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Synthesis and Characterization HY Zeolite from Natural Aluminosilicate for n-Hexadecane Cracking
Available online at www.sciencedirect.com
ScienceDirect Materials Today: Proceedings 13 (2019) 76–81
www.materialstoday.com/proceedings
ICAMST 2018
Synthesis and Characterization HY Zeolite from Natural Aluminosilicate for n-Hexadecane Cracking Indah Revita Saragia, Yuni Krisyuningsih Krisnandia, Riwandi Sihombinga* Chemistry Department, Faculty of Mathematics and Natural Science, Universitas Indonesia, Jalan Margonda Raya, Depok, 16424, Indonesia
Abstract Synthesis of NaY zeolite using natural sources of alumina and silica is interesting yet challenging. Focused on reducing synthetic material, in this research, synthesis has been carried out using Bangka Belitung natural Kaolin as silica and alumina sources. Furthermore, NaY zeolites were also synthesized using synthetic materials such as Ludox and Silica Water. It can be seen that NaY from Ludox gives the best NaYwith ratio of Si/Al is ~1.78. To conclude, synthesis of NaY using natural alumina silicates as source is considerably successful. The cracking results show the catalyst with synthetic material has high conversion, yield and selectivity. © 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science and Technology 2018, 6th ICAMST. Keywords: NaY zeolit; kaoli; catalyst; cracking; hexadecane
1. Introduction Zeolite HY is a material that contains acid sites in internal porous structure,which can convert long chain molecules to short chain molecules [1]. Generally, zeolite is a tetrahedral linked silicate [2]. But, in some position, aluminum replaces silicon and make negative charge in the framework [3]. The negative charge can be counterbalanced by protonation and form a Bronsted acid site [4]. Basically, acidity in zeolite can be found at Si-Al interfaces (Bronsted acid) and also at Al2O3 surface (Lewis site)[1].
* Corresponding author. Tel.: +62-2-727-0027; fax: +62-21-786-3432 E-mail address: [email protected] 2214-7853© 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science and Technology 2018, 6th ICAMST.
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Fuel demand, which is increasing rapidly from year to year, thus requiring an increase in conversion of the breakdown of hydrocarbon chains [1]. Conventional hydrothermal methods in zeolite synthesis are still quite popular today. Synthesis is carried out by adding a certain ratio of alumina and silica in a medium at a temperature of 60-200 ⁰C for some time [5]. However, this zeolite synthesis is generally not an environmentally friendly process [6]. Green chemistry concept began to be applied in renewing the method of zeolite synthesis to reduce its negative impact on the environment. Besides, this is also caused by synthetic materials that are expensive and difficult to obtain. So, this research will report about HY zeolite synthesis from natural alumina-silica and its comparison with synthetic zeolite as catalyst for catalytic cracking in hexadecane. 2. Materials and Methods 2.1. Materials Bangka Belitung natural kaolin, colloidal silica-Ludox HS40 (Sigma Aldrich), CH3COOH (glacial, Merck), CH3COOHNa.3H2O (Merck), H2O2 (30%, Merck), HNO3 (Merck), HCl (Merck), NaOH (pellet, 99%,Merck), Na3C6H5O7.2H2O (Merck), NaHCO3 (Merck), Hexadecane (Sigma Aldrich), deionized water. 2.2. Modification of Natural Kaolin Bangka Belitung kaolin as precursor material was consisted of several steps physical activation, purification and calcinations[7-8]. Natural kaolin was filtered using a sieve until 100 µm. Activation of natural kaolin was performed by washing the kaolin with deionized water (1:3 w/v) under stirring for 3 h in room temperature. The solid phase then was dried at 105 ºC. Purification process was conducted by treating activated kaolin with 1 M NaOAc buffered to pH 5, 30% H2O2, and dithionite-citrate-bicarbonate. After purification, calcination or dehidroxilation was done by calcination of the purified kaolin in 800 ⁰C. Characterization of natural zeolite was done using XRD, FTIR, and SEM. 2.3. Silica Extraction Silica extraction was carried out by dissolving some metakaolin into aquaregia (HCl:HNO3 with ratio 3:1 (v/v)) for 4 h at 100 ⁰C. After this process, some silica could be collected and washed using deionized water until pH was neutral. 