Dye rejection from industrial textile wastewater using

Graphene oxide (GO) - Ceramic Hollow Fibers

1 Literature Review

1.1 Background of Graphene Oxide (GO) membrane

Graphene oxide (GO) is a highly oxidized form of graphene which is produced by

chemical exfoliation of graphite using oxidizing agent in the presence of mineral acid. GO

can be synthesized by three different methods namely Brodie’s, Staudenmaier’s and

Hummers’ method. Brodie firstly found that the oxidizing mixture (KClO 4 with fuming

HNO4) could form GO only with graphitizable carbons that contain regions of graphitic

structure [1]. Staudenmaier then reported the formation of GO when graphite was heated

with H2SO4, HNO3, and KClO4 [2]. Finally, Hummers and Offeman introduced a convenient

method to prepare GO using H2SO4 and KMnO4 [3]. Among the various methods available

for GO synthesis, Hummer’s method is commonly used as it is simpler protocol which can

obtain higher yield, higher efficiency, fewer defects and no toxic gas emission during the

synthesis process [4]. The oxidation of graphite breaks the extended two-dimensional π-

conjugation of the stacked graphene sheets into a mixture of sp2 domains surrounded by

disordered, highly oxidized sp3 domains and carbon vacancies [5]. The resulting GO sheets

are shown in Figure 1 where carboxylic acid is located at the edges while phenol, hydroxyl

and epoxide groups are located at the basal plane.

Figure 1: GO sheet structure [4].

1.2 Dye rejection mechanism using GO membrane

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 Dye removal via GO sheet is carried out by a combination of mechanical sieve and

Donnan exclusion [6]. For the mechanical sieve separation, solutes are rejected via the holes

and inter edges found on the GO sheet with the typical dye molecule having a size between

300 - 970 Da [6]. Therefore, dye molecules with molecular size larger than the holes and

inter edges will be rejected by the mechanical sieve. In cases where dye molecules have

molecular size smaller than the holes and inter edges found on the GO sheet, Donnan

exclusion mechanism will occur to further reject the passage of dye molecules via

absorption or repulsion. Donnan exclusion mechanism is the behavior of charged particles

near a semi-permeable membrane where similarly charged solute and membrane results in

electrostatic repulsion and oppositely charged results in electrostatic attraction [7]. The GO

sheet carries negative charges because of the oxygen functionalities and has displayed

greater dye removal efficiency via absorption than repulsion [8]. Ramesha et al. compared

the removal efficiency GO membranes to dyes of different electrical properties and

concluded that an GO membranes achieved an efficiency of 95% when treating cationic

dyes while negligible removal efficiency was found with anionic dyes which can only be

improved by reducing or modifying GO [9]. Therefore, dye rejection via absorption is the

more favorable mechanism with absorption efficiency highly dependent on the pH of

solution, interaction of dye solute with the filtration membrane and the ionic strength of the

solute [6,7].

1.3 Dye rejection efficiency of modified GO membrane

The GO membrane is further developed or modified to improve its properties for dye

rejection in extreme conditions like textile wastewater. Besides, GO membranes are also

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 modified to customize the pore size or interlayer spacing for different purposes and to

overcome their weakness like low stability and water permeability [9,12,13]. In most

studies, dye rejection efficiency of the modified GO membrane was carried out to ensure

that dye separation was high despite modifications. According to Table 1, the dye separation

efficiency of various modified GO membrane was commonly reported to be above 95% with

some dyes being completely removed by the modified GO membrane.

Table 1: Dye rejection of various modified GO membrane [14, 15, 16, 17, 18].

Modified GO Membrane Dye Molecular size Rejection (%)

(Da)
GO - Ceramic Hollow Fibers Methyl Orange 327.30 97

Brilliant Blue 792.85 100

Yellow Tartazine 534.36 100

Crystal Viole 407.98 99

Rose Bengal 973.67 100

GO - intercalated Carbon Direct Yellow 624.55 99

Nanotube Methyl Orange 327.30 96

Ultra-Thin Graphene Methylene Blue 284.00 99

Membrane Direct Red - 99

GO - cross-linked by 1,3,5- Methylene Blue 284.00 46 – 66

benzenetricarbonyl trichloride Rhodamine WT 487.00 93 – 95

3D GO Sponge Methylene Blue 333.6 99.1

Methyl Violet 393.96 98.8

2. Problem Statement

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 The diverse application of dyes in various industries as well as it’s detrimental effects on

the environment is highly attributed to its high stability and resistance to light, temperature,

chemicals and biodegradation [19,20]. There are currently over 10,000 different dyes used

worldwide with an estimated 700,000 tons of dyes produced and up to 200,000 tons of these

dyes are lost to effluents as wastewater annually on a global scale [19, 21]. In relation to

every other industry, the textile industry contributes around 17 - 20% of global wastewater

pollution and is deemed highly difficult to treat due to its complex wastewater composition,

extreme pH, high chemical oxygen demand (COD) and biochemical oxygen demand (BOD)

and rich in colour [22, 23].

