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AQUEOUS PHASE REFORMING OF SORBITOL WITH
VALUE ADDED CHEMICALS PRODUCTION
Name: Nur Fatin Dariah binti Mohamad DaudID Number: 15668
SV: Dr. Mohammad Tazli bin Azizan
Background Study• Biomass is a highly useful and renewable resource
countless potential for utilization as a basis for hydrogen production (Florin & Harris, 2007).
• Sorbitol is selected as one of the 12 biomass derived molecules that can be used for the production of fuels and chemicals.
Background Study• Transformation of sorbitol into hydrocarbons is currently
considered to be as a promising technology for the production of second-generation biofuels.
• A new pathway was proposed for biofuels production. It isthe direct transformation of biomass derived-product,which is sorbitol into liquid hydrocarbon in aqueousmedium over a heterogeneous acid-metallic bi-functionalcatalyst (Carol et al., 2013).
Problem Statement• Liquid biofuels used most widely for transportation are ethanol and biodiesel.
• Both of them are oxygenated fuels with molecular compositions that differ from the petroleum-
derived fuels today.
• However, these biofuels do not meet the criteria required for transportation fuels (to burn cleanly
and have high energy densities for efficient storage at ambient conditions)
• Therefore, it is desirable to utilize biomass to generate liquid fuels that met the physical quality
requirement.
• An expensive energy-consuming distillation step to purify ethanol can be eliminated as HC are
able to separate spontaneously from the water solvent during biofuels production process.
• Motivate the researches to develop technologies for processing biomass to biofuels.
Objectives
To conduct aqueous phase reforming of sorbitol to identify the value added chemical
produced.
To synthesize and characterize Ni/Al2O3catalyst promoted by Ca for APR of sorbitol.
1.
2.
Scope of StudySetting up an experimental work to prepare Ni/Al2O3 catalyst using incipient wetness
impregnation method.
Studying the effect of promoting the catalyst with metal (Ca).
Characterization of catalysts using TGA, SEM, SEM-EDS, and H2-TPR.
Evaluating the performance of catalysts.
Identification of value added chemical produced with its product distribution.
APR of sorbitol
1933
•Zartman & Adkins attempted to convert various sugars and polyols dissolved in ethanol on a CuCrOx catalyst in the presence of H2 & observed the formation of water, diols and triols.
•Hydrogen consuming.
1958
•Clark proposed the synthesis of glycerol from lignocellulose-derived sorbitol using the nickel-based catalyst in a basic environment.
•He observed the formation of shorter polyols.
1986-1996
•Montassier,Giraud et al studied the transformation of sorbitol and glycerol in an aqueous phase on supported metal catalysts, under hydrogen pressure.
1989
•Montassier et al. proposed the first mechanism for the sorbitol transformation in aqueous phase on a Raney Cu catalyst, then applied to a Ruthenium/Carbon (Ru/C) catalyst and then Ru/C modified by sulphur in the presence of hydrogen.
2000
•The transformation of polyols in aqueous phase has been focused on the production of hydrogen and alkanes using APP (Aqueous Phase Processing)
2004
•APR of sorbitol was oriented to the production of alkanes using a bi-functional catalyst combining a metal phase (platinum) on an acid support (silica-alumina).
Figure 1: Reaction pathways for the production of alkanes from sorbitol over catalysts with metal and acidic components (Huber et al., 2014).
APR of sorbitol
Figure 2: The reaction pathways of sorbitol hydrogenolysis into hexane over Pt/NbOPO4(J. Xi et al., 2015).
APR of sorbitol
Past Researches of APR sorbitolWho Title of Article Catalyst Preparation Products
Kirilin et al., 2002.Kinetic Modeling of Sorbitol Aqueous-Phase Reforming over Pt/Al2O3
Incipient wetness impregnation method.
Isosorbide
Qing Zhang et al., 2011.
Isoparaffin production by aqueous phase processing of sorbitol over the Ni/HZSM-5 catalysts : Effect of the calcination temperature of the catalyst.
Incipient wetness impregnation method.
Isoparaffin
Qi Zhang et al., 2012.
Aqueous phase reforming of sorbitol to bio-gasoline over Ni/HZXM-5 catalysts.
Incipient wetness impregnation method.
Bio-gasoline
Qing Zhang et al.,2014.
Production of liquid alkanes by controlling reactivity of sorbitol hydrogenation with a Ni/HZSM-5 catalyst in water.