2.4. Synthesis of NaY Zeolite Synthesis of NaY zeolite followed the molar composition (Na2O: Al2O3: SiO2: H2O = 10,67: 1: 10: 180) [9]. Metakaolin was used as Al and Si source and certain amount of colloidal silica (Ludox 40), silica extraction, sodium silica water were add as additional Si source. The crystalization was carried out in autoclave and polypropylene bottle at 100 oC for 24 hours. Extensive characterization techniques such as XRD, XRF, FTIR, SEM were carried out on metakaolin and the as-synthesized material. 3. Results and discussions 3.1 Characterization Raw Material Fig. 1. shows the spectra of activated, purified, dehydroxylation kaolin (metakaolin) and silica extraction. The peaks at 1106-1118 cm-1 shows differences purity because SiO2 that shifts from 1116 cm-1 to 1109 cm-1. From metakaolin spectrum, it can be seen that metakaolin has broad peak in 3500 cm-1 and doesn’t have a peak in 700 cm1 that indicate the peak from Si-O and Al-O because the structure has been destructed. Silica extraction spectrum shows that peak in 1100 cm-1 is higher that the other that indicate its only silicon in the structure.
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Fig. 1. FTIR of raw materials
Fig. 2. shows the comparison of XRD patterns among activated, purified, metakaolin and silica extraction. The data from XRD pattern supported the FTIR results. It can be seen that metakaolin does not have quartz peak anymore at 2ϴ of 110 and 220 that indicate typical peak for SiO2. The XRD pattern for silica extraction confirmed that silica has amorphous phase.
Fig. 2. XRD of raw material
Mineral and Chemical Analysis of Kaolin Bangka Belitung inTable 1 shows the result of oxide and mineral phase composition of kaolin and metakaolinunder the analysis using XRF. The result identified that SiO2 and Al2O3 as the predominant oxides and it confirmed that metakaolin process doesnot change the composition. Table 1. XRF Compositon of Kaolin and Metakaolin Kaolin Metakaolin Element Concentration Na2O/K2O
4.48
5.31
Al2O3
33.39
33.39
SiO2
57.11
56.70
Cl
0.59
0.53
CaO
0.68
0.59
Fe2O3
3.75
3.57
3.2 Synthesis NaY Zeolite Fig. 3. shows the NaY zeolite’s FTIR spectra from different source of syntetic silica indicate a double six ring absorption of D6R with a structure of Faujasite(FAU). The peaks at 3751-3501 cm-1 affirms the existence of hydroxyl groups (-OH) from silanol (Si-OH). Peak at 1501-1701 cm-1fits to hydroxyl vibration of water molecules
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and also there is a peak of silanol and aluminol asymmetry vibration at 1251-951 cm-1 globular number which is the characteristic peak of the Si and Al. Based on characterization, synthesis of NaY zeolites had been successful a
b
Fig. 3(a). FTIR spectra and (b) XRD of NaY zeolite from synthetic materials
Fig. 3(b). show that NaY zeolite from synthesis with XRD was done to observe and verify from the crystalinity, that the zeolite formed is NaY zeolite. So, XRD of NaY zeolite results from synthesis and standard NaY zeolite from International Zeolite Association-online. It is possible because there are still other impurities such as Fe2O3. this figure inform that synthesis NaY zeolite using Ludox has been done succesfully, the typical zeolite peak is similar with commercial NaY zeolite. But, unfortunately that NaY zeolite from silica water cannot be done succesfully. This might be cause by different consentration of silica in the solution. Fig. 4. shows the XRD characterization ofNaY zeolite using metakaolin as silica and alumina sources (Fig. 4a) and silica extraction as silica source (Fig. 4b). From the figure, it can be seen that both metakaolin and silica extraction donot have typical peak of NaY zeolite. It might be cause by impurity of natural sources, so both of them cannot form NaY zeolite structure perfectly. Fig. 5. shows SEM result from NaY Zeolite synthetic source in 5000x magnification. a
b
Fig. 4. XRD of NaY zeolite from synthetic material
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Fig. 5. SEM of NaY zeolite from synthetic material
3.4 Preparation of HY Zeolite NaY zeolite was converted into HY zeolite by using ammonium ion exchange method. It was treated with ammonium chloride. Fig. 6. shows the XRD comparison between NaY and HY from synthetic materials. It shows that modification of NaY into HY zeolite destruct the structure of zeolite.
