# Patent

## Title
Method to remove organic pollutants by electrocatalysis

## Abstract

A method for removing chlorinated organic pollutants from an aqueous composition by electrocatalysis, including electrolyzing the aqueous composition, in a capillary reactor, with an applied potential of 1-5 kV, in which, during the electrolyzing, the aqueous composition is in contact with porous silica supported-sol-gel coated platinum and titanium catalysts and the electrolyzing forms hydrogen and hydrogen chloride.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Disclosure
The present invention relates to a method for removal of organic pollutants (OPs) by electrocatalysis.
2. Description of Related Art
In recent years, anti-pollution electrocatalysis and electrical-catalyzed membrane-separation for water treatment has been developed. Techniques to solve fundamental problems such as energy, resource and environment problems have been investigated.
U.S. 2012/0090988 A1 is related to anti-pollution electrocatalysis composite membrane and membrane reactor. The electrocatalytic composite membrane consists of a substrate and catalytic coating and the membrane reactor provides a trans-membrane pressure as the membrane separation power generated by a pump. The electrocatalytic composite membrane as anode and an auxiliary electrode as cathode are connected to a direct current regulated power supply separately by conducting wires so that an electrolysis apparatus is formed to degrade the pollutant attached on the surface and in the pores of the membrane by electrocatalytic oxidation. The direct current regulated power supply provides 0-30 V of supply voltage and 0-10 A of current.
CN101104537A relates to electrocatalysis using a separation film for a water treatment device. The separation membrane divides internal space of shell into dope space and filtration space. The dope space has raw water inlet and dope outlet and a net-like conductor. The separation membrane and net-like conductor are separately connected with constant current power supply to form electron emission area and electron receiving area. The current adjusting scope of the constant current power supply is between 0 and 50 A, the input pressure voltage is 220 V, and the output voltage is 24 or 12 V. This approach only requires low voltages.
Development of a more effective means of cleaning water by removing organic pollutants by electrocatalysis is essential. Therefore, the present invention applies porous silica supported sol-gel coated platinum and titanium catalysts in which the porous support silica are synthesized from a rice husk material. Due to employment of a glass capillary microreactor, catalytic activity is enhanced by electrokinetic mobility of the target analytes which does not require physical pumps and shortens the time required for removal. The use of rice husk as support for platinum (RHA-Pt) and titanium (RHA-Ti) catalysts for removal of organic pollutants in a glass capillary microreactor has not been previously reported.
BRIEF SUMMARY
An object of the invention is a method for removing chlorinated organic pollutants from an aqueous composition by electrocatalysis.
In an embodiment the method includes electrolyzing the aqueous composition in a capillary reactor, with an applied potential of 1-5 kV.
In another embodiment the aqueous composition is in contact with porous silica supported-sol-gel coated platinum and titanium catalysts.
In another embodiment the electrolyzing forms hydrogen and hydrogen chloride.
In one embodiment of the invention, the electrolyzing is carried out at a constant current of 200 μA.
In another embodiment, the aqueous composition passes through the capillary reactor during the electrolyzing without mechanical pumping.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a scanning electron micrograph showing the percentage of the component in the sample of RHA-silica.
FIG. 1B is a scanning electron micrograph showing the percentage of the component in the sample of RHA-Pt.
FIG. 1C is a scanning electron micrograph showing the percentage of the component in the sample of RHA-Ti.
FIG. 1D is an EDX spectrum and inset showing the percentage of the component in the sample of RHA-silica.
FIG. 1E is an EDX spectrum and inset showing the percentage of the component in the sample of RHA-Pt.
FIG. 1F is an EDX spectrum and inset showing the percentage of the component in the sample of RHA-Ti.
FIG. 2A shows a glass capillary microreactor for removal of MegaMix® Standard OPs using the electrocatalysis method.
FIG. 2B is a schematic of the glass capillary microreactor for removal of MegaMix® Standard OPs using the electrocatalysis method.
FIG. 3A is a graph showing an effect of different reaction times on the removal ratio of chlorophenols (CP)s in the capillary microreactor of 21 cm length, applied potential 3 kV, using pH 7 and RHA-Pt catalyst.
FIG. 3B is a graph showing an effect of different reaction times on the removal ratio of chlorophenols (CP)s in the capillary microreactor of 21 cm length, applied potential 3 kV, using pH 10 and RHA-Ti catalyst.
FIG. 4A is a graph showing effect of different applied potentials on the removal ratio at reaction time 20 min and pH 10 by using RHA-Pt in the electrocatalysis method.
FIG. 4B is a graph showing effect of different applied potentials on the removal ratio at reaction time 20 min and pH 10 by using RHA-Ti in the electrocatalysis method.
FIG. 5A is a graph showing effect of reaction pH on the removal ratio of (CPs) by using electrocatalysis method in the capillary-microreactor (at 20 min and applied potential (3 kV) by using RHA-Pt.
FIG. 5B is a graph showing effect of reaction pH on the removal ratio of (CPs) by using electrocatalysis method in the capillary-microreactor (at 20 min and applied potential (3 kV) by using RHA-Pt.
FIG. 6 is a GC-MS chromatogram of OPs as CPs before and after the removal of OPs using the electrocatalysis method in a glass capillary-microreactor method.