Incipient wetness impregnation method.
Liquid alkanes
J. Xi et al., 2015.Production of hexane from sorbitol in aqueous medium over Pt/NbOPO4 catalyst
Incipient wetness impregnation method.
Hexane, Pentane
Table 1: Past Researches of APR sorbitol
Catalyst• Nickel catalysts have gained tremendous
attention because they are active inhydrogenation, hydro-treating and steamreforming reactions.
• The idea supporting nickel catalysts on highsurface area ceramic substrates like alumina is toincrease the surface area.
Project Activities
Catalyst Preparation
Catalyst Characterization
Catalytic Activity Test
Figure 3: Project Activities Flow Diagram
Key Project Milestone# Detail 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1 2 3 4 5 6 7 8 9 10 11 12 13 14
1 Selection of Project Topic
2Critical literature review of aqueous
phase reforming
3Requisition of chemicals and laboratory
apparatus
4Research methodology and Project
Activities
5Submission of Extended Proposal to
Supervisor
6 Proposal Defense
7 Project Work Continue
8 Submission of Interim Draft Report
9 Submission of Final Interim Report
10 Synthesis of catalyst
11
Characterization of catalysts and
evaluation of catalytic activity of the
catalysts
12 Submission of Progress Report
13 Pre-Sedex
14 Submission of Draft Report
15 Submission of Dissertation (soft bound)
16 Submission of Technical Paper
17 Viva
18Submission of Project Dissertation
(Hard Bound)
FYP 1 FYP 2
Legend Duration Interval FYP I Key Milestone FYP II Key Milestone
Table 2: Key Project Milestone
Incipient Wetness Impregnation (IWI) method
Preparation flow diagram
Catalyst Preparation
Aluminium Oxide Nickel (II) Nitrate Hexahydrate
Calcium ChlorideDehydrate
Magnesium NitrateHexahydrate
Stirring Drying CalcinationReduction
with hydrogen flow
Figure 4: Preparation flow diagram
Sample(s)Composition of
Al2O3:Ni:Ca:Mg
1. 10% Ni/γ-Al2O3 90 : 10 : 0 : 0
2. 0.5% Ca + 10% Ni/γ-Al2O3 89.5 : 10 : 0.5 : 0
3. 3% Ca + 10% Ni/γ-Al2O3 87 : 10 : 3 : 0
4. 5% Ca + 10% Ni/γ-Al2O3 85 : 10 : 5 : 0
5. 0.5% Mg + 10% Ni/γ-Al2O3 89.5 : 10 : 0 : 0.5
6. 3% Mg + 10% Ni/γ-Al2O3 87 : 10 : 0 : 3
7. 5% Mg + 10% Ni/γ-Al2O3 85 : 10 : 0 : 5
8. 0.5% Ca + 0.5% Mg + 10% Ni/γ-Al2O3 89 : 10 : 0.5 : 0.5
9. 5% Ca + 5% Mg + 10% Ni/γ-Al2O3 80 : 10 : 5 : 5
Catalyst Preparation
With addition of Calcium(greenish)
With addition of Magnesium(greenish-blue / turquoise)
Table 3: Composition of catalysts
Catalysts Characterization
ThermogravimetricAnalysis (TGA)
• To identify the catalysts’ thermal stability and composition.
• To know the calcinationtemperature of the catalysts
Scanning Electron Microscopy (SEM)
Characterization of nano-structure
To observe the real surface structures with
optimum contrast.
H2 Temperature Reduction Programmed
(H2-TPR)To distinguish the reducible species
existence, their interaction and degree of reducibility.
Figure 5: Equipment used to characterize the catalysts
TGA
Graph 1: TGA Profiles for 10% Ni/Al2O3
Graph 2: TGA Profiles for 0.5% Mg + 10% Ni/Al2O3
Graph 3: TGA Profiles for 3% Mg + 10% Ni/Al2O3
Graph 4: TGA Profiles for 5%Mg + 10% Ni/Al2O3
TGA
• The most suitable temperature for calcination is where the graph shows the weight loss starts to be
constant which is approximately at 500oC. Most of the research paper also used 500oC.
• Calcination is the process of subjecting a substance to the action of heat, but without causing some
change in its physical or chemical constitution.
• To drive off water, carbon dioxide and volatile constituent.
