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33
AQUEOUS PHASE REFORMING OF SORBITOL WITH VALUE ADDED CHEMICALS PRODUCTION Name: Nur Fatin Dariah binti Mohamad Daud ID Number: 15668 SV: Dr. Mohammad Tazli bin Azizan

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Page 1: APR of sorbitol viva

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

Page 2: APR of sorbitol viva

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.

Page 3: APR of sorbitol viva

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).

Page 4: APR of sorbitol viva

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.

Page 5: APR of sorbitol viva

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.

Page 6: APR of sorbitol viva

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.

Page 7: APR of sorbitol viva

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).

Page 8: APR of sorbitol viva

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

Page 9: APR of sorbitol viva

Figure 2: The reaction pathways of sorbitol hydrogenolysis into hexane over Pt/NbOPO4(J. Xi et al., 2015).

APR of sorbitol

Page 10: APR of sorbitol viva

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

Page 11: APR of sorbitol viva

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.

Page 12: APR of sorbitol viva

Project Activities

Catalyst Preparation

Catalyst Characterization

Catalytic Activity Test

Figure 3: Project Activities Flow Diagram

Page 13: APR of sorbitol viva

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

Page 14: APR of sorbitol viva

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

Page 15: APR of sorbitol viva

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

Page 16: APR of sorbitol viva

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

Page 17: APR of sorbitol viva

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

Page 18: APR of sorbitol viva

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)

Page 19: APR of sorbitol viva

SEM10% Ni/Al2O3 0.5% Ca + 10% Ni/Al2O3 3% Ca + 10% Ni/Al2O3 5% Ca + 10% Ni/Al2O3Al2O3

50µm

100µm

Page 20: APR of sorbitol viva

H2-TPR

T =514ºC

Graph 6: H2-TPR Analysis for 10% Nickel/Alumina

Page 21: APR of sorbitol viva

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

Page 22: APR of sorbitol viva

Catalysts Reduction

Figure 6: Tubular Furnace Reactor

N2 Flow

H2 Flow

Page 23: APR of sorbitol viva

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

Page 24: APR of sorbitol viva

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

Page 25: APR of sorbitol viva

GCMS

Page 26: APR of sorbitol viva

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

Page 27: APR of sorbitol viva

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)

Page 28: APR of sorbitol viva

Catalytic Activity Test

• Conversion of Sorbitol:

• Unreacted sorbitol:

Page 29: APR of sorbitol viva

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

Page 30: APR of sorbitol viva

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.

Page 31: APR of sorbitol viva

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.

Page 32: APR of sorbitol viva

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

Page 33: APR of sorbitol viva

The End