Nanofiltration is currently is the most attractive method as it offers high pollutant

reduction, water reusability and low operating costs compared to the other treatment methods

available [6,22]. GO membrane is a nanofiltration material which has sparked the interest of

many researchers as it displays its capability to be easily functionalize or modified, ease to be

produced at low cost for industrial application, chemical inertness and its superior

hydrophilic surface and mechanical properties [6,10,11]. However, the GO membrane is

unable to withstand high pressure due to its extremely thin feature [14]. Ceramic hollow

fibers provide a good support for GO membranes as it is strong, rigid, chemically and

thermally stable allowing them to operate under extreme operating conditions [14].

Therefore, the modification of GO membrane with ceramic hollow fibers will allow it to

reject dye in the extreme conditions found in textile wastewater.

2 Project Summary

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2.1 Objective

The specific objectives that are required to be achieved are stated as shown below:

 To use Hummer’s Method for synthesis of GO membrane.

 To deposit GO membrane onto the surface of ceramic hollow fibers by vacuum

filtration.

 To determine the dye rejection of textile wastewater using GO – ceramic hollow

fiber membrane for dyes of different size and at different pH value.

2.2 Strategy

We would expect that not all dyes found in the industrial textile wastewater will be

removed as it contains both cationic and anion dyes. Not only that, molecular sieve

separation has low rejection efficiency for dye molecules whose size are below 300 Da

[14]. For dyes that can be removed, we would expect the dye rejection to be above 95%

for each individual dye found in textile wastewater.

2.3 Expected Outcome

According to Aba et al, the molecular sieve separation has low rejection efficiency for

dye molecules with molecular size below 300 Da while having 100% rejection for

molecular size above 534.3 Da [14]. Since most dye molecules have a molecular size

between 300 – 970 Da [6], we would expect that most dyes would be removed via

molecular sieve separation and the remaining dyes with molecular size below 300 Da to

be removed via Donnan exclusion mechanism. Unfortunately, not all dyes found in the

textile wastewater can be removed by the GO – ceramic hollow fiber membrane as it is

negatively charged and textile wastewater should contain both cationic and anionic dyes.

As for the dyes that can be removed by GO – ceramic hollow fiber membrane, we would

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 expect the dye rejection to be above 95% for each individual dye found in textile

wastewater based on the results seen in Table 1.

3 Methodology

3.1 Fabrication of GO – ceramic hollow fiber membrane

Expanded graphite GFG 130, H2SO4 (97%), H3PO4 (85%), H2O2 (30%), KMnO4,

Rhodamine B, Methyl blue, Congo red and methanol would be purchased at Aldrich and

used without pretreatment.

GO sheets would be synthesized by modified Hummers method [13]. First,

concentrated H2SO4 and H3PO4 are prepared at a ratio of 9:1 and the total volume is

500mL. Then 10g graphite flakes and 40g KMnO4 powder are added to the prepared

solution under constant magnetic stirring condition. The color change of solution from

green to violet indicates the reaction between KMnO4 and the solution. Then the solution

is cooled to around 25℃ and then ice water together with 6mL of 30% H 2O2 solution are

added and stirred to remove the remaining manganese ions. The suspension is then

centrifuged at 3500 and 9000rpm for 30min and washed with 10% hydrochloric acid,

water and methanol to remove the metallic contamination and to get the GO flakes [25].

After washing, the product is either dried or kept as methanol dispersion. The yield is

about 16g of dried GO. Ceramic hollow fiber membrane was fabricated using Al 2O3 by

phase-inversion/sintering process [14].

