Date of Award
12-2023
Document Type
Thesis
Degree Name
Master of Science in Chemical Engineering (MSChE)
Department
Chemical and Petroleum Engineering
First Advisor
Mohammednoor Altarawneh
Second Advisor
Muhammad Z. Iqbal
Abstract
Levoglucosan (LG) or (1,6-anhydro-β-D-glucopyranose) signifies important sugar derivatives produces in appreciable quantities from thermochemical and biochemical degradation of biomass. It is often regarded as an important platform chemical for the synthesis of value-added products, most notably styrene and furans. The work in this thesis entails two broad aims; to produce LG from pyrolysis of date pits; and then convert the LG into transportation fuels through a hydrodeoxygenation (HDO) reaction. The particular choice of date pits stems from its local relative abundance as a waste biomass. Aiming to further improve the yield of levoglucosan yields from pyrolysis of date pits, pre-treatment methods were carried out via washing the biomass with different concentrations of selected acids (sulfuric acid: 1M /3M, nitric acid: 1M / 3M), also well as with hot water. Chemical and elemental compositions of the five considered samples were thoroughly analyzed and characterized by a wide array of techniques such as Neutral Detergent Fiber (NDF%), ASH content and organic Matter (%) and Mineral Nutrients Profile (ppm). By utilizing Py-GC/MS system, the products distribution from pyrolysis of raw and treated date pits were obtained at a range of temperatures between 300-500°C. Compared to the raw date pits, pyrolysis of treated date pits by 1 M H2SO4 acid exhibited a dramatic increase in the concentration of levoglucosan due to the profound removal of the various categories of minerals in date pits and increasing the NDF%. Results show that the highest yield of (~ 72%) was attained after pre-treatment with 1 M H2SO4 solution at a temperature 300°C. A positive correlation prevails between the removal efficiency of alkali/alkaline earth metals (AAEMs) and the yield of LG. The former catalyzes ring opening reaction that results in the destruction of sugar derivatives. Similarly, the water pretreatment increases the yield of LG compared to the raw date pits. Outcomes demonstrated herein convey a practical method to enhance the production of commodity chemicals from waste biomass. The second part of the thesis presents a viable gaseous hydrodeoxygenation (HDO) route for Levoglucosan (LG) that leads to the formation of non-oxygenated hydrocarbon cuts that make commercial transportation fuels, namely gasoline, diesel, and jet fuels. The outlined process encompasses HDO of an evaporated stream of dissolved LG over 5% Ni-CeO2 catalysts between 100°C–500°C. It is found that the load of the aliphatic compounds attains values between 68.1% and 75.3% across the investigated temperature window. Similarly, fractions of aromatic compounds remain within 8.1%–13.9%. Major observed aliphatic compounds include tetradecane, dodecane, octane, and decane. Alkylated benzenes appear in appreciable quantities. Governing HDO’s mechanisms were mapped out by density functional theory (DFT) calculations. Utilizing a 10% load of Ni has slightly reduced the relative area of aliphatic compounds. The combined area of the oxygenated compounds remains less than 10% at all temperatures. This finding entails a profound HDO’s capacity of the deployed catalyst and opens a direct venue for the effective utilization of LG in fuel production. Overall, this research underscores the utilization of lignocellulosic biomass, specifically date pits, as a valuable carbon source in the biorefinery concept.
