (3-Aminopropyl) trimethoxysilane

B BIS BPAPEEK and TBPEEK

N,N-methylenebis-(acrylamide) structure

O

O O O

BPEi

O

n n

O

branched polyethylene imine

Reverse Osmosis. https://doi.org/10.1016/B978-0-12-811468-1.00010-4 # 2019 Elsevier Inc. All rights reserved.

249

250 CHAPTER 10 Organic Solvent NF (OSN)

C cellulose acetate structure [1]

CA Catalyst complex L Me N Me2 2 N L

32.1 Å

M

NMe2Me2 N

M

M O

O

Me2 N Me2N L

L

NMe2Me2N

M

O

L NMe2 NMe2

O

M L

M

Me2N Me2N

O

O

O

O

NMe2 NMe2

L M

M L

Me2N Me2 N L

O

NMe2 NMe2

O O

O M

M N Me2 Me2N

M

NMe2Me2N

L

M

L

N NMe2 Me2

L

>99.9% Retention in a membrane reactor

Cotype Jacobsen catalyst structure [2]

trihexyl(tetradecyl)phosphonium structure

CyPhos 101

O N

CH3

N 3

O

O 2

S O O

chloride,

Acronym 251

D DBB DBX DEO DF DMAc DMF DMSO

1,4-dibromobutane α,α00 -dibromo-p-xylene 1,2,7,8-diepoxyoctane diafiltration dimethylacetamide dimethyl formamide dimethylsulfoxide

E ECOENG 500 EDA EDC [EMIM]OAc

cocosalkyl pentaethoxi Me ammonium methosulfate ethylenediamine 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide 1-Ethyl-3-methylimidazolium acetate

G GA GO GTI

glutaraldehyde graphene oxide genotoxic impurities

H HDA HEMA HPB

hexane diamine 2-(hydroxy) ethyl methacrylate hexaphenyl benzene

M MEK MEOA MMM MOF MPD MSA MSTFA MWCO

methylethylketone monoethanolamine mixed matrix membrane metal organic frame work m-phenylene diamine methanesulfonic acid N-methyl-N-(trimethylsilyl) trifluoroacetamide (97%) molecular weight cutoff

N NHS NMP NIPAM

N-hydroxysuccinimide N-methylpyrrolidone N-isopropylacrylamide

252 CHAPTER 10 Organic Solvent NF (OSN)

O ODA Organic-inorganic hybrid network formation by ATPMS O

4,400 -Oxydianiline Reaction Scheme [3]

O

N

C H2

N

O

O

O

Polyimide repeate unit

+ OMe Si

H2N

OMe OMe

O

O N

N O

Aminopropyl trimethoxysilane

O

C H2

H N

O O

O

O

Si O Si

O H N

C H2

O

O

N

O N

O

O

Crosslinked structure

P PAN-H PDA PDCPD PDDA PDMS PEEK PEEKWC PEG

hydrolyzed PAN piperazine diacrylamide polydicyclopentadiene poly(diallyldimethylammonium chloride) polydimethylsiloxane polyetheretherketone phenolphthalein based poly(ether ether ketone) polyethylene glycol

Acronym 253

PEGDEG PI PIM PMP Polyanion in LBL assembly

poly(ethylene glycol) diglycidyl ether polyimide polymers of intrinsic microporosity poly(4-methyl-2-pentyne) structures [4]

Polyimide synthesized

structure [5]

CF3 N

OC

C

CO

OC

CF3

CO

PPSF PPy PSf PTMSP PTMSP (left), PMP (center), PIM1(right) H3C

CH3 C CH3

C

n Si CH3 CH3

N

Ar

n

polyphenylsulfone polypyrrole polysulfone poly[1-(trimethylsilyl)-1-propyne] structure [6]

CH

CH3

O

C

C n

O

CH3

CN O O CN

254 CHAPTER 10 Organic Solvent NF (OSN)

Q structure [7]

Quinidine based organic catalyst O

NO2

O

O

MeO

MeO

OMe Catalyst:

S

S

O OMe NO2

N N

OH

N

HO

O N

O

HO

O

N

N

R (R,R)-TADDOL

Ru-BINAP

(4R,5R)-()-2,2-dimethyl,α,α,α00 ,α00 -tetraphenyl-1,3dioxolane-4,5-dimethanol structure [8]

(R)-(+)-2,20 -bis(diphenylphosphino)-1,10  binaphthyl] ruthenium(II)

S SA SDS SPEEK SPESS Suzuki coupling reaction product

Sulfuric acid Dodecyl sulfate sodium salt Sulfonated polyetheretherketone poly(ether sulfide sulfone) structure [9]

Acronym 255

CH3

CH3

H3CO

3

CH3 91%

9 OCH3 H3CO 5 OCH3

O

4

9 O 90% H CO OCH3 3 6 OCH3

O

CH3 H O 5 2 2 45%

6 OH

4b

OCH3 OCH3

CH3

OH

7

4a

2

Pd(AcO)2, Et3N, PPh3, >95% OCH3 OCH3 H3CO H3CO N2,µW, t =30 min. 2 OCH3 1 OCH3 4a + 4b = 67%

H2, Pd/C 3

OH

CH3

7 OH

Br

1

CH3 9

H3CO O 7 OCH3

CH3

O O

O 6

H3CO

85%

H3CO

CH3

Overall yield: 20% OH Mean step yield: 76%

8

O

T tetrabutylammonium bromide triethylamine triethylenetetramine thin-film nanocomposite tetrahydrofuran 2,4,6-Trimethylbenzoyl-diphenyl-phosphine

TBAB TEA TETA TFN THF TPO

V VAPEEK reaction Scheme [10] OH O O

CH3 +

+

K2CO3

F HO

F

OH OH O

O CH3 +

170°C DMSO, toluene

2KF

O O n

VESTAKEEP

PEEK polymer from Evonik Industries

+

CO2

+

H2O

256 CHAPTER 10 Organic Solvent NF (OSN)

Separation processes play a key role in the chemical and pharmaceutical industries, where the chemical synthesis is often performed in organic solvents. The highly valued products have to be separated from the organic solvent. As well, the organic solvent has to be recovered or discarded after the products are removed. Many conventional separation processes can be used for these purposes. Distillation, evaporation, adsorption, extraction, and chromatography are the examples. Recently, more attentions are focused on membrane separation due to the substantially lower energy requirement than the conventional processes [11]. The thermal damage of the heat-sensitive product molecules due to the room temperature operation of the membrane process is another reason. However, most of reverse osmosis (RO) works are for desalination and water treatment except for very few that are dealing with the treatment of organic solvents. The reason is that the molecular size of organic solvents is larger than water molecules, which makes the separation by the size exclusion of the solute less effective. Moreover, the electrostatic repulsive force working between the membrane and the solute is much weaker in the organic solvent due to the solvent’s low dielectric constant. Therefore, the charged solute will pass through the pore even when the pore is only slightly larger than the solute. The development of RO membrane for organic solvent remains as one of the future challenges. Compared with RO, a vast amount of papers has been published on the so-called organic solvent nanofiltration (OSN). This chapter is dedicated to OSN because of its importance in the pharmaceutical and chemical industries. Especially, new membrane materials and membranes have been proposed recently, which can widen the scope of OSN applications in the future. It should be noted that this chapter is written mainly based on the comprehensive review paper written by Livingstone and his group [11]. As usual, membranes are characterized by the flux (or pressure normalized solvent permeance) of the chosen solvent and the solute rejection. Unlike RO of aqueous solutions, inorganic salts are not used for the solute, instead the following organic solutes are used to measure the rejection. Linear and branched n-alkanes, dyes (rose bengal MW ¼ 973.7 is often used), hexaphenyl benzene, polyethylene glycol (PEG), polyisobutylene, and oligostyrenes.

10.1 OSN Membranes 257

10.1 OSN MEMBRANES The membranes used for OSN are classified as follows: (1) (2) (3) (4)

Polymeric membranes Integrally skinned asymmetric membranes Thin-film composite (TFC) membranes Ceramic membranes

The membranes used for OSN are listed in Tables 10.1–10.5 according to the above classification.