Graph 5: TGA Profiles for 0.5% Ca + 0.5% Mg + 10% Ni/Al2O3
(450-550ºC)
SEM10% Ni/Al2O3 0.5% Ca + 10% Ni/Al2O3 3% Ca + 10% Ni/Al2O3 5% Ca + 10% Ni/Al2O3Al2O3
50µm
100µm
H2-TPR
T =514ºC
Graph 6: H2-TPR Analysis for 10% Nickel/Alumina
H2-TPR
0.5% Ca497ºC3% Ca
(i) 376ºC(ii) 497ºC
5% Ca(i) 398ºC(ii) 497ºC
Reduction temperature used: 500ºC
Graph 7: H2-TPR Analysis for different Ca loadings on10% Nickel/Alumina
Catalysts Reduction
Figure 6: Tubular Furnace Reactor
N2 Flow
H2 Flow
Catalytic Activity Test
Constant VariableTemperature: 230oC
Pressure: 20 bar
Gas type: Nitrogen (N2)
Speed of rotation: 450 rpm @ 7.5 hertz
Duration: 1 hour
Concentration of sorbitol : 0.05 mol of sorbitol with 150 ml
distilled water
Manipulated variable Composition of catalysts
Responding variable The types of value added chemicals that are produced.
PREMEX Autoclave Reactor
Experimental Variables
Catalytic Activity Test
• Produce pungent smell
0.05 mol of sorbitolsolution
10% Ni/Al2O3 + sorbitol solution
0.5% Ca + 10% Ni/Al2O3
+ sorbitol solution3% Ca + 10% Ni/Al2O3
+ sorbitol solution5% Ca + 10% Ni/Al2O3
+ sorbitol solution
GCMS
HPLC Analysis
• HPLC Operating Conditions
HPLC equipment
Injection Volume: 30µL
Flow rate: 0.6 mL/min
Pressure: 48 bar
Temperature: 30oC
Mobile Phase: 0.005M of H2SO4
Detector: UV
Column: Eclipse XDB C18, 5 Agilent
Runtime: 35 minutes
Signal: 215 nm and above
Sorbitol Calibration Curve
Species Concentration (wt%)
Area (mAU*s) Retention time (min)
Sorbitol-1 (a) 1% 116.1097 4.168
Sorbitol-2 (b) 5% 242.14 4.169
Sorbitol-3 (c) 10% 339.2267 4.1
y = 2457.1x + 101.45
R² = 0.9809
0
50
100
150
200
250
300
350
400
0% 2% 4% 6% 8% 10% 12%
Are
a (
mA
U*
s)
Concentration of Sorbitol (wt%)
Area (mAU*s) vs Concentration (wt%)
Area
(mAU*s)
Linear (Area
(mAU*s))
(b)
(c)
(a)
Catalytic Activity Test
• Conversion of Sorbitol:
• Unreacted sorbitol:
Expected Product based on
Literature
• Based on the research study on the catalytic performance of aqueous phasereforming of sorbitol, it can be modified to produce a clean stream ofheavier alkanes consisting mainly of butane, pentane and hexane (Cortright,R. D. et al., 2002).
• It has been reported that Ni is one of the metals that favors the production of alkanes from polyols (sorbitol) to the fact that C-O bond cleavage is favored more than C-C bond cleavage over these metals.
Hexane Pentane Butane
Limitations
The malfunctioned equipment led to the
time consuming.
The catalysts were suggested to be reduced in the reactor before the catalytic activity test with
sorbitol is conducted.
Purified hydrogen is highly flammable.
Alternative way: The catalysts are reduced with
hydrogen flow tubular furnace reactor with
supervision.
Recommendations
1. A mixture of N2/H2 gases should be used to reduce the hazard.
2. To conduct the GCMS and HPLC analysis for all the standards solution that have
the potential to become the value added chemicals.
3. To use different catalysts to widen the study on the effect of APR of sorbitol.
4. To collect the gas product from APR of sorbitol that may has valuable product.
5. The catalysts residues after the APR of sorbitol should be kept for further study.
Conclusions
The main objectives of this project , to synthesize and characterize Ni/Al2O3 catalyst promoted by Ca for aqueous phase
reforming of sorbitol are achieved.
The characterization of the catalysts are conducted using few techniques which are TGA, SEM, and H2-TPR to know the
behaviour of the catalysts.
The catalytic activity test of APR of sorbitol is conducted with appropriate conditions.
The value added chemicals produced are identified from GCMS and HPLC analysis
The End