DETAILED DESCRIPTION
The present invention includes a method for removing organic pollutants (OPs) by electrocatalysis from an aqueous composition. The method comprises electrolyzing the aqueous composition, in a capillary reactor, wherein during the electrolyzing, the aqueous composition is in contact with porous silica supported sol-gel coated platinum and titanium catalysts. In this method, the electrolyzing forms hydrogen and hydrogen chloride.
The porous silica supported sol-gel coated platinum and titanium catalysts are prepared from rice husk-ash by a sol-gel method. Rice husks as used herein are the hard protecting coverings of grains of rice. Combustion of rice hulls yields rice husk ash as used herein. Rice husk ash is a potential source of amorphous reactive silica.
In the preparation, clean rice husk (RH) is mixed with HNO3 (1.0 M) at room temperature. The cleaned RH is washed with distilled water to a constant pH and then dried in an oven at a temperature of 120° C. and burned in a muffle furnace at a temperature of from 550 to 650° C. for a time period of 6-7 hours, to obtain white rice husk-ash (RHA).
The RHA is then added to NaOH (1.0 M) and stirred at room temperature for at least 24 hours to obtain sodium silicate solution. CTAB (cetyltrimethyl ammonium bromide) is then added into the sodium silicate solution and stirred until completely dissolved. A molar ratio of CTAB to Si is about 1:1.2. The solution is titrated with HNO3 (0.1 M) with constant stirring until reaching a pH of from 2.5 to 3.5. The resulting gel is then aged for at least five days, then filtered and washed thoroughly with distilled water, and washed with acetone to obtain RHA-silica powder. The gel is dried at a temperature of 110° C., for 24 hours, ground to fine powder, and calcined at a temperature of 500° C. in a muffle furnace for at least five hours.
For the preparation of RHA-Pt catalyst, from 1 to 3% Pt of PtCl2 (weight/volume ratio of RHA to PtCl2) was dissolved in HNO3, and then titrated and the RHA-Pt catalysts were dried in an oven.
A BET surface area of the RHA-silica was measured and is about 225 m2/g. A pore volume (cm3/g) of the RHA-silica catalyst is from 0.15 to 0.35. An average pore size of the RHA-silica is from 4.75 to 5.0 nm.
A BET surface area of the RHA-Pt catalyst is from 535 to 540 m2/g with a pore volume (cm3/g) of from 0.60 to 0.70 and an average pore size of from 4.70 to 4.75 nm
A BET surface area of the RHA-Ti catalyst is from 12 to 14 m2/g with a pore volume (cm3/g) of from 0.01 to 0.013 and a pore size of 4.10 nm
The catalysts are employed for removal of OPs in a glass capillary reactor. The capillary and reservoirs A(+) and B(−) are filled with a buffer solution and the catalyst, and a mixture standard is introduced into the capillary reactants at the reservoir A. Platinum wires are used as the electrodes and high voltage is applied. The electrocatalysis is conducted in an aqueous medium with an applied potential of from 1 to 5 kV, preferably about 3 kV. The applied potential produces OH− and H+ ions and electrons which activate the catalysis process to degrade OPs. A current of from 150 to 250 μA, preferably about 200 μA, is also applied to the reservoir A, while reservoir B is connected to ground. The reaction time applied is controlled in a range from 10 to 30 min.
The main advantage of using the proposed method is shorter reaction time and complete degradation of 76 organic compounds. In this disclosure, chlorophenol is utilized as a model compound for method optimization. Various experimental conditions influencing removal were optimized. Reaction performance using electrocatalysis was compared with conventional catalysis. The instant process is simple, easy to use and suitable for the removal of wide range of OPs.
EXAMPLE
Catalysts were prepared from RHA by sol-gel method1; 30 g of clean rice husk (RH) was stirred with 750 mL of 1.0 M HNO3 at room temperature for 24 hrs. The cleaned RH was washed with copious amount of distilled water to constant pH, then dried in an oven at 100° C. for 24 hr and burned in a muffle furnace at 600° C. for 6 hr so as to obtain white rice husk-ash (RHA). About 3.0 g of RHA was added to 350 mL of 1.0 mol L−1NaOH in a plastic container and stirred for 24 hrs at room temperature to get sodium silicate solution. About 3.6 g of CTAB (1:1.2, Si: CTAB molar ratio) was added into the sodium silicate solution and stirred to dissolve completely. This solution was titrated with 3.0 mol L−1HNO3 at a rate of ca. 1.0 mL min−1 with constant stirring until pH 3.0. The resulting gel was aged for 5 days, then filtered and washed thoroughly with distilled water, finally washed with acetone. The gel was dried at 110° C. for 24 hr ground to fine powder and was calcined at 500° C. in a muffle furnace for 5 hrs, then labeled as RHA-silica powder. Same procedure followed for the preparation of RHA-silica Solution of 1.0 wt. % Pt of (PtCl2) which dissolved in 50 mL of 3 mol L−1 HNO3 and titrated. Similarly, solution of 1.0 wt. % Ti of (TiO2) dissolved in 50 mL of 3 mol L−1 HNO3 was titrated. The resulting gels were treated as described above. The resulting powders were labeled as RHA-Pt and RHA-Ti, respectively.
The prepared catalysts were characterized using Fourier transform infrared (FTIR) spectroscopy, N2 adsorption-desorption analysis, Field-Emission Scanning Electron Microscope (FESEM), and Energy dispersive spectrometry (EDX).