Table 10.1 Integrally Skinned Asymmetric Membranes (See the Acronym in the End of the Chapter) Polymer Dissolved in Solvent

Post Treatment

Phase inversion method P84 in DMF + Cross-linking dioxane with 1,6 hexane diamine Ultem 1000 Cross-linking Matrimid 5218 with P84 1,6 hexane HT P84 in diamine mixed solvent P84 in mixed Cross-linking solvent with 1,6 hexane diamine Polyimide Cross-linking (laboratory with synthesized) in 1,6 hexane DMF + dioxane diamine P84 in DMF + Cross-linking dioxane with diamines, ODA, EDA, PDA, HAD Udel in NMP and THF PSf Udel P1835 in NMP, DMAc, DMF, DMSO, with various additives

Permeance (L/m2 h bar)

Solute Rejection (%)

References

Styrene oligomers

ca 3

< 200 (MWCO)

[12]

Styrene oligomers

0.5

220 (MWCO)

[13]

Styrene oligomers

1.3

220 (MWCO)

[14]

DMF

Styrene oligomers

4.4

220 (MWCO)

[15]

DMF

Styrene oligomers

1–8

250–400 (MWCO)

[16]

Isopropanol

Rose bengal Rose bengal

37–92 47–76 > 90

[17, 18]

Isopropanol

9.7–0.07 2.4–0.08 4.5

Solvent

Solute

DMF toluene

DMF

DMS

[19]

(Continued)

258 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.1 Integrally Skinned Asymmetric Membranes (See the Acronym in the End of the Chapter)—cont'd Polymer Dissolved in Solvent

Post Treatment

PSf Udel P1835 in NMP/THF with PEG, PVDF additive PPSf in DMAc, NMP DMF/NMP PPSf PPSf/Matrimid in NMP PEEKWC BPAPEEK and TBPEEK in NMP/THF TBPEEK in NMP and THF VAPEEK in THF/ EDC/NHS VESTAKEEP 4000P in MSA/SA at high temperature P84 in THF/NMP

P84

Torlon in NMP PSf or PI

Cross-linked with 1,6-hexane diamine Solvent exchange and drying

Cross-linked with pxylylenediamine added to the gelation bath Cross-linker Jeffamine 400 with no pore preserving agent Cross-linking with Diisocyanate Cross-linked with photoinitiator and UV

Solvent

Solute

Permeance (L/m2 h bar)

Solute Rejection (%)

References

Isopropanol

Rose bengal

0.1

ca 96

[20]

Methanol

Rose bengal

1.8

88

[21]

Isopropanol MEK Acetone Isopropanol Methanol Isopropanol

Rose bengal Sudan II

98.6 95 96.9 99.8 90 90 87

[22] [23]

Isopropanol

Rose Bengal

0.02 2.1 1.8 0.9 1.7 0.4(TBPEEK) 0.1 (BPAPEEK) 1

90

[26]

Isopropanol Acetone

Rose bengal

0.1 0.2

ca 90 ca 90

[10]

THF

Polystyrene

0.4

250 (MWCO)

[27]

DMF NMP

Rose bengal

0.4 0.2

98 98

[28]

Acetone Toluene

–

Very low

–

[29]

Acetone

Polystyrene

1.2

260 (MWCO)

[30]

PSf with ethyl acetate isopropanol PI with isopropanol

Rose bengal 8.1 0.2 1.4

91 94 96

Rose bengal Rose bengal

[24] [25]

[31]

10.1 OSN Membranes 259

Table 10.1 Integrally Skinned Asymmetric Membranes (See the Acronym in the End of the Chapter)—cont'd Polymer Dissolved in Solvent PSf

PSf in DMF/THF

P84 coated Polyamic acid blend

PBI in DMAc

Post Treatment

Solvent

Solute

Permeance (L/m2 h bar)

Solute Rejection (%)

References

Cross-linker pentaacrylate, photoinitiator acyl phosphine oxide and UV Cross-linker pentacrylate, photoinitiator TPO and UV Cross-linked by heating Thermal treatment in a bath of dioctyl sebacate Cross-linkers DBX, DBB

Stable in acetone, butyl acetate, ethyl acetate, toluene, xylene Isopropanol

–

–

–

[32]

Rose bengal

1.2

94

[33]

–

–

–

[34]

Gasoline/ kerosene mixture

–

Drastically reduced –

[35]

Acetonitrile

PEG 2000

10 by DBX

Ethanol Ethyl acetate DMAc

Brilliant blue R

3.7 5.2

19.5 (gasoline/ kerosene separation factor) 100% rejection by DBX 100% rejection oligonucleotides and carbon capture and storage

PBI in [EMIM] OAc Commercially available Celazole PBI (30,000 Da)

Cross-linkers GA or DEO Crosslinking with 3 wt% p-α,αdibromoxylene (DBX)

Good rejection performance even after extreme acid and base treatment PI

[38]

Tris was added to the dope.

Isopropyl alcohol

Polystyrene oligomers dissolved in solvent mixtures used for the synthesis of peptides,

Dye

270% increase in permeance by Tris addition

Slight decline in separation

[36]

[37]

[39]

Substrate

Monomers in In Situ Polymerization (polymer used in thin layer coating)

P84 UF

TMC MPD, Piperazine, Hexanediamine

P84 UF

TMC + Fluoroacylchloride, MPD, Fluoroalkylamine, Siliconealkylamine Same as [41]

PI, PEEK

Permeance (L/m2 h bar)

Rejection

Reference

Polystyrene (Mw 220)

1.5

100

[40]

Polystyrene (Mw 220)

0.3

95

[41]

1.9

99

Posttreatment

Solvent

Solute

In situ polymerization, posttreatment with DMF In situ polymerization

THF

Toluene THF

In situ polymerization, posttreatment with DMF In situ polymerization

THF

Polystyrene

0.9

99

[42]

Methanol

Oleic acid

6

93

[43]

Oleic acid

6 –

92 –

[44]

13 1.2

92

[45]

1 4.8

96 90

[46]

28.6

99

[47]

0.79 (without GO) 3.17 (with GO) 2.4

99.1

[48]

PAN

TMC, Piperazine/MPD

PAN

TMC/PDMS, Piperazine/MPD blended with PDMS Isophthaloyl chloride, Polyethyleneimine

In situ polymerization

PI

(PTMSP)

Coated

Ethanol

PSf/PEEK PSf/PI PAN-H PAN-H

(PTMSP)

Casting

THF

Bromothymol blue Crystal violet Remazol brilliant blue R Rose bengal

(PPy)

In situ polymerization with and without GO

Isopropanol

Rose bengal

Dip-coated and cross-linked by PEGDEG

n-Heptane

PSf/SPESS

PAN

(PIM-1)

In situ polymerization

Acetone Methanol Acetone n-Hexane Methanol

HPB

98.5 97

[49]

260 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.2 Thin-Film Composite (TFC) Membranes

Cellophane

(PIM1, PMP, PTMSP)

Dip-coated

Ethanol

Free standing transferred to polymeric or ceramic support Polymeric or ceramic support PAN

(PIM-1)

Spin-coated

(Polystyrene-b-poly (ethylene oxide)/ polyacrylic acid blend) (Polyacrylic acid crosslinked by bisacrylate terminated polyethylene oxide in situ polymerized)

PAN-H

(PDDA/SPEEK)

0.05

98

[6]

n-Heptane

Remazol brilliant blue R HPB

18

90

[50]

Spin- or dipcoated

–

–

–

–

[51]

Thin layer formation of amphiphilic segmented polymer networks Layer-by-layer assembly

Isopropanol

Rose bengal

0.4

99

[52]

Ispropanol THF DMF

Rose bengal

0.5

99

[53]

98 92 99

[4]

(PDDA/PSSNa, PSSH, PVSNa, PVSH)

Layer-by-layer assembly

Isopropanol DMF

Rose bengal

PAN-H

(PDDA/PAA)

THF

Rose bengal

0.2 13

98 99

[54]

PSf

(Branched BPEi/PAA)

THF

Anthracene

29.6

68

[55]

Charged silicon composite with PAN-H Polyimide

(PDDA/SPEEK)

Layer-by-layer assembly Layer by layer assembly Layer-by-layer assembly

Isopropanol THF DMF

Rose bengal

0.1

99

[56]

10 0.07

Water, Methanol, Acetonitrile Water

Methylene blue

98 89 >99.9

[57]

86.5

97.5

[58]

74.2

88.5

Nylon MF membrane or anodic aluminum oxide membrane

Polybenzimidazole

Hollow fiber coextrusion

Reduced GO (r-GO)

Vacuum filtration of r-GO on the substrate and washed by solvent or water

Methanol

Basic fuchsin

10.1 OSN Membranes 261

PAN-H

8.82 0.05 1.6

Polymer and Filler

Solute

Solvent

Permeance (L/m2 h bar)

Rejection (%)

Polystyrene

DMF

21

240 (MWCO)

[59]

Bromothymol blue

Ethanol

0.5

80.5–82.5

[60]

Bromothymol blue, Methyl orange

Isopropanol

35

97.1

[61]

Heated by argon ion laser beam

Rose bengal

Isopropanol

0.8

99.5 95

[62]

Organic inorganic hybrid network formed by APTMS MOF (HKUST-1)

Styrene oligonmers

Dichloromethane

0.8

236 (MWCO)

[3]

Lower flux decline with MOF

Higher rejection with MOF

[63, 64]

Posttreatment

Integrally skinned asymmetric membrane P84 in Cross-linked by 1,6DMF/1,4 dioxane hexanediamine mixture TiO2 Cellulose acetate in Heated by argon ion acetone/formamide laser beam mixture, Gold nanoparticles PDMS in hexane, Heated by argon ion Gold nanoparticles laser beam precross-linked at room temperature Matrimid 9725 P84 in DMA, DMA/ Dioxane, DMA/THF and DMF/Dioxane mixture P84 in DMF/Dioxane/Maleic acid mixture P84

Styrene oligomers

References

262 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.3 Mixed Matrix Membranes (Asymmetric Membrane by Phase Inversion)

Table 10.4 MMM for TFC

Substrate

Monomer (Polymer Used for Thin Layer Coating) and Filler

Posttreatment

Solvent

Solute

Permeance (L/m2 h bar)

Rejection

References

0.58

98.5

[65]

0.132

96

[66]

(PDMS) with zeolite ZSM-5 and USY

Cross-linked

Toluene

Matrimid 5218

(PDMS) with silicalite zeolites (CBV3002, PQ-Corporation, USA) (PDMS) with MOF [Cu3(BTC)2], MIL-47, MIL-53(Al), Zif-8 silylated by MSTFA MPD and TMC with ZIF-8, MIL-53(Al), NH2MIL-53(Al) and MIL101(Cr) in organic phase Ethylenediamine and Isophthaloyl chloride (Precoated with polyethleneimine solution) with TiO2 filler fuctionalized by MEOA or TETA TMC and MPD

Cross-linked

n-Propanol

Wilkinson catalyst (925 Da) Rose bengal

Cross-linked

Isopropanol

Rose bengal

0.7

98

[67]

In situ polymerization

THF

Styrene oligomer

11

200 (MWCO)

[68]

In situ polymerization

Methanol

Bromothymol blue

25

94.7

[69]

In situ polymerization

MEK/Toluene mixture

Lune oil

0.7

94.7

[70]

Polymerized by UV photoinitiation

Acetone Toluene

–

–

200 (MWCO)

[71]

Mtrimid 9725

P84

Matrimid 5218

PEI with silica nanoparticles functionalized by APDEMS PI

NIPAM, HEMA are polymerized in the presence of cross-linker BIS and stabilizer SDS and TEA.