Arabic Abstract
ﺗﺤﻮﯾﻞ اﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮﺳﺎن إﻟﻰ وﻗﻮد ﺳﺎﺋﻞ ﻋﻦ طﺮﯾﻖ ﻣﺤﻔﺰات Ni-CeO2 واﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺴﺒﻘﺔ ﻟﺒﺬور اﻟﺘﻤﺮ ﻟﺘﺤﺴﯿﻦ إﻧﺘﺎﺟﯿﺔ اﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮﺳﺎن
ﯾﺸﯿﺮ اﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮزان (LG) أو (1،6-أﻧﮭﯿﺪرو-β-D-ﺟﻠﻮﻛﻮﺑﯿﺮاﻧﻮز) إﻟﻰ ﻣﺸﺘﻘﺎت اﻟﺴﻜﺮ اﻟﮭﺎﻣﺔ اﻟﺘﻲ ﺗﻨﺘﺞ ﺑﻜﻤﯿﺎت ﻣﻠﺤﻮظﺔ ﻣﻦ اﻟﺘﺤﻠﻞ اﻟﻜﯿﻤﯿﺎﺋﻲ اﻟﺤﺮاري واﻟﻜﯿﻤﯿﺎﺋﻲ اﻟﺤﯿﻮي ﻟﻠﻜﺘﻠﺔ اﻟﺤﯿﻮﯾﺔ. ﻏﺎﻟﺒًﺎ ﻣﺎ ﯾُﻨﻈﺮ إﻟﯿﮫ ﻋﻠﻰ أﻧﮫ ﻣﺎدة ﻛﯿﻤﯿﺎﺋﯿﺔ أﺳﺎﺳﯿﺔ ﻣﮭﻤﺔ ﻟﺘﺨﻠﯿﻖ اﻟﻤﻨﺘﺠﺎت ذات اﻟﻘﯿﻤﺔ اﻟﻤﻀﺎﻓﺔ، وأﺑﺮزھﺎ اﻟﺴﺘﺎﯾﺮﯾﻦ واﻟﻔﯿﻮران. اﻟﻌﻤﻞ ﻓﻲ ھﺬه اﻷطﺮوﺣﺔ ﯾﻨﻄﻮي ﻋﻠﻰ ھﺪﻓﯿﻦ واﺳﻌﯿﻦ؛ ﻹﻧﺘﺎج إل ﺟﻲ ﻣﻦ اﻻﻧﺤﻼل اﻟﺤﺮاري ﻟﻨﻮاة اﻟﺘﻤﺮ؛ وﻣﻦ ﺛﻢ ﺗﺤﻮﯾﻞ LG إﻟﻰ وﻗﻮد اﻟﻨﻘﻞ ﻣﻦ ﺧﻼل ﺗﻔﺎﻋﻞ إزاﻟﺔ اﻷﻛﺴﺠﯿﻦ (HDO). وﯾﻨﺒﻊ اﻻﺧﺘﯿﺎر اﻟﺨﺎص ﻟﻨﻮاة اﻟﺘﻤﺮ ﻣﻦ وﻓﺮﺗﮭﺎ اﻟﻨﺴﺒﯿﺔ اﻟﻤﺤﻠﯿﺔ ﻛﻜﺘﻠﺔ ﺣﯿﻮﯾﺔ ﻣﻦ اﻟﻨﻔﺎﯾﺎت. ﺑﮭﺪف ﺗﺤﺴﯿﻦ إﻧﺘﺎﺟﯿﺔ ﻣﺤﺼﻮل اﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮزان ﻣﻦ اﻻﻧﺤﻼل اﻟﺤﺮاري ﻟﻨﻮى اﻟﺘﻤﺮ، ﺗﻢ ﺗﻨﻔﯿﺬ طﺮق اﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺴﺒﻘﺔ ﻋﻦ طﺮﯾﻖ ﻏﺴﻞ اﻟﻜﺘﻠﺔ اﻟﺤﯿﻮﯾﺔ ﺑﺘﺮﻛﯿﺰات ﻣﺨﺘﻠﻔﺔ ﻣﻦ اﻷﺣﻤﺎض اﻟﻤﺨﺘﺎرة (ﺣﻤﺾ اﻟﻜﺒﺮﯾﺘﯿﻚ: 1م/3م وﺣﻤﺾ اﻟﻨﯿﺘﺮﯾﻚ: 1م/3م) وﻛﺬﻟﻚ وﻛﺬﻟﻚ ﻣﻊ اﻟﻤﺎء اﻟﺴﺎﺧﻦ. ﺗﻢ ﺗﺤﻠﯿﻞ اﻟﺘﺮﻛﯿﺒﺎت اﻟﻜﯿﻤﯿﺎﺋﯿﺔ واﻟﻌﻨﺼﺮﯾﺔ ﻟﻠﻌﯿﻨﺎت اﻟﺨﻤﺲ اﻟﻤﺪروﺳﺔ ﺑﺪﻗﺔ وﺗﻢ ﺗﻤﯿﯿﺰھﺎ ﺑﻤﺠﻤﻮﻋﺔ واﺳﻌﺔ ﻣﻦ اﻟﺘﻘﻨﯿﺎت ﻣﺜﻞ أﻟﯿﺎف اﻟﻤﻨﻈﻔﺎت اﻟﻤﺤﺎﯾﺪة (NDF%) وﻣﺤﺘﻮى ASH واﻟﻤﻮاد اﻟﻌﻀﻮﯾﺔ (٪) وﻣﻠﻒ اﻟﻌﻨﺎﺻﺮ اﻟﻐﺬاﺋﯿﺔ اﻟﻤﻌﺪﻧﯿﺔ (ﺟﺰء ﻓﻲ اﻟﻤﻠﯿﻮن). ﺑﺎﺳﺘﺨﺪام ﻧﻈﺎم Py-GC/MS، ﺗﻢ اﻟﺤﺼﻮل ﻋﻠﻰ ﺗﻮزﯾﻊ اﻟﻤﻨﺘﺠﺎت ﻣﻦ اﻻﻧﺤﻼل اﻟﺤﺮاري ﻟﻨﻮاة اﻟﺘﻤﺮ اﻟﺨﺎم واﻟﻤﻌﺎﻟﺠﺔ ﻓﻲ ﻧﻄﺎق درﺟﺎت ﺣﺮارة ﺗﺘﺮاوح ﺑﯿﻦ 500-300 درﺟﺔ ﻣﺌﻮﯾﺔ. ﺑﺎﻟﻤﻘﺎرﻧﺔ ﻣﻊ ﻧﻮى اﻟﺘﻤﺮ اﻟﺨﺎم، أظﮭﺮ اﻻﻧﺤﻼل اﻟﺤﺮاري ﻟﻨﻮاة اﻟﺘﻤﺮ اﻟﻤﻌﺎﻟﺠﺔ ﺑﺤﻤﺾ ١ ﻣﻮﻻر ﻣﻦ ﺣﻤﺾ H2SO4 زﯾﺎدة ﻛﺒﯿﺮة ﻓﻲ ﺗﺮﻛﯿﺰ اﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮزان ﺑﺴﺒﺐ اﻹزاﻟﺔ اﻟﻌﻤﯿﻘﺔ ﻟﻤﺨﺘﻠﻒ ﻓﺌﺎت اﻟﻤﻌﺎدن ﻓﻲ ﻧﻮاة اﻟﺘﻤﺮ وزﯾﺎدة ﻧﺴﺒﺔ NDF. أظﮭﺮت اﻟﻨﺘﺎﺋﺞ أﻧﮫ ﺗﻢ اﻟﺤﺼﻮل ﻋﻠﻰ أﻋﻠﻰ إﻧﺘﺎﺟﯿﺔ (~ 72%) ﺑﻌﺪ اﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺴﺒﻘﺔ ﺑﻤﺤﻠﻮل 1 ﻣﻮﻻر ﻣﻦ H2SO4 ﻋﻨﺪ درﺟﺔ ﺣﺮارة 300 درﺟﺔ ﻣﺌﻮﯾﺔ. ﯾﺴﻮد ارﺗﺒﺎط إﯾﺠﺎﺑﻲ ﺑﯿﻦ ﻛﻔﺎءة إزاﻟﺔ اﻟﻔﻠﺰات اﻟﻘﻠﻮﯾﺔ/اﻟﻘﻠﻮﯾﺔ اﻷرﺿﯿﺔ (AAEMs) وإﻧﺘﺎﺟﯿﺔ LG. اﻷول ﯾﺤﻔﺰ ﺗﻔﺎﻋﻞ ﻓﺘﺢ اﻟﺤﻠﻘﺔ اﻟﺬي ﯾﺆدي إﻟﻰ ﺗﺪﻣﯿﺮ ﻣﺸﺘﻘﺎت اﻟﺴﻜﺮ. وﻣﻦ ﻧﺎﺣﯿﺔ أﺧﺮى، ﻓﺈن اﻟﻤﻌﺎﻟﺠﺔ اﻟﻤﺴﺒﻘﺔ ﻟﻠﻤﯿﺎه ﺗﺰﯾﺪ ﻣﻦ إﻧﺘﺎﺟﯿﺔ الـ LG ﻣﻘﺎرﻧﺔ ﺑﻨﻮاة اﻟﺘﻤﺮ اﻟﺨﺎم. اﻟﻨﺘﺎﺋﺞ اﻟﻤﺒﯿﻨﺔ ھﻨﺎ ﺗﻨﻘﻞ طﺮﯾﻘﺔ ﻋﻤﻠﯿﺔ ﻟﺘﻌﺰﯾﺰ إﻧﺘﺎج اﻟﻤﻮاد اﻟﻜﯿﻤﯿﺎﺋﯿﺔ اﻟﺴﻠﻌﯿﺔ ﻣﻦ اﻟﻜﺘﻠﺔ اﻟﺤﯿﻮﯾﺔ ﻟﻠﻨﻔﺎﯾﺎت. ﯾﻘﺪم اﻟﺠﺰء اﻟﺜﺎﻧﻲ ﻣﻦ اﻷطﺮوﺣﺔ طﺮﯾﻘًﺎ ﻓﻌﺎﻻً ﻟﻨﺰع اﻷﻛﺴﺠﯿﻦ اﻟﮭﯿﺪروﺟﯿﻨﻲ اﻟﻐﺎزي (HDO) ﻟﻠﯿﻔﻮﺟﻠﻮﻛﻮزان (LG) واﻟﺬي ﯾﺆدي إﻟﻰ ﺗﻜﻮﯾﻦ ﻗﻄﻊ ھﯿﺪروﻛﺮﺑﻮﻧﯿﺔ ﻏﯿﺮ ﻣﺆﻛﺴﺠﺔ ﺗﺼﻨﻊ وﻗﻮد اﻟﻨﻘﻞ اﻟﺘﺠﺎري، وﺗﺤﺪﯾﺪاً اﻟﺒﻨﺰﯾﻦ واﻟﺪﯾﺰل ووﻗﻮد اﻟﻄﺎﺋﺮات اﻟﻨﻔﺎﺛﺔ. ﺗﺸﺘﻤﻞ اﻟﻌﻤﻠﯿﺔ اﻟﻤﻮﺿﺤﺔ ﻋﻠﻰ HDO ﻟﺘﯿﺎر ﻣﺒﺨﺮ ﻣﻦ LG اﻟﻤﺬاب اﻟﺬي ﯾﺰﯾﺪ ﻋﻦ 5% ﻣﻦ ﻣﺤﻔﺰات Ni-CeO2 ﺑﯿﻦ 100 درﺟﺔ ﻣﺌﻮﯾﺔ إﻟﻰ 500 درﺟﺔ ﻣﺌﻮﯾﺔ. ﻟﻘﺪ وﺟﺪ أن ﺣﻤﻞ اﻟﻤﺮﻛﺒﺎت اﻷﻟﯿﻔﺎﺗﯿﺔ ﯾﺼﻞ إﻟﻰ ﻗﯿﻢ ﺗﺘﺮاوح ﺑﯿﻦ 68.1% و75.3% ﻋﺒﺮ ﻧﺎﻓﺬة