TABLE 1







Nitrogen adsorption-desorption analysis parameters of materials













BET Surface
Pore Volume
Average Pore



Catalyst
Area (m2/g)
(cm3/g)
Size (nm)
















RHA-silica
225.4306
0.273179
4.84725



RHA-Pt
538.0725
0.637532
4.73938



RHA-Ti
12.6548
0.012738
4.02638










The catalysts were used for removal MegaMix® Standard OPs in in a capillary-micro-reactor. Several glass capillary microreactors (7 cm, 14 cm and 21 cm) were designed for the electrocatalysis method (as shown in FIGS. 2A and 2B). The capillary and reservoirs A(+) and B(−) were filled with 2.5 mmol of buffer solution of different pH (2, 7, and 10) and 12.5 mg catalyst and 100 μL of the mixture standard (8270 MegaMix®) were introduced into the capillary reactants at the reservoir A. Platinum wires were used as the electrodes and high voltage (1-5 kV) were applied. No air bubbles were found inside the capillary tube during the reaction. A reaction potential of (1-5 KV) and 200 μA current were applied to reservoir A, while reservoir B was connected to ground.
To optimize the electrocatalysis method for removal of OPs, analytical factors such as reaction time, applied potential, length of the capillary and pH of buffer solution were investigated to determine the most favorable reaction conditions. Temperature was kept constant at room temperature throughout the reactions. The identification and quantitative yields were determined which were obtained from (GC-MS) data.
Effect of Reaction Time
Reaction time is an important factor in the reactions. Various reaction times (10 min, 20 min and 30 min) were applied. The reaction time was controlled manually. FIG. 3) shows the removal (%) of CPs with respect to these reaction times. The removal increases with increase in reaction time, up to 20 min, by using RHA-Pt catalyst as seen in FIG. 3A, while the best time for the removal of CPs by using RHA-Ti as catalyst was 10 min as shown in FIG. 3B.
Applied Potential
In order to achieve a high removal ratio of OPs from 8270 MegaMix® Standard different potential applied in the range of 1-5 kV at a constant current of 200 μA FIG. 4) shows the influence of the applied potential on the HDC reactions. As can be seen, a maximum degradation of CPs by both catalysts (RHA-Pt and RHA-Ti) was obtained by using 3 kV. In electrocatalysis method high potential (in Kv range) was applied to create in-situ generation of hydrogen as well as to expedite the activation of catalysts for the removal of OPs. Moreover, the higher applied potential increases the analyte interaction with the catalyst particles and enhances the reaction to the remove OPs in the 8270 MegaMix® Standard.
Length of the Capillary-Microreactor
For micro devices using an electrophoretic separation at constant field, resolution is proportional to the square of the channel length. Various lengths (7 cm, 14 cm, 21 cm) of the capillary were studied and significant improvement was obtained in the removal of OPs when the length of the capillary was increased from 7 cm to 21 cm as shown in Table 2.