10.1 OSN Membranes 263

PAN

264 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.5 Inorganic Membranes Material

Method

Solute

Solvent

Permeance (L/m2 h bar)

Rejection (%)

Reference

Carbon nanosheet SilicaZirconia coated on alphaalumina Titania SilicaZirconia coated on alphaalumina Methylated SiO2 colloid sol γ-Alumina/ anataseTiO2

Plasma-enhanced vapor deposition Sol-gel method

Ethanol

Azobenzene

26–250

23–94.4

[72, 73]

Methanol at 50 °C

PEG

1.8

600 (MWCO)

[74]

Sol-gel method Sol-gel method

Hexane Ethanol at 60°C

– 0.06

– 80 for MW ¼ 200

[75] [76]

Sol-gel method

n-Hexane

Linoleic acid Alcohols and hydrocarbon of different molecular weight Polyolefin oligomers

7.2–27

1000–2000 (MWCO)

[77]

Treated by organo-silane reagents, (CH3)2SiCl2 and C8H17CH3SiCl2 Functionalized with methyl, pentyl, octyl, dodecyl groups by Grignard reagent

n-Hexane (Water)

PEG

3–5

410–650 (PEG MWCO in water)

[78]

Acetone

PS580

81

[79]

TiO2

10

Other interesting works on the fabrication of OSN membranes are as follows: According to Marchetti et al. recent OSN membrane development is more focused on ultrathin membrane with high flux. But the development of OSN membranes with high selectivity is equally important [80]. Mautner et al. manufactured OSN membranes from nanocellulose by applying paper making process. (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) oxidized nanofibrillated cellulose (NFC) (called NFC-O) fibers were suspended in water and multivalent cations were added. The suspension was then filtered and the resulting filter cake, that is, the fiber mat, was pressed to remove water. The filter cake was further hot pressed at 120°C. The OSN performance of the membrane was as follows. The permeance depended on the

10.2 OSN Membrane Applications 265

grammage (g/m2, gsm) of the nanopaper. At 65 gsm, the permeance for water, tetrahydrofuran (THF), and n-hexane was ca. 3, 10, and 17 L/m2 h MPa, respectively. Molecular weight cut-off (MWCO) measured by PEG and polystyrene (PS) oligomers in THF was 3.2 and 6 kDa [81]. Amirilargani et al. made a comprehensive review on the surface modification of membranes for OSN. A major challenge of OSN membrane is to maintain membrane stability in terms of selectivity and permeability. For this purpose, the selective layer of OSN membranes was functionalized by grafting, light-induced modification, plasma treatment, polyelectrolyte modification, etc. This paper reviews the recent progress in this field on the surface modification of different types of polymeric and ceramic OSN membranes [82].

10.2 OSN MEMBRANE APPLICATIONS Priske et al. recently wrote a review article on the applications of OSN. According to Priske et al. the first commercial successes were in the early 1990s and since then a number of new applications and processes were developed that prove the potential of OSN as a resource-efficient cold separation technology that enables new processes and even new products [83]. Buonomenna and Bae wrote a review article on the OSN applications in pharmaceutical industry, focusing on all aspects related to OSN (i.e., membrane materials, commercial membranes, transport theories, and applications) to understand the role of this technology in pharmaceutical industry [84]. According to Marchetti et al. [11] the OSN applications are classified to concentration, solvent exchange, and purification. In concentration, solute is separated from solvent to obtain a high-value solute or to recover the solvent. OSN is an excellent alternative to distillation due to mild operating conditions. In the pharmaceutical industry, isolation and concentration of the bioproducts such as antibiotics, pharmaceutical intermediates, or peptides from organic solvents are necessary. Interest in the natural compounds with biological activities and benefits for the human health has grown recently. Those are vitamins, antioxidants, flavonoids, terpenoids, carotenoids, catechins, phytoestrogens, and minerals found in aromatic herbs and other plants. Extraction and concentration are necessary to recover those natural compounds. A large amount of solvent is used in organic synthesis and the solvent is lost unless it is recovered. As well, purification of industrial products often requires a large volume of solvent.

266 CHAPTER 10 Organic Solvent NF (OSN)

Handling organic solvent has undesirable effects such as risk of cancer, mental diseases, air and water pollution, soil contamination, degradation of ozone layer, and greenhouse gas effect. Reduction in the amount of solvent used in the industry by solvent recovery is thus necessary. For this purpose, the impurities in the solvent should be removed. One thing common in solute enrichment and solvent recovery is that solutes should be retained by the membrane while solvent passes through the membrane. In solvent exchange, the solution changes from being rich in solvent A to solvent B. The main advantage of using OSN in solvent exchange is that a high boiling solvent A can be changed to low boiling solvent B without applying heat. Thus, the removal of solvent from the high-value product can be done by evaporation with less heat requirement. The chemical reaction is performed by several reaction steps and often different solvents are required to obtain the final product. As well, concentration and purification steps also need solvents. Thus, solvent exchange is an important process for chemical reaction and reaction product recovery. After product enrichment, the purification is necessary to obtain high-value products. In fact, the purification process accounts for up to 90% of the total production cost. As well, more than one-half of capital investment in the pharmaceutical industries is related to purification processes. In general, low energy consumption, continuous operational mode, and modularity are the main advantages of the membrane-based processes. It should be emphasized that purification is different from solute enrichment because high selectivity is required among different solute species, that is, the membrane should exhibit high selectivity for one major product component over the other contaminants. In this respect, the current OSN membrane’s selectivity is not necessarily high enough and improvement of membrane is needed to compete with the conventional purification processes such as chromatography and recrystallization. Another application where high selectivity of one solute over the other solutes is required is OSN-assisted chemical reaction. One of the examples is the membrane-enhanced peptide synthesis (MEPS). The first amino acid is attached to PEG and then chain extension is performed by repeating coupling and deprotection steps. At each step, the reaction byproducts and excess reactants are removed by diafiltration through the OSN membrane while the growing chain of peptide is retained. Isolation of stereo isomer is another example. Physical or biological receptors are often capable of distinguishing stereoisomers since different isomers may have different physical and biological properties. Thus, it is

10.2 OSN Membrane Applications 267

important to isolate one enantiomer from the racemic mixture. Often, one enantiomer is enlarged by the complex formation with resolver (or catalysis, etc.) and precipitates while the other passes through OSN membrane. OSN is a new membrane technology with many applications in pharmaceutical and fine chemicals development and manufacture, from laboratory through production scales. One application of particular industrial relevance is the ability to recover and recycle homogeneous catalysts, in particular asymmetric, organometallic, homogeneous transition metal catalysts. Industrial application of this group of catalysts is often limited due to the cost of applying these catalysts to single reactions and the subsequent product yield losses associated with removal of the catalyst from solution. OSN provides a technique that can maximize the value of the catalyst through catalyst recycle from one reaction batch to the next, whilst minimizing the concentration of catalyst present in the reaction product. OSN application examples are listed in Tables 10.6–10.8. The following papers have been published recently on the characterization of OSN membranes. A new method for determining the MWCO of an OSN membrane was proposed by Davey et al. utilizing poly(propylene) glycol (PPG) oligomers instead of currently popular polystyrene oligomer and PEG. The accuracy of the method was demonstrated in three different solvents (methanol, acetone, and toluene) and five different commercially available OSN membranes (DuraMem 150, 200, 500, PuraMem 280, and StarMemTM 240) [123]. The radius of gyration of the solute, which determines its size, can be completely different in water than in acetone due to different solvation. In this work, the diffusion of different PEG oligomers in water and acetone through a ceramic TiO2 membrane is studied in three steps. (1) The radius of gyration of PEG oligomers in water or acetone is obtained. (2) TiO2 membrane is characterized by pore size and pore size distribution. (3) Information obtained in the previous steps will be combined to model the diffusion of the solvated PEG oligomers through the membrane [124]. When the molecular weights of the solutes are closer, their fractionation becomes more difficult. A single membrane stage is insufficient and a multistage system is required. Abejo´n et al. established mathematical models for nanofiltration membrane cascades aiming at the reduction of solvent consumption in a pharmaceutical separation process [125].

