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Minggu 10 – Termodinamika, Kinetika Reaksi dan Aplikasi

Teknologi Fotokatalitik untuk CCUS

Termodinamika, Kinetika Reaksi

dan Aplikasi Teknologi
Fotokatalitik Dr. Wibawa Hendra Saputera (WHS)
TK4039 Teknologi Fotoelektrokimia dan Fotokatalitik Prof. Dwiwahju Sasongko (DS)
Dr. Pramujo Widiatmoko (PW)
Dr. Hary Devianto (HD)
21 Maret 2022 Kadarsah Suryadi
KK SIK
FTI ITB- Teknik Industri - FTI ITB

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 Thermodynamics of Photocatalysis Processes 2

• In a photocatalytic reaction, the bottom of CB should be more

negative than the reduction potential of the reactant to be
reduced (Pred), while the top of VB is suggested to be more
positive than the oxidation potential of the reactant to be
oxidized (Pox). The difference between Pred and Pox is the overall
change in Gibbs Free energy (∆G) (Figure a and b).
• When Pred is more anodic than Pox, the ∆G is negative. Notably,
the partial ∆G in the steps of reduction and oxidation by e− and
h+ must be negative to drive a chemical reaction
• Reactions with both positive and negative ∆G values can be
driven by photocatalysis. For example, photodegradation of
organic compounds in the existence of oxygen is generally a
• When a photocatalyst fulfills the thermodynamic downhill reaction (Figure c), while water splitting and CO2
requirements for a particular redox process, the reaction reduction are thermodynamic uphill reactions with large
may take place and the rate of the reaction can be
positive change in ∆G (Figure d).
predicted by kinetics.
• Different kinetic models have been developed to evaluate
the photocatalytic activity, which generally involve the
formation and migration of electron–hole pairs, bulk and
surface recombination of electron–hole pairs, followed by
the oxidation and reduction reaction with reactants
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 Thermodynamics of Photocatalysis Processes 3

The photoinduced electrons in the CB and holes in the VB Thermal-induced electrons and holes in non-degenerated
are delocalized and can freely move in TiO2. The semiconductors follow the Boltzmann distribution, with
thermalization of lattice vibration makes them quickly their product being a constant:
relax to their corresponding quasi-equilibrium states,
forming electron and hole quasi equilibrium systems (e-
system and h-system). The chemical potentials of e- and
h-systems are the quasi-Fermi levels of electrons and where Eg is bandgap, n0 and p0 are concentrations of
holes. thermal-induced electrons and holes, respectively.

Under light excitation with energy greater than Eg, the

maximum thermodynamic driving force for electrons
and holes to induce photocatalytic reactions are
Ec and Ev are the energy level positions of the CB bottom
(CBB) and VB top (VBT); kB is the Boltzmann constant; T
is the thermal absolute temperature; n and p are
concentrations of electrons and holes, respectively; Nc
The ΔG of a single electron–hole can be formulated:
and Nv are the effective densities of states at CBB and
CBT, respectively.
Quasi Equilibrium: a thermodynamic process that happens slowly enough for the system to remain in internal physical (but not necessarily chemical) thermodynamic equilibrium.
A quasi Fermi level describes the population of electrons separately in the conduction band and valence band, when their populations are displaced from equilibrium.
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 Thermodynamics of Photocatalysis Processes 4

How do you convert Ag/AgCl reference electrode potential to NHE?

• The general equation for this conversion at any pH using Ag/AgCl
reference electrode is:
E(NHE) = EAg/AgCl + 0.059 pH + E°Ag/AgCl
For example, if the measured potential of our
electrochemical system –0.460V with respect
where E°Ag/AgCl = 0.1976 V at 25°C and EAg/AgCl is working potential.
to Ag/AgCl, what is the potential with respect
to NHE?
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 Kinetic of Photocatalysis Processes 5

Langmuir-Hinshelwood mechanism
(A), Eley-Rideal mechanisms (B) and
Mars-Van Krevelen mechanism (C)