TABLE 2







Effect of Length of the capillary microreactor on the Removal


ratio of CPs by using electrocatalysis method









% of degradation



Length of the



capillary-microreactor












Compound name
7 cm
14 cm
21 cm







2CP
72
81
90



2,4-DCP
81
83
85



2,4,5-TCP
81
88
96



2,4,6-TCP
95
98
99



2,3,4,6-TeCP
59
70
81



2,3,5,6-TeCP
65
78
90



PCP
52
69
85










Reaction pH
The pH of the solution is an important parameter which controls the rate of the reaction. The pH of the solution studied was (2.0, 7.0 and 10). FIG. 5 shows the removal of the OPs involving different catalysts. The maximum removal by using RHA-Pt catalyst was observed in neutral range (pH 7) compared to other buffer solutions, which may be due to the dissolving of platinum particles, whereas when RHA-Ti was used as catalyst, the maximum removal was obtained in alkaline range (pH 10).
Quantitative determination of removal of OPs using electrocatalysis method with (GC-MS)
In order to evaluate the most favorable reaction conditions, i.e. the optimum removal conditions for reaction of OPs, a reaction time of 20 min, pH 7 and applied potential of 3 kV was used with 21 cm long capillary-microreactor when using RHA-Pt as the catalyst, and a reaction time of 10 min, pH 10 and applied potential of 3 kV was used with 21 cm long capillary-microreactor when using as RHA-Ti as the catalyst. The electrocatalysis method using capillary-microreactor provided high removal ratio of CPs in a short time (10 min and 20 min) using little amount of the reactant. FIG. 6 shows GC-MS chromatogram of OPs as CPs before and after the removal of OPs using electrocatalysis method in a glass capillary-microreactor method. In FIG. 6, a GC-MS chromatogram of CPs using a conventional method, the control 100 ppm before a reaction occurs (Top), after 10 Min (middle) and after 20 Min (bottom) is shown, in which the peaks are: 1 (2-chloroPhenol), 2 (2,4-dichloroPhenol), 3 (2,4,6-trichlorophenol), 4 (2,4,5-trichlorophenol), 5 (2,3,4,6-trichlorophenol), 6 (2,3,5,6-trichlorophenol), 7 (pentachlorophenol).
In summary, optimization of the removal ratio of OPs to achieve better reaction performance by an electrocatalysis method using a glass capillary-microreactor with high removal ratio in comparison with conventional method and the most favorable reaction conditions are demonstrated. The RHA-Ti and RHA-Pt catalysts show catalytic activity in the removal of OPs under mild condition at room temperature and ambient pressure by using buffered solution in the presence of supported catalysts of RHA-Ti and RHA-Pt. A reaction time of 20 min is sufficient to completely remove OPs by the electrocatalysis method in the capillary micro reactor. The method of this invention is suitable for the degradation of wide range of chlorinated organic pollutants. Rice husk supported platinum (RHA-Pt) and titanium (RHA-Ti) catalysts and a high potential (in the Kv range) were applied to enhance the catalytic activity via electrokinetic mobility of the target analytes, in which no physical pumps were required, leading to a shorter reaction time required for removal. The electrocatalysis is environmentally benign and is suitable for application in water decontamination or waste disposal pre-treatment.

## Claims

1. A method for removing chlorinated organic pollutants from an aqueous composition by electrocatalysis, comprising:
electrolyzing the aqueous composition, in a capillary reactor, with an applied potential of 1-5 kV,
wherein during the electrolyzing, the aqueous composition is in contact with at least one of a porous silica supported-sol-gel coated platinum catalyst or a porous silica supported-sol-gel coated titanium catalyst; and
wherein the electrolyzing forms hydrogen and hydrogen chloride.

2. The method of claim 1, wherein the electrolyzing is carried out at a constant current of from 150 to 250 μA.

3. The method of claim 1, wherein the aqueous composition passes through the capillary reactor during the electrolyzing without mechanical pumping.

4. The method of claim 1, wherein the capillary reactor is a glass capillary microreactor.

5. The method of claim 1, wherein during the electrolyzing, the aqueous composition is in contact with porous silica supported-sol-gel coated platinum catalysts.

6. The method of claim 5, wherein a reaction time in the electrolyzing is about 20 min.

7. The method of claim 5, wherein a pH of the aqueous composition is about 7.

8. The method of claim 5, wherein a pH of the aqueous composition is about 10.

9. The method of claim 1, wherein during the electrolyzing, the aqueous composition is in contact with porous silica supported-sol-gel coated titanium catalysts.

10. The method of claim 9, wherein a reaction time in the electrolyzing is about 10 min.

11. The method of claim 1, wherein a length of the capillary is from 7 to 21 cm.

12. The method of claim 1, wherein the applied potential is about 3 kV.