Solvent

Solute

Permeance (L/m2 h bar)

Butyl acetate Ethanol

Spiramycin (antibiotic) Rosemary (antioxidant)

1 –

–

Rice bran oil

γ-oryzanol (antioxidant)

39–53 L/m2 h

DK (GE-Osmonic), NF-45 (Film Tec), TFC-SR1(Koch)

Ultrafiltered corn extract

Xanthophyll

Starmem 122 DuraMem 150

Methanol, Ethanol, Isopropanol, Ethyl acetate Crystallization mother liquor (Hybrid with distillation) Decane (low boiler) MEK/toluene

Imatinib, Riluzole, Donepezil, Atenolol, Alprazolam Drug product API (Active pharmaceutical ingredients)

DK: 0.16–0.37 NF-45: 0.45–0.63 TFC-SR1: 1.20–2.34 All at 50 °C 0.35 (DuraMem 150/Atenolol/ Methanol)

Membrane Polyimide synthesized DuraMem 4in Spiral module

a

Starmem 122

GMT oNF1 TFN with aminofunctionalized UZM-5 nanoparticles PVDF coated with Siloc (PDMS) or CA STARMEMTM122, SOLSEP NF030306

STARMEM

Crude soybean oil/n-hexane mixture Soybean oil/ acetone

Ethyl acetate

Rejection (%)

References

99 Antioxidant capacity of retentate is not low. Higher molecular weight oxidant does not go into the permeate. Oryzanol enriched from 0.5 to 4.1 wt% 98–99

[5] [85]

98 (DuraMem 150/ Atenolol/Methanol)

[88]

1.2

99.9

[89]

Hexacosane (heavy boiler)

1.4

80

[90]

Oil

0.92

96.3

[91]

Oil

1 (with Siloc coating)

80 (with Siloc coating) 58(with Siloc coating)

[92]

16.8 L/m2 h (STARMEMTM) 4.8 L/m2 h (SOLSEP) 2.3

70 (STARMEMTM)

[93]

Fatty acid Oil

Cyphos 101 (MW: 519) ionic liquid

[86] [87]

78 (SOLSEP) 97.3

[94]

268 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.6 Application Examples

DuraMem™ membrane

Methyl oleate and Palargonic acid permeate

Ionic liquid rejected 96%, monomethyl azelate is also rejected.

[95]

Erythromycin

0.3 (NF)

95 (NF)

[96]

0.17 (DF)

>95 of Erythromycin (DF)

MEK

API and GTI

>3 (Solsep and MEK)

300 (MWCO)

[97]

–

Intermediate I (MW 221, API) and bromomethane (MW 188, GTI)

–

–

[98]

Toluene, Ethyl acetate

Palladium catalyst on adsorbent, API

–

–

[99]

THF/water with HCl

Dimer (API)

0.3 (Duramem)

99.8 (Duramem)

[100]

API-intermediate (GTI)

66 (Duramem)

–

C (API), A (excess reagent)

–

–

[101]

DMF,THF

Janssen PharmaceuticaNV Intermediate of drug candidate (MW 675) Oligomeric impurities (MW > 1000) Roxithromycin macrolide antibiotic (Roxi) (API),

–

99% of oligomeric impurity removed with >99% of API-int recovery.

[102]

–

95% product yield with

[103]

– Two cascade DF and

[MOct3N] {Tf2N} ionic liquid

(Continued)

10.2 OSN Membrane Applications 269

MPF-50 and MPF-60 (Koch) (Ethyl acetate is exchanged with methanol in DF, while retaining erythromycin in the feed.) GMT-oNF-2, SolSep NF010206, GTI (MWCO h300) is removed from API (MWCO >300). DuraMem150 and 200 GTI removal from API using membrane cascade (Product yield increased from 35.5 to 84.3.) Palladium (GTI) is adsorbed to the adsorbent (polystyrenebound trimercaptotriazine) and retained by membrane while the product permeates. Duramem, Starmem, Solsep, Inopor Puramem and Duramem used in stripping cascade for enrichment of API that is further purified by crystallization Duramem spiral wound module, by DF The second diafiltration for solvent recovery is required.

Methyl oleate (reactant), Palargonic acid + Monomethyl azelate First NF with Ethyl acetate

Membrane

Solvent

solvent purification by active charcoal PBI membrane, Two-stage membrane cascade Duramem, Puramem and Kock SelRo

Solute

Permeance (L/m2 h bar)

4-Dimethylaminopyridine (DMAP) and ethyl tosylate (EtTS)(GTIs) Feed stream containing API of 78% Ethyl acetate

Puramem was found best

Rejection (%)

References

GTI, 5 ppm in the final solution

Roxithromycin (API), 4-dimethylaminopyridine (DMAP) (GTI) High value monomeric chemicals (vanillin, methyl vanillate, 2-benzyl phenol, benzyl phenyl ether) separated from high MW byproducts of lignin oxidation Transesterification products

–

API purity >99%

[104]

–

–

[105]

0.4–1.4 (Solsep 30,705 at pH 9)

Date for Solsep 30,705 at pH 9 100 (triolein) 97 (diolein) 70 (glycerol) 30 (monoolein) Very low (ester) > 98 Both for total phenolics and total flavonoids –

[106]

Cis-fatty acids combine with triisobutylamine and rejected. Trans- and saturated fatty acids go through the membrane.

[109]

Desal, MPF, STARMEM, Solsep their capability in biodiesel separation process

Methanol

Duramem 300 and 500

Ethanol

Polyphenol Flavonoids

0.65–0.8

Review Starmem 200 & 400, Duramem 200 to 900 Combination with other separation processes PDCPD membrane for separation of fatty acids soybean oil

Plant extracts from sideritis, grape seeds, propolis, etc.

Polyphenols

–

Toluene/hexane mixture

Cis-fatty acid (oleic, petroselinic, vaccenic, linoleic, linolenic) from saturated (stearic), and trans-fatty acid (elaidic)

39 L/m2 h

[107]

[108]

270 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.6 Application Examples—cont'd

Starmem 122

Methanol

Membrane-enhanced peptide synthesis (MEPS) DF removes byproducts and excess reagents of coupling and deprotection. Separation of rasemic tartaric acid to its enanciomers

–

STARMEM 122

Hexane for resolution, Toluene for decomplexation

Acetone

13.6

55.2

[110]

–

–

[111]

Diastereomeric salt formation of α-phenylethylamine with D-tartaric acid and di-ptoluoyl-D-tartaric acid as resolving agents The complex is rejected by the membrane while L-tartaric acid passes through. S-phenethylalcohol forms complex with resolver ((R,R)-TADDOL) and precipitates while R-enantiomer passes through the membrane. Catalyst (see Acronym, Quinidine-based organic catalyst)

–

–

[112]

–

–

[8]

[Pd0(PPh3)OAc] catalyst and Suzuki coupling reaction product (See acronym Suzuki coupling reaction product 4a and 4b)

About 2

[7]

Catalyst 98% Reaction product 78%

[9]

10.2 OSN Membrane Applications 271

Asymmetric API synthesis Quinidine-based organocatalyst is designed for high enantioselectivity and high membrane rejection. Commercially available second-generation membranes (Evonik MET Ltd., UK) Polyimide MWCO 200

–

Half generation (amidoamine) dendrimers (MW ¼ 404) and Rhodamine B (MW ¼ 479) were used as sarrogate. Pentapeptide

Table 10.7 Catalyst Recycling in Various Reactions with Homogeneous Metal Organic Catalyst Membrane

Solvent

Reaction

Starmem 228, Puramem 280 Catalyst successfully retained

Toluene

–

Methanol

Starmem 228

Octene/ tetradecene mixture

Starmem 122

50/50:Ethyl acetate/ionic liquid (ECOENG 500, TBAB, CyPhos1101)

POSS (polyhedral oligomeric silsesquioxane) enlarged Ru catalysts and (Ring closing methathesis) RCM reaction product of diethyl diallylmalonate Ru-BINAP Asymmetric hydrogenation of dimethyl itaconate (DMI) to dimethyl methylsuccinate (DMMS) Metathesis reaction of 1-octene to 7-tetradecene and ethene 4-bromoacetophenone (BrAP) and phenylboronic acid

Poly (dimethylsiloxane) (PDMS) layer cast on a porous sublayer of poly(acrylonitrile) (PAN)

Suzuki coupling of aryl chloride and bromide

Catalyst

Product

Reference [113]

–

–

Various Ru-type catalysts

Pd type catalyst for Suzuki coupling + ionic liquid

Suzuki catalyst imidazolylidene catalyst, bis(1,3dibenzylimidazoline-2-ylidene)diiodopalladium (II) and palladium(II) acetate stabilized by the quaternary phosphonium salt (quat) tetraphenylphosphonium bromide Palladium complexes with the phosphinated polymer

[114]

[115]

4-Acetyl-biphenyl (ABP)

[116]

[117]

[118]

N30F

Isopropanol

Hydrolytic kinetic resolution of epoxyhexane

Cotype Jacobsen catalyst

Epoxidation, Alcohol oxidation, Heteroatom oxidation

Sandwich type polyoxometalate ([MeN(n-C8H17)3]12[WZn3(ZnW9O34)2]) catalyst

[119]

Multiple NCN-palladium, NCN-platinum catalyst Rigidity of polymer backbone is important. Ligand stabilized copper

[1]

MPF-60 (MWCO ¼ 400) Laboratory made Polyimide membrane

DMF

Polymer functionalized by click reaction

95% (Catalyst rejection) 0.23 L/m2 h bar (permeance)

96%(Polymer rejection), 45% (catalyst rejection), Flux 0.67 After five stages of diafiltration 99% of catalyst is removed.