Fig. 6. XRD Comparison BetweenNaY and HY Zeolite
3.5 Application Test of Catalytic Cracking From the characterization, it conclude that synthesis zeolite using metakaolin and silica extraction cannot form NaY structure, so for the catalytic cracking application test, it only used NaY zeolite synthetic. Before it can be used as a catalyst it should be protonated in to HY zeolite [10]. Fig. 7. shows the result from application test in hexadecane cracking.
78.17082912
99.19654201
78.17082912
Conversion(%) Selectivity(%) Yield(%)
Conversion(%)
Selectivity(%)
Yield(%)
Fig. 7. Percentage of Conversion, Yield and Selectivity from Cataytic Test
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From the data, it can be concluded that HYzeolite can be used as catalyst for catalytic cracking with percent conversion about 78%, percent yield about 78%, and selectivity about 99%. 4
Conclusion
With a SiO2/Al2O3 ratio, additional silica was needed for NaY zeolite synthesis. In this research, silica sources were provided by metakaolin, coloidal silica, sodium silica water, and silica extraction. There were several steps that should be done before kaolin can be used as silica and alumina source such as activation, purification, and calcination. Zeolite NaY with coloidal silica as silica source showed the best similarity with the standard peak of NaY zeolite. NaY zeolite using sodium silica water, metakaolin, and silica extraction did not show the similarity with commercial NaY zeolite. So for the catalytic test, only HY zeolite from synthetic material could be done. Acknowledgement This worked is funded by Hibah Publikasi Internasional Terindeks Untuk Tugas Akhir Mahasiswa UI (Hibah PITTA) year 2018 and Pertamina Grant. References [1] [2] [3]
E.T.C. Vogt, B.M. Weckhuysen, Chem. Soc. Rev., 44 (2015) 7342–7370. E.B.G. Johnson, S.E. Arshad, Appl. Clay Sci., 97–98, (2014) 215–221. P.J. Kunkeler, B.J. Zuurdeeg, J.C. Van Der Waal, J.A. Van Bokhoven, D.C. Koningsberger, H. Van Bekkum, J. Catal., 180, (1998) 234– 244. [4] A. Primo, H. Garcia, Chem. Soc. Rev., 43 (2014) 7548–7561. [5] M. Maldonado, M.D. Oleksiak, S. Chinta, J. Am. Chem. Soc.,135 (2013) 2641–2652. [6] X. Meng, F. Xiao, Chem. Rev., 114 (2014) 1521–1543. [7] A. S. Kovo, O. Hernandez, S. M. Holmes, J. Mater. Chem., 19 (2009) 6207. [8] T. Abdullahi, Z. Harun, M.H.D. Othman, Adv. Powder Technol., 28 (2017) 1827–1840. [9] C.J.R.D.M. Ginter, G.T.Went, A.T. Bell, Zeolites, 12 (1992) 733–741. [10] Z. Liu, C. Shi, D. Wu, S. He, B. Ren, Journal of Nanotechnology, 2016.