GO flakes are deposited onto the ceramic hollow fiber membrane through vaccum

fitration method [14, 26]. The prepared ceramic hollow fiber membrane is firstly

immersed into a GO dispersion with one end sealed and the other connected to a vacuum

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 pump, which directs water containing GO flakes into the hollow fiber substrate. And GO

membranes is formed due to the pressure difference and water permeation. The thickness

of fabricated GO – ceramic hollow fiber membrane can be manipulated by changing the

GO concentration in the dispersion and the loading period. After drying in vacuum at

50℃ for four hours, the GO -- ceramic hollow fiber membrane is fabricated [14].

3.2 Characterization

The properties of GO – ceramic hollow fiber membrane would be characterized by

scanning electron microscope (SEM) using a Zeiss Supra 35 VP microscope. X-ray

photoelectron spectroscopy (XPS) using a TFA XPS model is used to identify the

chemical composition of the fabricated membranes and to check if there are other

substances present.

3.3 Experiments of dye removal using the fabricated GO – ceramic hollow fiber

membranes

The water permeance and dyes rejection of the membranes are measured using a

home-made dead-end vacuum filtration device. The GO – ceramic hollow fiber

membrane is placed into the sample cylinder which was filled with dye solution and

pressurized to 10 bars [14]. The volume of feed solution is 250mL. Different organic

dyes are used to test the rejection performance under the same operation condition. The

dye concentrations of the feed and permeate are analyzed using a UV-spectrometer (UV-

2101PC). The rejection R (%) are calculated according to Eq. (1) where C p and Cf

represented the dye concentration of permeate and feed respectively [25]. The as-

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 prepared membranes are then statically immersed in pure water (pH=7±0.2), HCl

aqueous solution (pH=1.5), and NaOH aqueous solution (pH=11), respectively, at room

temperature for a certain time to test the stability in solutions of different pH values.

(Eq.1)

4 Milestone

The project involves four stages: literature review, chemical purchasing and material

preparation, experiment and conclusion. The first stage, literature review lasts three weeks.

During this stage, many papers are reviewed and summarized for future reference. Also, the

modification plan is proposed in this stage. Then proceeds to the second stage, chemical

purchasing and material preparation. Before purchasing chemicals, a detailed plan is

submitted for approval. Then the chemicals would be purchased from qualified suppliers.

The time needed to receive all the items depends on the suppliers and the duration is set to

be six weeks. During this period, some start-up works can be done. It is planned that all the

membranes are fabricated before the end of week 14. The third stage, experiment stage starts

before the end of the former stage as some chemicals may be prepared earlier. During this

stage, the physiochemical properties of membranes are characterized and dye rejection

performances are tested and analyzed accordingly. Considering the possible problems during

the real-case experiments, the whole process is planned to take seven weeks. Lastly, the

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 conclusion stage including comparing the rejection performance under different conditions

and concluding would take 2 weeks.

5 Conclusion and Future suggestions

The addition of ceramic substrate improves GO membrane stability to high pressure,

increases the membrane area per volume ratio and reduce the size of separation plants.

Hence, hollow fiber membranes are suitable for industrial-scale usage. Besides, the

preparation method is relatively cheap which is practical for industrial production [13]. XPS

may confirm the relatively pure components of oxygen and carbon element and that there

are impurities, such as sulfur, present at very low concentrations because of the addition of

H2SO4. The fabricated membranes can show good dye retention performances with overall

rejection rate higher than 99% especially for dye of molecular size exceeding 534.3 Dalton

which could reach 100% [14]. And the pH value of feed solution also has an impact on the

dye rejection performance and stability of the GO – ceramic hollow fiber membrane. Lastly,

as is common for all membranes, the thickness of GO – ceramic hollow fiber membrane

depends on the balance between rejection performance and flux. When GO loading time is

increased, the membrane becomes denser and thicker which are favorable for better filtration

result but unfavorable for short processing time. Furthermore, the smaller flux in dense

membrane system can be explained by the formation of cake layer which can be more

obvious when the feed dye concentration is high. Hence, for feed with high dye

concentration, the thickness of membrane should not be too thick considering the negative

impact of cake formation.

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 Further modifications on membranes could be made in terms of membrane structure. Due

to the intrinsic properties of GO membrane, they tend separate from each other due to the

electrostatic repulsion, leading to breaking apart of GO membranes [25]. It is reported that

the stability of GO membranes in water can be improved by using cross-linking reagents

containing multivalent metal ions such as Al [27]. And to avoid the irreversible shrinkage,

the prepared GO – ceramic hollow fiber membrane should be kept wet.

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