[2]

[120]

274 CHAPTER 10 Organic Solvent NF (OSN)

Table 10.8 OSN with Crystallization Membrane

Solvent

In Permeate

In Retentate

Effect

References

PI, PBI, and PEEK membranes Mixedsuspension, mixed-productremoval (MSMPR) crystallization

THF/ ethanol/ water

Purge impurity 4-hydrazinobenzoic acid (MW ¼ 152 Da)

Concentrate API (deferasirox, MW ¼ 373 Da)

98.0% and 98.7% yield is achieved.

[121]

API (griseofulvin)

Crystal size is large at high flux and small at low flux of the membrane.

[122]

10.3 ORGANIC LIQUID RO Despite the attempt of separating inorganic electrolytes from methanol and ethanol by using cellulose acetate RO membrane in as early as 1983 [126–128], there are only few reports on organic solvent RO since then. Some examples are as follows. A comprehensive patent was granted to Exxon Mobile in 1992 for the recovery of aromatic solvents, such as N-methyl pyrollidone (NMP), phenol, sulfolane, furfural, N,N-dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and dimethyl-acetamide (DMAc), preferably NMP, phenol, or furfural which were used for oil extraction, by interfacially in situ polymerized TFC membranes. The in situ interfacial polymerization is carried out on a solvent resistant ultrafiltration membrane composed of generally insoluble polymers such as nylon 6,6, cellulose, polyester, Teflon, polypropylene, and other insoluble polymers, preferably nylon 6,6 with pore sizes in the range of 0.02–0.1 μm. For in situ polymerization, the multifunctional amino group reactants include polyethylenimine, polyvinylamine, polyvinylanilines, polybenzylamines, polyvinylimidazolines, amine modified polyepihalohydrins, and other amine containing compounds, m-phenylene diamine, p-phenylene diamine, triaminobenzene, piperazine, piperidine, 2,4-bis (p-aminobenzyl) aniline, cyclohexane diamine, cycloheptane diamine, etc. and mixtures thereof, which are reacted with chlorides, acid anhydrides, aliphatic and aromatic diisocyanates, thioisocyanates, haloformates (e.g., chloroformates) and sulfonyl halides, (e.g., sulfonyl chlorides), and mixtures thereof. A few examples of these agents are trimesoyl chloride, cyclohexane-1,3,5 tricarbonyl chloride, isophthaloyl chloride, terephthaloyl

References 275

chloride, diisocyanatohexane, cyanuric chloride, diphenylether disulfonyl chloride, formyl chloride, acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride, caproyl chloride, heptanoyl chloride, octanoyl chloride, pelargonyl chloride, capryl chloride, lauryl chloride, myristyl chloride, palmityl chloride, margaryl chloride, stearyl chloride, etc., oxalyl chloride, malonyl chloride, succinyl chloride, glutaryl chloride, fumaryl chloride, glutaconyl chloride, acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, ethylene diisocyanate, propylene diisocyanate, benzene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, methylene bis (4-phenylisocyanate), ethylene thioisocyanate, toluene thioisocyanate, naphthalene thioisocyanate, ethylene bischloroformate, propylene bischloroformate, butylene bischloroformate, 1,3-benzenedisulfonyl chloride, 1,4benzene disulfonyl chloride, 1,3-naphthalene disulfonyl chloride and 1,4naphthalenedisulfonyl chloride, etc., and mixtures thereof. Following the sequential deposition of these solutions, the resulting film is heated to promote crosslinking of any unreacted amine. This post-heating step can be at a temperature of about 60–150°C, preferably 80–120°C, for from 1 to 20 min. RO performance of one of those membrane was tested with a sample of an extract oil solution (average molecular weight of oil ¼ 400 g/mol) containing 12 vol% oil in NMP at 70°C and feed pressure of 500 psig. Fluxes ranging from about 200 to 750 L/m2 day with corresponding oil rejections of 98 vol% to 88 vol% were obtained [129]. Lively prepared asymmetric carbon molecular sieve (CMS) hollow fibers with thin selective skin layers from poly(vinylidene fluoride) (PVDF). Cross-linking of as-spun hollow fibers “locked-in” the porous substructure and the fiber morphology even after the cross-linking and high-temperature pyrolysis. This organic solvent reverse osmosis (OSRO) membranes could be used to purify xylene without phase change [130]. Halford highlighted the above CMS membrane for the purification of p-xylene from an isomer mixture by RO [131].

REFERENCES [1] H.P. Dijkstra, C.A. Kruithof, N. Ronde, R. van de Coevering, D.J. Ramo´n, D. Vogt, G.P.M. van Klink, G.J. van Koten, Shape-persistent nanosize organometallic complexes: synthesis and application in a nanofiltration membrane reactor, Org. Chem. 68 (2003) 675–685.

276 CHAPTER 10 Organic Solvent NF (OSN)

[2] S. Aerts, A. Buekenhoudt, H. Weyten, L.E.M. Gevers, I.F.J. Vankelecom, P.A. Jacobs, The use of solvent resistant nanofiltration in the recycling of the co-Jacobsen catalyst in the hydrolytic kinetic resolution (HKR) of epoxides, J. Membr. Sci. 280 (2006) 245–252. [3] H. Siddique, E. Rundquist, Y. Bhole, L.G. Peeva, A.G. Livingston, Mixed matrix membranes for organic solvent nanofiltration, J. Membr. Sci. 452 (2014) 354–366. [4] P. Ahmadiannamini, X. Li, W. Goyens, B. Meesschaert, W. Vanderlinden, S. De Feyter, I.F.J. Vankelecom, Influence of polyanion type and cationic counter ion on the SRNF performance of polyelectrolyte membranes, J. Membr. Sci. 403404 (2012) 216–226. [5] D. Shi, Y. Kong, J. Yu, Y. Wang, J. Yang, Separation performance of polyimide nanofiltration membranes for concentrating spiramycin extract, Desalination 191 (2006) 309–317. [6] S. Tsarkov, V. Khotimskiy, P.M. Budd, V. Volkov, J. Kukushkina, A. Volkov, Solvent nanofiltration through high permeability glassy polymers: Effect of polymer and solute nature, J. Membr. Sci. 423424 (2012) 65–72. [7] W.E. Siew, C. Ates, A. Merschaert, A.G. Livingston, Efficient and productive asymmetric Michael addition: development of a highly enantioselective quinidine-based organocatalyst for homogeneous recycling via nanofiltration, Green Chem. 15 (2013) 663–674. [8] N.F. Ghazali, F.C. Ferreira, A.J.P. White, A.G. Livingston, Enantiomer separation by enantioselective inclusion complexation-organic solvent nanofiltration, Tetrahedron Asymmetry 17 (2006) 1846–1852. [9] A. Tsoukala, L. Peeva, A.G. Livingston, H.R. Bjorsvik, Separation of reaction product and palladium catalyst after a heck coupling reaction by means of organic solvent nanofiltration, ChemSusChem 5 (2012) 188–193. [10] K. Hendrix, M. Van Eynde, G. Koeckelberghs, I.F.J. Vankelecom, Crosslinking of modified poly(ether ether ketone) membranes for use in solvent resistant nanofiltration, J. Membr. Sci. 447 (2013) 212–221. [11] P. Marchetti, M.F.J. Solomon, G. Szekely, A.G. Livingston, Molecular separation with organic solvent nanofiltration: a critical review, Chem. Rev. 114 (2014) 10735–10806. [12] Y.H. Toh, M. Silva, A.G. Livingston, Controlling molecular weight cut-off curves for highly solvent stable organic solvent nanofiltration (OSN) membranes, J. Membr. Sci. 324 (2001) 220–232. [13] I. Soroko, M.P. Lopes, A.G. Livingston, The effect of membrane formation parameters on performance of polyimide membranes for organic solvent nanofiltration (OSN): Part A. Effect of polymer/solvent/non-solvent system choice, J. Membr. Sci. 381 (2011) 152–162. [14] I. Soroko, M. Makowski, F. Spill, A.G. Livingston, The effect of membrane formation parameters on performance of polyimide membranes for organic solvent nanofiltration (OSN). Part B: Analysis of evaporation step and the role of a co-solvent, J. Membr. Sci. 381 (2011) 163–171. [15] I. Soroko, M. Sairam, A.G. Livingston, The effect of membrane formation parameters on performance of polyimide membranes for organic solvent nanofiltration (OSN). Part C. Effect of polyimide characteristics, J. Membr. Sci. 381 (2011) 172–182.