ScienceDirect Materials Today: Proceedings 13 (2019) 76–81
www.materialstoday.com/proceedings
ICAMST 2018
Synthesis and Characterization HY Zeolite from Natural Aluminosilicate for n-Hexadecane Cracking Indah Revita Saragia, Yuni Krisyuningsih Krisnandia, Riwandi Sihombinga* Chemistry Department, Faculty of Mathematics and Natural Science, Universitas Indonesia, Jalan Margonda Raya, Depok, 16424, Indonesia
Abstract Synthesis of NaY zeolite using natural sources of alumina and silica is interesting yet challenging. Focused on reducing synthetic material, in this research, synthesis has been carried out using Bangka Belitung natural Kaolin as silica and alumina sources. Furthermore, NaY zeolites were also synthesized using synthetic materials such as Ludox and Silica Water. It can be seen that NaY from Ludox gives the best NaYwith ratio of Si/Al is ~1.78. To conclude, synthesis of NaY using natural alumina silicates as source is considerably successful. The cracking results show the catalyst with synthetic material has high conversion, yield and selectivity. © 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science and Technology 2018, 6th ICAMST. Keywords: NaY zeolit; kaoli; catalyst; cracking; hexadecane
1. Introduction Zeolite HY is a material that contains acid sites in internal porous structure,which can convert long chain molecules to short chain molecules [1]. Generally, zeolite is a tetrahedral linked silicate [2]. But, in some position, aluminum replaces silicon and make negative charge in the framework [3]. The negative charge can be counterbalanced by protonation and form a Bronsted acid site [4]. Basically, acidity in zeolite can be found at Si-Al interfaces (Bronsted acid) and also at Al2O3 surface (Lewis site)[1].
* Corresponding author. Tel.: +62-2-727-0027; fax: +62-21-786-3432 E-mail address: [email protected] 2214-7853© 2019 Elsevier Ltd. All rights reserved. Peer-review under responsibility of the scientific committee of The 6th International Conference on Advanced Materials Science and Technology 2018, 6th ICAMST.
Saragi et al. / Materials Today: Proceedings 13 (2019) 76–81
77
Fuel demand, which is increasing rapidly from year to year, thus requiring an increase in conversion of the breakdown of hydrocarbon chains [1]. Conventional hydrothermal methods in zeolite synthesis are still quite popular today. Synthesis is carried out by adding a certain ratio of alumina and silica in a medium at a temperature of 60-200 ⁰C for some time [5]. However, this zeolite synthesis is generally not an environmentally friendly process [6]. Green chemistry concept began to be applied in renewing the method of zeolite synthesis to reduce its negative impact on the environment. Besides, this is also caused by synthetic materials that are expensive and difficult to obtain. So, this research will report about HY zeolite synthesis from natural alumina-silica and its comparison with synthetic zeolite as catalyst for catalytic cracking in hexadecane. 2. Materials and Methods 2.1. Materials Bangka Belitung natural kaolin, colloidal silica-Ludox HS40 (Sigma Aldrich), CH3COOH (glacial, Merck), CH3COOHNa.3H2O (Merck), H2O2 (30%, Merck), HNO3 (Merck), HCl (Merck), NaOH (pellet, 99%,Merck), Na3C6H5O7.2H2O (Merck), NaHCO3 (Merck), Hexadecane (Sigma Aldrich), deionized water. 2.2. Modification of Natural Kaolin Bangka Belitung kaolin as precursor material was consisted of several steps physical activation, purification and calcinations[7-8]. Natural kaolin was filtered using a sieve until 100 µm. Activation of natural kaolin was performed by washing the kaolin with deionized water (1:3 w/v) under stirring for 3 h in room temperature. The solid phase then was dried at 105 ºC. Purification process was conducted by treating activated kaolin with 1 M NaOAc buffered to pH 5, 30% H2O2, and dithionite-citrate-bicarbonate. After purification, calcination or dehidroxilation was done by calcination of the purified kaolin in 800 ⁰C. Characterization of natural zeolite was done using XRD, FTIR, and SEM. 2.3. Silica Extraction Silica extraction was carried out by dissolving some metakaolin into aquaregia (HCl:HNO3 with ratio 3:1 (v/v)) for 4 h at 100 ⁰C. After this process, some silica could be collected and washed using deionized water until pH was neutral. 