1. Full name: Lưu Văn Bac                                                         2. Sex: Male

3. Date of birth: 25/07/1982                                            4. Place of birth: Bac Ninh

5. Admission decision number: 4092/QD-ĐHKHTN on 27/11/2013 VNU University of Science.

6. Changes in academic process: Non

7. Official thesis title: “Study on conversion of waste vegetable oil into liquid fuels using catalysts based on regenerated FCC and hydrotalcite”

8. Major: Petroleum Chemistry                                         9. Code: 62440115

10. Supervisors:  Associate Prof. Dr.  Tran Thi Nhu Mai

                                    Dr. Nguyen Thi Minh Thu 

11. Summary of the new findings of the thesis:

- Study on the regeneration of spent FCC D1506 catalyst of Dung Quat Refinery by calcining coke method and extracting contaminated FCC as Fe, Ni, Ca and Na using oxalic acid with a concentration of 5% in water solvent. Regenerated FCC (FCC-TS) was characterized by EDX, XRD, SEM, BET and XRF methods. The surface area of regenerated FCC catalyst was 170m2/g in comparison with 112m2/g of spent FCC. The obtained XRF result showed that the removed amount of Fe, Ni and V were 54%, 54% and 26% respectively, that of Ca and Na were about 58% and 69%. Consider the structure of the obtained coke, which are mainly the derivative of two or three aromatic hydrocarbon rings such as 3,6-dimethyl-phenanthrene, naphthalene, indane và 4-methyl-phenanthrene...

- Exchanging of NaZSM-5 and NaY into HZSM-5 and LaY respectively, the addition of this additives into FCC-TS to produce 2% HZSM-5/FCC-TS, 5% HZSM-5/FCC-TS, 5% LaHY /FCC-TS. Study on cracking of waste cooking oil in gas-phase over SR-SCT-MAT at 500oC for 12 seconds. The obtained products were analyzed by online equipment, were mainly gasoline fraction.  The catalyst was supplemented HZSM-5 exhibited light olefin effect, in which the amount of ethylene, propylene and butene were higher than the addition of LaHY. For example, The amount of propylene obtained from 2% HZSM-5/FCC-TS, 5% HZSM-5/FCC-TS, 5% LaHY /FCC-TS were 6,73% mole, 11,63% mole và 4,6% mole respectively, the corresponding value for butene were 2,9% mole, 4,0% mole và 1,9% mole. Additionally, the decarboxylation, decarbonylation and dehydration activity were taken place due to the existence of H2, CO and CO2.

- Study on cracking of waste cooking oil in the liquid phase at 370oC, 400 oC and 420oC with its acid number of 63 by using FCC-TS with no addition of zeolite. Aromatic hydrocarbon did not exist in the obtained product. The product performance reach the highest at 420oC, the obtained product was mainly the linear hydrocarbon with C12-C17 accounted for 80%, had the acid number about 17-20 in ten consecutive reactions. GC-MS showed the existence of pentadecanoic acid, hexadecanoic acid, cis-9 octadecenoic acid.

- The preparation of hydrotalcite HT Mg-Al//g-Al2O3 and HT Mg-Al//g-Al2O3 contained Ni with Ni particle size about 4-5 nm. These catalyst was characterized by XRD, BET, TG/DTA and TEM. The obtained XRD showed the conservation of hydrotalcite after calcined 300oC.

- Study on decarboxylation of the product after cracking waste cooking oil that includes fatty acid using HT Mg-Al//g-Al2O3 and Ni- HT Mg-Al//g-Al2O3. Ni- HT Mg-Al/g-Al2O3 exhibited higher decarboxylation activity than HT Mg-Al/g-Al2O3. The liquid product selected green diesel fraction was linear hydrocarbon with the content of C14-C18 of 85%, C7-C12 and C12-C13 accounted for 10% and 5%, respectively.

 12. The new findings of this thesis:

- Study on the regeneration of spent FCC D1506 catalyst of Dung Quat Refinery by calcining coke method and extracting contaminated FCC as Fe, Ni, Ca and Na using oxalic acid, citric acid and lactic acid. The obtained result showed that oxalic acid had highest performance in removing contaminated metals like Fe, Ni and V. The obtained XRF result showed that the removed amount of Fe, Ni and V were 54%, 54% and 26% respectively, that of Ca and Na were about 58% and 69%. The surface area of regenerated FCC catalyst was 170m2/g in comparison with 112m2/g of spent FCC. Removing contaminated metals in FCC catalyst by using organic acid and hydroxyl acid, which were compounds exist in nature, so safety, the removing metal process was carried out at room temperature, not need digestion, was environmentally friendly.