References 277

[16] Y.H. Toh, F.W. Lim, A.G. Livingston, Polymeric membranes for nanofiltration in polar aprotic solvents, J. Membr. Sci. 301 (2007) 3–10. [17] A.K. Holda, B. Aernouts, W. Saeys, I.F.J. Vankelecom, Study of polymer concentration and evaporation time as phase inversion parameters for polysulfone-based SRNF membranes, J. Membr. Sci. 442 (2013) 196–205. [18] A.K. Holda, M. De Roeck, K. Hendrix, I.F.J. Vankelecom, The influence of polymer purity and molecular weight on the synthesis of integrally skinned polysulfone membranes, J. Membr. Sci. 446 (2013) 113–120. [19] A.K. Holda, I.F.J. Vankelecom, Integrally skinned PSf-based SRNF-membranes prepared via phase inversion—Part B: Influence of low molecular weight additives, J. Membr. Sci. 450 (2014) 499–511. [20] A.K. Holda, I.F.J. Vankelecom, Integrally skinned PSf-based SRNF-membranes prepared via phase inversion—Part A: Influence of high molecular weight additives, J. Membr. Sci. 450 (2014) 512–521. [21] S. Darvishmanesh, J.C. Jansen, F. Tasselli, E. Tocci, P. Luis, J. Degre`ve, E. Drioli, B. Van der Bruggen, Novel polyphenylsulfone membrane for potential use in solvent nanofiltration, J. Membr. Sci. 379 (2011) 60–68. [22] S. Darvishmanesh, F. Tasselli, J.C. Jansen, E. Tocci, F. Bazzarelli, P. Bernardo, P. Luis, J. Degre`ve, E. Drioli, B. Van der Bruggen, Preparation of solvent stable polyphenylsulfone hollow fiber nanofiltration membranes, J. Membr. Sci. 384 (2011) 89–96. [23] J.C. Jansen, S. Darvishmanesh, F. Tasselli, F. Bazzarelli, P. Bernardo, E. Tocci, K. Friess, A. Randova, E. Drioli, B. Van der Bruggen, Influence of the blend composition on the properties and separation performance of novel solvent resistant polyphenylsulfone/polyimide nanofiltration membranes, J. Membr. Sci. 447 (2013) 107–118. [24] M.G. Buonomenna, G. Golemme, J.C. Jansen, S.H. Choi, Asymmetric PEEKWC membranes for treatment of organic solvent solutions, J. Membr. Sci. 368 (2011) 144–149. [25] K. Hendrix, G. Koeckelberghs, I.F.J. Vankelecom, Study of phase inversion parameters for PEEK-based nanofiltration membranes, J. Membr. Sci. 452 (2014) 241–252. [26] K. Hendrix, M. Van Eynde, G. Koeckelberghs, I.F.J. Vankelecom, Synthesis of modified poly(ether ether ketone) polymer for the preparation of ultrafiltration and nanofiltration membranes via phase inversion, J. Membr. Sci. 447 (2013) 96–106. [27] J.d.S. Burgal, L. Peeva, P. Marchetti, A.G. Livingston, Controlling molecular weight cut-off of PEEK nanofiltration membranes using a drying method, J. Membr. Sci. 493 (2015) 524–538. [28] K. Vanherck, A. Cano-Odena, G. Koeckelberghs, T. Dedroog, I.F.J. Vankelecom, A simplified diamine crosslinking method for PI nanofiltration membranes, J. Membr. Sci. 353 (2010) 135–143. [29] H. Siddique, Y. Bhole, L.G. Peeva, A.G. Livingston, Micellar-enhanced untrafiltration of methylene blue from dye wastewater via polysulfone hollow fiber membrane, J. Membr. Sci. 465 (2014) 138–144. [30] S.M. Dutczak, F.P. Cuperus, M. Wessling, D.F. Stamatialis, New crosslinking method of polyamide–imide membranes for potential application in harsh polar aprotic solvents, Sep. Purif. Technol. 102 (2013) 142–146.

278 CHAPTER 10 Organic Solvent NF (OSN)



[31] I. Struzy
nska-Piron, J. Loccufier, L. Vanmaele, I.F.J. Vankelecom, Synthesis of solvent stable polymeric membranes via UV depth-curing, Chem. Commun. 49 (2013) 11494–11496. [32] I. Struzy
nska-Piron, J. Loccufier, L. Vanmaele, I.F.J. Vankelecom, Parameter study on the preparation of UV depth-cured chemically resistant polysulfone-based membranes, J. Macromol. Chem. Phys. 215 (2014) 614–623. [33] I. Struzy
nska-Piron, M.R. Bilad, J. Loccufier, L. Vanmaele, I.F.J. Vankelekom, Influence of UV curing on morphology and performance of polysulfone membranes containing acrylates, J. Membr. Sci. 462 (2014) 17–27. [34] E. Fontananova, G. Di Profio, F. Artusa, E. Drioli, Polymeric homogeneous composite membranes for separations in organic solvents, J. Appl. Polym. Sci. 129 (2013) 1653–1659. [35] H. Ohya, I. Okazaki, M. Aihara, S. Tanisho, Y. Negishi, Study on molecular weight cut-off performance of asymmetric aromatic polyimide membrane, J. Membr. Sci. 123 (1997) 143–147. [36] I.B. Valtcheva, S.C. Kumbharkar, J.F. Kim, Y. Bhole, A.G. Livingston, Beyond polyimide: Crosslinked polybenzimidazole membranes for organic solvent nanofiltration (OSN) in harsh environments, J. Membr. Sci. 457 (2014) 62–72. [37] D.Y. Xing, S.Y. Chan, T.S. Chung, The ionic liquid [EMIM]OAc as a solvent to fabricate stable polybenzimidazole membranes for organic solvent nanofiltration, Green Chem. 16 (2014) 1383–1392. [38] R. Liu, I. Valtcheva, P. Gaffney, P. Marchetti, A.G. Livingston, in: Polybenzimidazole Based Membranes for Organic Solvent Nanofiltration (OSN), Proceeding: 2017 AIChE Annual Meeting, Minneapolis, MN, 2017. [39] Y.C. Xu, X.Q. Cheng, J. Long, L. Shao, A novel monoamine modification strategy toward high-performance organic solvent nanofiltration (OSN) membrane for sustainable molecular separations, J. Membr. Sci. 497 (2016) 77–89. [40] M.F. Jimenez Solomon, Y. Bhole, A.G. Livingston, High flux membranes for organic solvent nanofiltration (OSN)—interfacial polymerization with solvent activation, J. Membr. Sci. 423424 (2012) 371–382. [41] M.F. Jimenez Solomon, Y. Bhole, A.G. Livingston, High flux hydrophobic membranes for organic solvent nanofiltration (OSN)—Interfacial polymerization, surface modification and solvent activation, J. Membr. Sci. 434 (2013) 193–203. [42] M.F. Jimenez Solomon, P. Gorgojo, M. Munoz-Ibanez, A.G. Livingston, Beneath the surface: Influence of supports on thin film composite membranes by interfacial polymerization for organic solvent nanofiltration, J. Membr. Sci. 448 (2013) 102–113. [43] I.C. Kim, J. Jegal, K.H. Lee, Effect of aqueous and organic solutions on the performance of polyamide thin-film-composite nanofiltration membranes, J. Polym. Sci. B Polym. Phys. 40 (2002) 2151–2163. [44] I.C. Kim, K.H. Lee, Preparation of interfacially synthesized and silicone-coated composite polyamide nanofiltration membranes with high performance, Ind. Eng. Chem. Res. 41 (2002) 5523–5528. [45] M. Peyravi, A. Rahimpour, M. Jahanshahi, Thin film composite membranes with modified polysulfone supports for organic solvent nanofiltration, J. Membr. Sci. 423424 (2012) 225–237. [46] A.V. Volkov, V.V. Parashchuk, D.F. Stamatialis, V.S. Khotimsky, V.V. Volkov, M. Wessling, High permeable PTMSP/PAN composite membranes for solvent nanofiltration, J. Membr. Sci. 333 (2009) 88–93. 



References 279

[47] S. Tsarkov, A.-O. Malakhov, E.G. Litvinova, A. Volkov, Nanofiltration of dye solutions through membranes based on poly(trimethylsilylpropyne), Pet. Chem. 53 (2013) 537–545. [48] X. Li, P. Vandezande, I.F.J. Vankelecom, Polypyrrole modified solvent resistant nanofiltration membranes, J. Membr. Sci. 320 (2008) 143–150. [49] D. Fritsch, P. Merten, K. Heinrich, M. Lazar, M. Priske, High performance organic solvent nanofiltration membranes: Development and thorough testing of thin film composite membranes made of polymers of intrinsic microporosity (PIMs), J. Membr. Sci. 401-402 (2012) 222–231. [50] P. Gorgojo, S. Karan, H.C. Wong, M.F. Jimenez-Solomon, J.T. Cabral, A.G. Livingston, Ultrathin polymer films with intrinsic microporosity: anomalous solvent permeation and high flux membranes, Adv. Funct. Mater. 24 (2014) 4729–4737. [51] X. Li, C.A. Fustin, N. Lefevre, J.F. Gohy, S. De Feyter, J. De Baerdemaeker, W. Egger, I.F.J.J. Vankelecom, Ordered nanoporous membranes based on diblock copolymers with high chemical stability and tunable separation properties, Mater. Chem. 20 (2010) 4333–4339. [52] X. Li, M. Basko, F. Du Prez, I.F.J. Vankelecom, Multifunctional membranes for solvent resistant nanofiltration and pervaporation applications based on segmented polymer networks, Phys.Chem. B 112 (2008) 16539–16545. [53] X. Li, W. Goyens, P. Ahmadiannamini, W. Vanderlinden, S. De Feyter, I.F.J. Vankelecom, Morphology and performance of solvent-resistant nanofiltration membranes based on multilayered polyelectrolytes: study of preparation conditions, J. Membr. Sci. 358 (2010) 150–157. [54] P. Ahmadiannamini, X. Li, W. Goyens, N. Joseph, B. Meesschaert, I.F.J. Vankelecom, Multilayered polyelectrolyte complex based solvent resistant nanofiltration membranes prepared from weak polyacids, J. Membr. Sci. 394395 (2012) 98–106. [55] B. Tylkowski, F. Carosio, J. Castan˜eda, J. Alongi, R. Garcı´a-Valls, G. Malucelli, M. Giamberini, Permeation behavior of polysulfone membranes modified by fully organic layer-by-layer assemblies, Ind. Eng. Chem. Res. 52 (2013) 16406–16413. [56] D. Chen, Solvent-resistant nanofiltration membranes based on multilayered polyelectrolytes deposited on silicon composite, J. Appl. Polym. Sci. 129 (2013) 3156–3161. [57] S.-P. Sun, S.-Y. Chan, W. Xing, Y. Wang, T.-S. Chung, Facile synthesis of dual-layer organic solvent nanofiltration (OSN) hollow fiber membranes, ACS Sustain. Chem. Eng. 3 (2015) 3019–3023. [58] L. Huang, J. Chen, T. Gao, M. Zhang, Y. Li, L. Dai, L. Qu, G. Shi, Reduced graphene oxide membranes for ultrafast organic solvent nanofiltration. Adv. Mater. (2016), https://doi.org/10.1002/adma.201601606. [59] I. Soroko, A.G. Livingston, Impact of TiO2 nanoparticles on morphology and performance of crosslinked polyimide organic solvent nanofiltration (OSN) membranes, J. Membr. Sci. 343 (2009) 189–198. [60] K. Vanherck, S. Hermans, T. Verbiest, I.F.J. Vankelecom, Using the photothermal effect to improve membrane separations via localized heating, Mater. Chem. 21 (2011) 6079–6087. [61] Y. Li, T. Verbiest, I.F.J. Vankelecom, Improving the flux of PDMS membranes via localized heating through incorporation of gold nanoparticles, J. Membr. Sci. 428 (2013) 63–69.