درﺟﺔ اﻟﺤﺮارة اﻟﻤﺪروﺳﺔ. وﺑﺎﻟﻤﺜﻞ، ﺗﺒﻘﻰ أﺟﺰاء اﻟﻤﺮﻛﺒﺎت اﻟﻌﻄﺮﯾﺔ ﺿﻤﻦ 13.9-%8.1%. ﺗﺸﻤﻞ اﻟﻤﺮﻛﺒﺎت اﻷﻟﯿﻔﺎﺗﯿﺔ اﻟﺮﺋﯿﺴﯿﺔ اﻟﻤﺮﺻﻮدة رﺑﺎﻋﻲ دﯾﻜﺎن، دودﯾﻜﺎن، أوﻛﺘﺎن، ودﯾﻜﺎن. ﯾﻈﮭﺮ اﻟﺒﻨﺰﯾﻦ اﻟﻤﺆﻟﻜﻞ ﺑﻜﻤﯿﺎت ﻣﻠﺤﻮظﺔ. ﺗﻢ رﺳﻢ آﻟﯿﺎت إدارة HDO ﻣﻦ ﺧﻼل ﺣﺴﺎﺑﺎت ﻧﻈﺮﯾﺔ اﻟﻜﺜﺎﻓﺔ اﻟﻮظﯿﻔﯿﺔ (DFT). أدى اﺳﺘﺨﺪام ﺣﻤﻮﻟﺔ 10% ﻣﻦ اﻟﻨﯿﻜﻞ إﻟﻰ ﺗﻘﻠﯿﻞ اﻟﻤﺴﺎﺣﺔ اﻟﻨﺴﺒﯿﺔ ﻟﻠﻤﺮﻛﺒﺎت اﻷﻟﯿﻔﺎﺗﯿﺔ ﺑﺸﻜﻞ طﻔﯿﻒ. وﺗﺒﻘﻰ ﻟﻤﺴﺎﺣﺔ اﻟﻤﺠﻤﻌﺔ ﻟﻠﻤﺮﻛﺒﺎت اﻟﻤﺆﻛﺴﺠﺔ أﻗﻞ ﻣﻦ 10% ﻓﻲ ﺟﻤﯿﻊ درﺟﺎت اﻟﺤﺮارة. ﯾﺴﺘﻠﺰم ھﺬا اﻻﻛﺘﺸﺎف ﻗﺪرة HDO اﻟﻌﻤﯿﻘﺔ ﻟﻠﻤﺤﻔﺰ اﻟﻤﻨﺘﺸﺮ وﯾﻔﺘﺢ ﻣﻜﺎﻧًﺎ ﻣﺒﺎﺷﺮً ا ﻟﻼﺳﺘﺨﺪام اﻟﻔﻌﺎل ﻟـLG ﻓﻲ إﻧﺘﺎج اﻟﻮﻗﻮد. ﺑﺸﻜﻞ ﻋﺎم، ﯾﺆﻛﺪ ھﺬا اﻟﺒﺤﺚ ﻋﻠﻰ اﺳﺘﺨﺪام اﻟﻜﺘﻠﺔ اﻟﺤﯿﻮﯾﺔ اﻟﻠﺠﯿﻨﯿﺔ اﻟﺴﻠﯿﻠﻮزﯾﺔ، وﺗﺤﺪﯾﺪًا ﻧﻮاة اﻟﺘﻤﺮ، ﻛﻤﺼﺪر ﻗﯿﻢ ﻟﻠﻜﺮﺑﻮن ﻓﻲ ﻣﻔﮭﻮم اﻟﻤﺼﻔﺎة اﻟﺤﯿﻮﯾﺔ.
Recommended Citation
Higazi, Ala Hamid, "SELECTIVE PRODUCTION OF LEVOGLUCOSAN (LG) FROM PYROLYSIS OF DATE PITS AND ITS CATALYTIC TRANSFORMATION INTO TRANSPORTATION FUELS" (2023). Theses. 1301.
https://scholarworks.uaeu.ac.ae/all_theses/1301