2.4. Synthesis of NaY Zeolite Synthesis of NaY zeolite followed the molar composition (Na2O: Al2O3: SiO2: H2O = 10,67: 1: 10: 180) [9]. Metakaolin was used as Al and Si source and certain amount of colloidal silica (Ludox 40), silica extraction, sodium silica water were add as additional Si source. The crystalization was carried out in autoclave and polypropylene bottle at 100 oC for 24 hours. Extensive characterization techniques such as XRD, XRF, FTIR, SEM were carried out on metakaolin and the as-synthesized material. 3. Results and discussions 3.1 Characterization Raw Material Fig. 1. shows the spectra of activated, purified, dehydroxylation kaolin (metakaolin) and silica extraction. The peaks at 1106-1118 cm-1 shows differences purity because SiO2 that shifts from 1116 cm-1 to 1109 cm-1. From metakaolin spectrum, it can be seen that metakaolin has broad peak in 3500 cm-1 and doesn’t have a peak in 700 cm1 that indicate the peak from Si-O and Al-O because the structure has been destructed. Silica extraction spectrum shows that peak in 1100 cm-1 is higher that the other that indicate its only silicon in the structure.
78
Saragi et al./ Materials Today: Proceedings 13 (2019) 76–81
Fig. 1. FTIR of raw materials
Fig. 2. shows the comparison of XRD patterns among activated, purified, metakaolin and silica extraction. The data from XRD pattern supported the FTIR results. It can be seen that metakaolin does not have quartz peak anymore at 2ϴ of 110 and 220 that indicate typical peak for SiO2. The XRD pattern for silica extraction confirmed that silica has amorphous phase.
Fig. 2. XRD of raw material
Mineral and Chemical Analysis of Kaolin Bangka Belitung inTable 1 shows the result of oxide and mineral phase composition of kaolin and metakaolinunder the analysis using XRF. The result identified that SiO2 and Al2O3 as the predominant oxides and it confirmed that metakaolin process doesnot change the composition. Table 1. XRF Compositon of Kaolin and Metakaolin Kaolin Metakaolin Element Concentration Na2O/K2O
4.48
5.31
Al2O3
33.39
33.39
SiO2
57.11
56.70
Cl
0.59
0.53
CaO
0.68
0.59
Fe2O3
3.75
3.57
3.2 Synthesis NaY Zeolite Fig. 3. shows the NaY zeolite’s FTIR spectra from different source of syntetic silica indicate a double six ring absorption of D6R with a structure of Faujasite(FAU). The peaks at 3751-3501 cm-1 affirms the existence of hydroxyl groups (-OH) from silanol (Si-OH). Peak at 1501-1701 cm-1fits to hydroxyl vibration of water molecules
Saragi et al. / Materials Today: Proceedings 13 (2019) 76–81
79
and also there is a peak of silanol and aluminol asymmetry vibration at 1251-951 cm-1 globular number which is the characteristic peak of the Si and Al. Based on characterization, synthesis of NaY zeolites had been successful a
b
Fig. 3(a). FTIR spectra and (b) XRD of NaY zeolite from synthetic materials
Fig. 3(b). show that NaY zeolite from synthesis with XRD was done to observe and verify from the crystalinity, that the zeolite formed is NaY zeolite. So, XRD of NaY zeolite results from synthesis and standard NaY zeolite from International Zeolite Association-online. It is possible because there are still other impurities such as Fe2O3. this figure inform that synthesis NaY zeolite using Ludox has been done succesfully, the typical zeolite peak is similar with commercial NaY zeolite. But, unfortunately that NaY zeolite from silica water cannot be done succesfully. This might be cause by different consentration of silica in the solution. Fig. 4. shows the XRD characterization ofNaY zeolite using metakaolin as silica and alumina sources (Fig. 4a) and silica extraction as silica source (Fig. 4b). From the figure, it can be seen that both metakaolin and silica extraction donot have typical peak of NaY zeolite. It might be cause by impurity of natural sources, so both of them cannot form NaY zeolite structure perfectly. Fig. 5. shows SEM result from NaY Zeolite synthetic source in 5000x magnification. a
b
Fig. 4. XRD of NaY zeolite from synthetic material
80
Saragi et al./ Materials Today: Proceedings 13 (2019) 76–81
Fig. 5. SEM of NaY zeolite from synthetic material
3.4 Preparation of HY Zeolite NaY zeolite was converted into HY zeolite by using ammonium ion exchange method. It was treated with ammonium chloride. Fig. 6. shows the XRD comparison between NaY and HY from synthetic materials. It shows that modification of NaY into HY zeolite destruct the structure of zeolite.