280 CHAPTER 10 Organic Solvent NF (OSN)

[62] K. Vanherck, I.F.J. Vankelecom, T. Verbiest, Improving fluxes of polyimide membranes containing gold nanoparticles by photothermal heating, J. Membr. Sci. 373 (2011) 5–13. [63] J. Campbell, G. Sz
ekely, R.P. Davies, D.C. Braddock, A.G. Livingston, Fabrication of hybrid polymer/metal organic framework membranes: mixed matrix membranes versus in situ growth, J. Mater. Chem. A 2014 (2014) 9260–9271. [64] A.G. Livingston, Mixed Matrix Membranes for Organic Solvent Nanofiltration, in: Proceeding: 2017 AIChE Annual Meeting, 2017. [65] L.E.M. Gevers, I.F.J. Vankelecom, P.A. Jacobs, Solvent-resistant nanofiltration with filled polydimethylsiloxane (PDMS) membranes, J. Membr. Sci. 278 (2006) 199–204. [66] A. Dobrak-Van Berlo, I.F.J. Vankelecom, B. Van der Bruggen, Parameters determining transport mechanisms through unfilled and silicalite filled PDMS-based membranes and dense PI membranes in solvent resistant nanofiltration: Comparison with pervaporation, J. Membr. Sci. 374 (2011) 138–149. [67] S. Basu, M. Maes, A. Cano-Odena, L. Alaerts, D.E. De Vos, I.F.J. Vankelecom, Solvent resistant nanofiltration (SRNF) membranes based on metal-organic frameworks, J. Membr. Sci. 344 (2009) 190–198. [68] S. Sorribas, P. Gorgojo, C. T
ellez, J. Coronas, A.G. Livingston, High flux thin film nanocomposite membranes based on metal–organic frameworks for organic solvent nanofiltration, J. Am. Chem. Soc. 135 (2013) 15201–15208. [69] M. Peyravi, M. Jahanshahi, A. Rahimpour, A. Javadi, S. Hajavi, Novel thin film nanocomposite membranes incorporated with functionalized TiO2 nanoparticles for organic solvent nanofiltration, Chem. Eng. J. 241 (2014) 155–166. [70] M. Namvar-Mahboub, M. Pakizeh, Development of a novel thin film composite membrane by interfacial polymerization on polyetherimide/modified SiO2 support for organic solvent nanofiltration, Sep. Purif. Technol. 119 (2013) 35–45. [71] H. Siddique, L.G. Peeva, K. Stoikos, G. Pasparakis, M. Vamvakaki, A.G. Livingston, Membranes for organic solvent nanofiltration based on preassembled nanoparticles, Ind. Eng. Chem. Res. 52 (2013) 1109–1121. [72] S. Karan, S. Samitsu, X. Peng, K. Kurashima, I. Ichinose, Ultrafast viscous permeation of organic solvents through diamond-like carbon nanosheets, Science 335 (2012) 444–447. [73] S. Karan, Q. Wang, S. Samitsu, Y. Fujii, I. Ichinose, Ultrathin free-standing membranes from metal hydroxide nanostrands, J. Membr. Sci. 448 (2013) 270–298. [74] T. Tsuru, T. Sudoh, T. Yoshioka, M. Asaeda, Nanofiltration in non-aqueous solutions by porous silica–zirconia membranes, J. Membr. Sci. 185 (2001) 253–261. [75] T. Tsuru, M. Narita, R. Shinagawa, T. Yoshioka, Nanoporous titania membranes for permeation and filtration of organic solutions, Desalination 233 (2008) 1–9. [76] T. Tsuru, M. Miyawaki, H. Kondo, T. Yoshioka, M. Asaeda, Inorganic porous membranes for nanofiltration of nonaqueous solutions, Sep. Purif. Technol. 32 (2003) 105–109. [77] T. Tsuru, T. Nakasuji, M. Oka, M. Kanezashi, T. Yoshioka, Preparation of hydrophobic nanoporous methylated SiO2 membranes and application to nanofiltration of hexane solutions, J. Membr. Sci. 384 (2011) 149–156. [78] T. Van Gestel, B. Van der Bruggen, A. Buekenhoudt, C. Dotremont, J. Luyten, C. Vandecasteele, G. Maes, Surface modification of γ-Al2O3/TiO2 multilayer membranes for applications in non-polar organic solvents, J. Membr. Sci. 224 (2003) 3–10.

References 281

[79] B. Verrecht, R. Leysen, A. Buekenhoudt, C. Vandecasteele, B. Van der Bruggen, Chemical surface modification of γ-Al2O3 and TiO2 top layer membranes for increased hydrophobicity, Desalination 200 (2006) 385–386. [80] P. Marchetti, L. Peeva, A.G. Livingston, The selectivity challenge in organic solvent nanofiltration: membrane and process solutions, Annu. Rev. Chem. Biomol. Eng. 8 (2017) 473–497. [81] A. Mautner, K.-Y. Lee, P. Lahtinen, M. Hakalahti, T. Tammelin, K. Li, A. Bismarck, Nanopapers for organic solvent nanofiltration, Chem. Commun. 50 (2014) 5778. [82] M. Amirilargani, M. Sadrzadeh, E.J.R. Sudh€olter, L.C.P.M. de Smet, Surface modification methods of organic solvent nanofiltration membranes, Chem. Eng. J. 289 (2016) 562–582. [83] M. Priske, M. Lazar, C. Schnitzer, G. Baumgarten, Recent applications of organic solvent nanofiltration, Chem. Ing. Tech. 88 (2016) 39–49. [84] M.G. Buonomenna, J. Bae, Organic solvent nanofiltration in pharmaceutical industry, Sep. Purif. Rev. 44 (2) (2015) 157–182. [85] D. Peshev, L.G. Peeva, G. Peev, I.I.R. Baptista, A.T. Boam, Application of organic solvent nanofiltration for concentration of antioxidant extracts of rosemary (Rosmarinus officinalis L.), Chem. Eng. Res. Des. 89 (2011) 318–327. [86] I. Sereewatthanawut, I.I.R. Baptista, A.T. Boam, A. Hodgson, A.G. Livingston, Nanofiltration process for the nutritional enrichment and refining of rice bran oil, J. Food Eng. 102 (2011) 16–24. [87] E.M. Tsui, M.J. Cheryan, Membrane processing of xanthophylls in ethanol extracts of corn, Food Eng. 83 (2007) 590–595. [88] S. Darvishmanesh, L. Firoozpour, J. Vanneste, P. Luis, J. Degre`ve, B. Van der Bruggen, Performance of solvent resistant nanofiltration membranes for purification of residual solvent in the pharmaceutical industry: experiments and simulation, Green Chem. 13 (2011) 3476–3483. [89] E.M. Rundquist, C.J. Pink, A.G. Livingston, Organic solvent nanofiltration: a potential alternative to distillation for solvent recovery from crystallization mother liquors, Green Chem. 14 (2012) 2197–2205. [90] J. Micovic, K. Werth, P. Lutze, Hybrid separations combining distillation and organic solvent nanofiltration for separation of wide boiling mixtures, Chem. Eng. Res. Des. 92 (2014) 2131–2147. [91] M. Namvar-Mahboub, M. Pakizeh, S. Davari, Preparation and characterization of UZM-5/polyamide thin film nanocomposite membrane for dewaxing solvent recovery, J. Membr. Sci. 459 (2014) 22–32. [92] L.R. Firman, N.A. Ochoa, J. Marchese, C.L. Pagliero, Deacidification and solvent recovery of soybean oil by nanofiltration membranes, J. Membr. Sci. 431 (2013) 187–196. [93] S. Darvishmanesh, T. Robberecht, P. Luis, J. Degre`ve, B. Van der Bruggen, Performance of nanofiltration membranes for solvent purification in the oil industry, J. Am. Oil Chem. Soc. 88 (2011) 1255–1261. [94] S. Han, H.T. Wong, A.G. Livingston, Application of organic solvent nanofiltration to separation of ionic liquids and products from ionic liquid mediated reactions, Chem. Eng. Res. Des. 83 (2005) 309–316. [95] C. Van Doorslaer, D. Glas, A. Peeters, A. Cano-Odena, I. Vankelecom, K. Binnemans, P. Mertens, D. De Vos, Product recovery from ionic liquids by solvent-resistant nanofiltration: application to ozonation of acetals and methyl oleate, Green Chem. 12 (2010) 1726–1733.