Catalytic surface reactions mainly occur via three reaction mechanisms, i.e. Langmuir–Hinshelwood (L-H), Eley–Rideal (E-R)
or Mars Van Krevelen (MVK) mechanism.
1. L-H proposes that both reactants first adsorb onto the surface before a bimolecular reaction takes place. The vast
majority of catalytic reactions follow this mechanism.
2. E-R proposes only one of the reactants adsorbs onto the surface after which the other reactant interacts with the
adsorbed species directly from the gas–phase.
3. MVK mechanism proposes that the surface itself is an active part in the reaction: one reactant forms a chemical bond
with the catalytic surface forming a thin surface layer of metal–reactant (1a). The other reactant now directly reacts from
the gas–phase with the atoms from the chemically bonded reactant on the surface (1b).

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Kinetic model of Photocatalysis Processes 6

Photocatalytic pollutant degradation

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 Kinetic model of Photocatalysis Processes 7

Methyl orange

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 Kinetic of Photocatalytic Methyl Orange Degradation 8

Methyl orange

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Kinetic of Photocatalytic CO2 Reduction 9

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 Kinetic of Photocatalytic CO2 Reduction 10

Conversion: Yield:

Yield = (moles of desired product formed)/(moles that

would have been formed if there were no side reactions
Selectivity: and the limiting reactant had reacted completely

Yield (Theoretical) = amount of product that would be

formed if all the reactant were converted to the desired
product.

Yield (Theoretical) = ratio of the rate generation of a

desired product R (rR) to the rate of consumption of a
key reactant A (rA).

Yield = amount of desired product produced relative to

the amount that would be formed if there were no by
product and the main reaction went to completion.

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 P R O S E S C A R B O N C A P T U R E & U T I L I Z AT I O N 11

CCU
Memanfaatkan CO2 Capture untuk
METHANOL
menangkap CO2 dari gas buang
proses

CO2 yang ditangkap kemudian akan

FLUE GAS CAPTURED CO2 disintesis menjadi metanol
COAL METHANOL
CO2 CAPTURE
POWER PLANT SYNTHESIS

TREATED FLUE REJECTED CO2

GAS

Van-Dal, É.S.; Bouallou, C. Design and Simulation of a Methanol Production Plant from CO2 Hydrogenation. Journal of Cleaner Production 57(), 2013, 38-45.

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 Diagram alir CO2 to methanol secara umum 12

Purge
Gas recycle

Aliran umpan
Pemisahan Pemurnian
(CO2 captured) + Catalytic reactor Metanol
produk produk
Pereaksi

Data Input yang diperlukan dalam simulasi:

1. Aliran Umpan (laju alir, T, P, komposisi)
2. Spesifikasi katalis (Jenis dan sifat katalis)
3. Konfigurasi reaktor
➢ Termokatalitik
4. Kinetika reaksi
➢ Fotokatalitik
➢ Elektrokatalitik Data Output yang diperoleh dalam simulasi:
➢ Fotoelektrokatalitik 1. Kondisi operasi dan spesifikasi produk
2. Kebutuhan utilitas

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 T E K N O L O G I KO N V E R S I C O 2 M E N J A D I M E TA N O L 13