Fig. 6. XRD Comparison BetweenNaY and HY Zeolite
3.5 Application Test of Catalytic Cracking From the characterization, it conclude that synthesis zeolite using metakaolin and silica extraction cannot form NaY structure, so for the catalytic cracking application test, it only used NaY zeolite synthetic. Before it can be used as a catalyst it should be protonated in to HY zeolite [10]. Fig. 7. shows the result from application test in hexadecane cracking.
78.17082912
99.19654201
78.17082912
Conversion(%) Selectivity(%) Yield(%)
Conversion(%)
Selectivity(%)
Yield(%)
Fig. 7. Percentage of Conversion, Yield and Selectivity from Cataytic Test
Saragi et al. / Materials Today: Proceedings 13 (2019) 76–81
81
From the data, it can be concluded that HYzeolite can be used as catalyst for catalytic cracking with percent conversion about 78%, percent yield about 78%, and selectivity about 99%. 4
Conclusion
With a SiO2/Al2O3 ratio, additional silica was needed for NaY zeolite synthesis. In this research, silica sources were provided by metakaolin, coloidal silica, sodium silica water, and silica extraction. There were several steps that should be done before kaolin can be used as silica and alumina source such as activation, purification, and calcination. Zeolite NaY with coloidal silica as silica source showed the best similarity with the standard peak of NaY zeolite. NaY zeolite using sodium silica water, metakaolin, and silica extraction did not show the similarity with commercial NaY zeolite. So for the catalytic test, only HY zeolite from synthetic material could be done. Acknowledgement This worked is funded by Hibah Publikasi Internasional Terindeks Untuk Tugas Akhir Mahasiswa UI (Hibah PITTA) year 2018 and Pertamina Grant. References [1] [2] [3]
E.T.C. Vogt, B.M. Weckhuysen, Chem. Soc. Rev., 44 (2015) 7342–7370. E.B.G. Johnson, S.E. Arshad, Appl. Clay Sci., 97–98, (2014) 215–221. P.J. Kunkeler, B.J. Zuurdeeg, J.C. Van Der Waal, J.A. Van Bokhoven, D.C. Koningsberger, H. Van Bekkum, J. Catal., 180, (1998) 234– 244. [4] A. Primo, H. Garcia, Chem. Soc. Rev., 43 (2014) 7548–7561. [5] M. Maldonado, M.D. Oleksiak, S. Chinta, J. Am. Chem. Soc.,135 (2013) 2641–2652. [6] X. Meng, F. Xiao, Chem. Rev., 114 (2014) 1521–1543. [7] A. S. Kovo, O. Hernandez, S. M. Holmes, J. Mater. Chem., 19 (2009) 6207. [8] T. Abdullahi, Z. Harun, M.H.D. Othman, Adv. Powder Technol., 28 (2017) 1827–1840. [9] C.J.R.D.M. Ginter, G.T.Went, A.T. Bell, Zeolites, 12 (1992) 733–741. [10] Z. Liu, C. Shi, D. Wu, S. He, B. Ren, Journal of Nanotechnology, 2016.