282 CHAPTER 10 Organic Solvent NF (OSN)

[96] J.P. Sheth, Y. Qin, K.K. Sirkar, B.C. Baltzis, Nanofiltration-based diafiltration process for solvent exchange in pharmaceutical manufacturing, J. Membr. Sci. 211 (2003) 251–261. [97] G. Szekely, J. Bandarra, W. Heggie, B. Sellergren, F.C. Ferreira, Organic solvent nanofiltration: A platform for removal of genotoxins from active pharmaceutical ingredients, J. Membr. Sci. 381 (2011) 21–33. [98] J. Vanneste, D. Ormerod, G. Theys, D. Van Gool, B. Van Camp, S. Darvishmanesh, B. Van der Bruggen, Towards high resolution membrane-based pharmaceutical separations, J. Chem. Technol. Biotechnol. 88 (2013) 98–108. [99] C.J. Pink, H. Wong, F.C. Ferreira, A.G. Livingston, Organic solvent nanofiltration and adsorbents: a hybrid approach to achieve ultra low palladium contamination of post coupling reaction products, Org. Process. Res. Dev. 12 (2008) 589–595. [100] D. Ormerod, B. Sledsens, G. Vercammen, D. Van Gool, T. Linsen, A. Buekenhoudt, B. Bongers, Demonstration of purification of a pharmaceutical intermediate via organic solvent nanofiltration in the presence of acid, Sep. Purif. Technol. 115 (2013) 158–162. [101] W.E. Siew, A.G. Livingston, C. Ates, A. Merschaert, Continuous solute fractionation with membrane cascades—a high productivity alternative to diafiltration, Sep. Purif. Technol. 102 (2013) 1–14. [102] I. Sereewatthanawut, F.W. Lim, Y.S. Bhole, D. Ormerod, A. Horvath, A.T. Boam, A.G. Livingston, Demonstration of molecular purification in polar aprotic solvents by organic solvent nanofiltration, Org. Process. Res. Dev. 14 (2010) 600–611. [103] J.F. Kim, G. Szekely, I.B. Valtcheva, A.G. Livingston, Increasing the sustainability of membrane processes through cascade approach and solvent recoverypharmaceutical purification case study, Green Chem. 16 (2014) 133–145. [104] L. Peeva, J. da Silva Burgal, I. Valtcheva, A.G. Livingston, Continuous purification of active pharmaceutical ingredients using multistage organic solvent nanofiltration membrane cascade, Chem. Eng. Sci. 116 (2014) 183–194. [105] J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B.M. Weckhuysen, The catalytic valorization of lignin for the production of renewable chemicals, Chem. Rev. 110 (2010) 3552–3599. [106] R. Othman, A.W. Mohammad, M. Ismail, J. Salimon, Application of polymeric solvent resistant nanofiltration membranes for biodiesel production, J. Membr. Sci. 348 (2010) 287–297. [107] I.H. Tsibranska, B. Tylkowski, Concentration of ethanolic extracts from Sideritis ssp. L. by nanofiltration: comparison of dead-end and cross-flow modes, Food Bioprod. Process. 91 (2013) 169–174. [108] I. Tsibranska, I. Saykova, Combining nanofiltration and other separation methods (review), J. Chem. Technol. Metall. 48 (2013) 333–340. [109] A. Gupta, N.B. Bowden, Separation of cis-fatty acids from saturated and trans-fatty acids by nanoporous polydicyclopentadiene membranes, ACS Appl. Mater. Interfaces 5 (2013) 924–933. [110] J.T. Rundel, B.K. Paul, V.T.J. Remcho, Organic solvent nanofiltration for microfluidic purification of poly(amidoamine) dendrimers, Chromatogr. A 1162 (2007) 167–174. [111] S. So, L.G. Peeva, E.W. Tate, R.J. Leatherbarrow, A.G. Livingston, Organic solvent nanofiltration: A new paradigm in peptide synthesis, Org. Process. Res. Dev. 14 (2010) 1313–1325.

References 283

[112] N.F. Ghazali, D.A. Patterson, A.G. Livingston, Elucidation of the mechanism of chiral selectivity in diastereomeric salt formation using organic solvent nanofiltration, Chem. Commun. (8) (2004) 962–963. [113] L. Peeva, A.G. Livingston, Potential of organic solvent nanofiltration in continuous catalytic reactions, Procedia Eng. 44 (2012) 307–309. [114] D. Nair, H.T. Wong, S. Han, I.F.J. Vankelecom, L.S. White, A.G. Livingston, A.T. Boam, Extending Ru-BINAP catalyst life and separating products from catalyst using membrane recycling, Org. Process. Res. Dev. 13 (2009) 863–869. [115] P. Van der Gryp, A. Barnard, J.P. Cronje, D. De Vlieger, S. Marx, H.C.M. Vosloo, Separation of different metathesis Grubbs-type catalysts using organic solvent nanofiltration, J. Membr. Sci. 353 (2010) 70–77. [116] H. Wong, C.J. Pink, F.C. Ferreira, A.G. Livingston, Recovery and reuse of ionic liquids and palladium catalyst for Suzuki reactions using organic solvent nanofiltration, Green Chem. 8 (2006) 373–379. [117] D. Nair, J.T. Scarpello, I.F.J. Vankelecom, L.M. Freitas Dos Santos, L.S. White, R.J. Kloetzing, T. Welton, A.G. Livingston, Increased catalytic productivity for nanofiltration-coupled heck reactions using highly stable catalyst systems, Green Chem. 4 (2002) 319–324. [118] A. Datta, K. Ebert, H. Plenio, Nanofiltration for homogeneous catalysis separation: Soluble polymer-supported palladium catalysts for heck, Sonogashira, and Suzuki coupling of aryl halides, Organometallics 22 (2003) 4685–4691. [119] P.T. Witte, S.R. Chowdhury, J.E. ten Elshof, D. Sloboda-Rozner, R. Neumann, P. Alsters, Highly efficient recycling of a “sandwich” type polyoxometalate oxidation catalyst using solvent resistant nanofiltration, Chem. Commun. (9) (2005) 1206–1208. [120] A. Cano-Odena, P. Vandezande, D. Fournier, W. Van Camp, F.E. Du Prez, I.F.J. Vankelecom, Solvent-resistant nanofiltration for product purification and catalyst recovery in click chemistry reactions, Chem. Eur. J. 16 (2010) 1061–1067. [121] S. Ferguson, F. Ortner, J. Quon, L. Peeva, A.G. Livingston, B.L. Trout, A.S. Myerson, Use of continuous MSMPR crystallization with integrated nanofiltration membrane recycle for enhanced yield and purity in API crystallization, Cryst. Growth Des. 14 (2014) 617–627. [122] J. Campbell, L.G. Peeva, A.G. Livingston, Controlling crystallization via organic solvent nanofiltration: The influence of flux on griseofulvin crystallization, Cryst. Growth Des. 14 (2014) 2192–2200. [123] C. Davey, Z.X. Low, R. Wirawan, D. Patterson, Molecular weight cut-off determination of organic solvent nanofiltration membranes using poly(propylene glycol), J. Membr. Sci. 526 (2017) 221–228. [124] Van Speybroeck, V., Vanduyfhuys, L., Rogge, S.M.J., & Rijksen, B. Transport modeling for novel organic solvent nanofiltration membranes. Nanoporous Mater. Catal. https://molmod.ugent.be/subject/transport-modeling-novel-organic-solventnanofiltration-membranes-0. [125] R. Abejo´n, A. Garea, A. Irabien, Organic solvent recovery and reuse in pharmaceutical purification processes by nanofiltration membrane cascades, Chem. Eng. Trans. 43 (2015) 1057–1062. [126] B.A. Farnand, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Reverse osmosis separations of some organic and inorganic solutes in methanol solutions using cellulose acetate membranes, Ind. Eng. Chem. Proc. Des. Dev. 22 (1983) 179–187.

284 CHAPTER 10 Organic Solvent NF (OSN)

[127] B.A. Farnand, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Reverse osmosis separations of some inorganic solutes in ethanol solutions using cellulose acetate membranes, Sep. Sci. Technol. 19 (1984) 33. [128] B.A. Farnand, F.D.F. Talbot, T. Matsuura, S. Sourirajan, Reverse osmosis separations of some organic and inorganic solutes in ethanol solutions with cellulose acetate membranes, Ind. Eng. Chem. Res. 26 (1987) 1080–1087. [129] L.E. Black, Interfacially polymerized membranes for the reverse osmosis separation of organic solvent solutions, (1992). US Patent 5173191 A, publication data, Dec. 22, 1992. [130] R. Lively, Carbon Molecular Sieve Membranes as Enablers for Organic Solvent Reverse Osmosis. Proceeding, 2017 AIChE Annual Meeting, 2017. [131] B. Halford, Membrane separates hydrocarbon isomers in energy-saving process, Chem. Eng. News (2016). Aug. 22, 2016.