- FCC-TS was added additives phase HZSM-5 and LaHY to produce 2% HZSM-5/FCC-TS, 5% HZSM-5/FCC-TS, 5% LaHY /FCC-TS. The obtained products were analyzed by online equipment, were mainly gasoline fraction.  The catalyst was supplemented HZSM-5 exhibited light olefin effect, in which the amount of ethylene, propylene and butene were higher than the addition of LaHY. For example, The amount of propylene obtained from 2% HZSM-5/FCC-TS, 5% HZSM-5/FCC-TS, 5% LaHY /FCC-TS were 6,73% mole, 11,63% mole và 4,6% mole respectively, the corresponding value for butene were 2,9% mole, 4,0% mole và 1,9% mole. Additionally, the decarboxylation, decarbonylation and dehydration activity were taken place due to the existence of H2, CO and CO2.

- Study on cracking of waste cooking oil in the liquid phase at 370oC, 400 oC and 420oC with its acid number of 63 by using FCC-TS with no addition of zeolite, the corresponding amount of liquid product accounted for 78%, 80% and 85%, water about   3,9%, 4,3% and 5,1%, unconverted compound accounted for 11,%, 6,2% and 1% due to monoglyceride, diglyceride… wasn’t cracked. Aromatic hydrocarbon did not exist in the obtained product. The product performance reaches the highest at 420oC, resulting in the increasing intensity of dehydration. Using Ni- HT Mg-Al/g-Al2O3 for decarboxylation of the product after cracking waste cooking oil. The obtained product was mainly kerosene fraction and green diesel, not including aromatic hydrocarbon. Using two-stage process including cracking over acid catalyst and decarboxylation is the current trend in biomass conversion, this process does not need H2 and rare metals consumption.

13. Practical applicability:

Regenerate spent FCC D1506 catalyst by calcining coke method and extracting contaminated FCC as Fe, Ni, Ca and Na using organic acid and hydroxyl acid, which were compounds exist in nature, so safety, the removing metal process was carried out at room temperature, not need digestion, was environmentally friendly. Consequently, helping to reduce financial consumption, handle polluted environment due to using the industrial catalyst. Regenerated FCC can reuse for Refinery process.

Using Ni- HT Mg-Al/g-Al2O3 for decarboxylation of the product after cracking waste cooking oil to produce kerosene and green diesel, which were the linear hydrocarbon, can be directly used as fuel, this process does not need H2 and rare metals consumption.

14. Further research directions:

Study on developing in using environmentally friendly chemicals to enhance the removing performance of contaminated metals Fe, Ni, V in spent FCC catalyst of Dung Quat Refinery to reuse for bio-oil Refinery.

Study on developing catalyst for deoxylation purpose, which does not need H2 and rare metals consumption to convert biomass into green diesel. This product will replace gradually fossil fuel in the future.

15. Thesis-related publications:

[1]. Tran Thi Nhu Mai, Luu Van Bac, Vu Manh Hiep, Tran Chi Cong, Dang Thanh Tung (2014), “Study on the cracking of wasted vegetable oil over catalyst prepared from regenerated FCC and HZSM-5 zeolite”, Journal of Catalysis and Adsorption, 3(2), pp.76-82.

[2]. Luu Van Bac, Tran Thi Nhu Mai, Nguyen Dang Huan, Do Thanh Hai, Giang Thi Phuong Ly (2014), “Study on the cracking of wasted vegetable oil in liquid phase using spent FCC catalyst regenerated by solution of enthanedioic acid in xylene solvent”, Journal of Catalysis and Adsorption, 3(3), pp.24-33.

[3]. Tran Thi Nhu Mai, Luu Van Bac, Nguyen Van Manh, Nguyen Thi Minh Thu, Giang Thi Phuong Ly (2015), “Study on removing metals Fe, Ni, Ca and Na in FCC spent catalyst (S-cat) of Dung Quat Refinery by hydroxy cacboxylic acid”, Journal of Catalysis and Adsorption, 4(4B), pp.54-58.

[4]. Luu Van Bac, Tran Thi Nhu Mai, Tran Chi Cong, Vu Manh Hiep (2015), “Study on synthesis, characterization and a catalytic property of hydrotalcite/ γ-Al2O3 in decarboxylation cooking oil”, Journal of Chemistry, 53(4e1), pp.105-108.

[5]. Tran Thi Nhu Mai, Tran Chi Cong, Nguyen Van Manh, Luu Van Bac, Quach Vien Duong (2016), “Reuse of spent FCC of Dung Quat refinery for cracking wasted cooking oil in liquid phase”, Journal of Chemistry, 54(2), pp.194-198.

[6]. Luu Van Bac, Tran Thi Nhu Mai, Nguyen Van Manh, Giang Thi Phuong Ly, Nguyen Thi Minh Thu (2016), “Study on synthesis of hydrotalcite Mg-Al/ γ-Al2O3 for decarboxylation of cracking oil”, VNU Journal of Science: Natural Science and Technology, 32(3), pp.147-151.