[1]. Rosental, M.; Fröhlich, T.; Liebich, A. Life Cycle Assessment of Carbon Capture and Utilization for the Production of Large Volume Organic Chemicals. Front. Clim. 2. 2020. https://doi.org/10.3389/fclim.2020.586199
[2]. Yuan, Z.; Eden, M.R.; Gani, R. Toward the Development and Deployment of Largescale Carbon Dioxide Capture and Conversion Processes. Ind. Eng. Chem. Res. 55, 2016. 3383–3419. https://doi.org/10.1021/acs.iecr.5b03277.
[3]. Mota-Martinez, M.T.; Hallett, J.P.; Dowell, N. Mac. Solvent Selection and Design for CO2 Capture – How We Might Have Been Missing the Point. Sustain. Energ. Fuels 1. 2017. 2078–2090. https://doi.org/10.1039/c7se00404d.
[4]. Wang, L.; Wang, L.; Zhang, J.; Liu, X.; Wang, H.; Zhang, W.; Yang, Q.; Ma, J.; Dong, X.; Yoo, S.J.; Kum, J.-G.; Meng, X.; Xiao, F.-S. 2018. Selective Hydrogenation of CO2 to Ethanol Over Cobalt Catalysts. Angew. Chem. Int. Ed. 57. 2018. 6104–6108. https://doi.org/10.1002/ anie.201800729.
[5]. Wang, Y.; Zhang, J.; Qian, Q.; Bediako, B.B. Asare; Cui, M.; Yang, G.; Yan, J., Han, B. Efficient Synthesis of Ethanol by Methanol Homologation Using CO2 at Lower Temperature. Green Chem. 21. 2019c. 589–596. https://doi.org/10.1039/C8GC03320J.
[6]. Khoo, H.H.; Halim, I.; Handoko, A. D. LCA of Electrochemical Reduction of CO2 to Ethylene. J. CO2 Util. 41. 2020. 101229. https://doi.org/10.1016/j.jcou.2020.101229.
[7]. Nabil, S.; McCoy, S.; Kibria, M.G. Comparative Life Cycle Assessment of Electrochemical Upgrading of CO2 to Fuels And Feedstocks. Green Chem. 23. 2021. 867–880. https://doi.org/10.1039/D0GC02831B
[8]. Hussin, F., Aroua; M.K. Recent Development in the Electrochemical Conversion of Carbon Dioxide: Short Review. AIP Conference Proceedings. 2019. 2124, p. 030017 https://doi.org/10.1063/1.5117139.
[9]. Trudewind, C.A.; Schreiber, A.; Haumann, D. Photocatalytic Methanol and Methane Production Using Captured CO2 from Coal-Fired Power Plants. Part I–a Life Cycle Assessment. J. Clean. Prod. 70. 2014. 27–37. https://doi.org/10.1016/j.jclepro.2014.02.014.
[10]. Kho, E.T.; Tan, T.H.; Lovell, E.; Wong, R.J.; Scott, J.; Amal, R. A Review on Photothermal Catalytic Conversion of Carbon Dioxide. Green Energy Environ. 2. 2017. 204–217. https://doi.org/10.1016/j.gee.2017.06.003.

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 PROSES CAMERE 14

Basis : Termokatalisis
• Memanfaatkan reaksi RWGS[1]
• Perbandingan H2/CO2 : 3 :1[2]
• Reaktor RWGS dan sintesis metanol
terhubung secara seri[1]
• Air yang terbentuk dari reaksi dapat
dieliminasi secara reaksi kimia[1]
• Kapasitas produksi : 100 kg metanol/hari
(skala pilot)[1]
• Katalis berbasis CuO-ZnO-Al2O3[2]
• Perolehan metanol mencapai 67-70%[2]
• Kekurangan : Deaktivasi katalis
berpengaruh terhadap selektivitas[1]

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 PROSES MITSUI 15

Basis : Termokatalisis

• Memanfaatkan teknologi dari Carbon

Recycling International (CRI) dan
Greenhouse gases-to-chemical resources
(GTR)
• Kapasitas produksi : 50 kg metanol/hari
(skala pilot)
• Menggunakan katalis berbasis Cu
terokidasi, Zn, Al, Zr, dan Si
• Umpan produksi berasal dari gas buang
produksi etilen

[1] Samiee, L.; Gandzha, S. 2019. Power to Methanol Technologies via CO2 Recovery : CO2 Hydrogenation and Electrocatalytic Routes. Rev Chem Eng. DOI: 10.1515/revce-2019-0012

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 PROSES MITSUI (2) 16

Basis : Elektrokatalisis dan Fotokatalisis

• Memanfaatkan CO2 yang berasal dari gas

buang industri petrokimia
• Kapasitas produksi : 100 ton metanol/tahun
(skala pilot)
• Mengkonsumsi 150 – 160 ton CO2/tahun
• Memanfaatkan proses fotokatalisis untuk
menghasilkan gas H2 dengan bantuan katalis
thin film TiO2 dan bahan baku air (efisiensi
kuantum 60%)
• Proses elektrokatalisis dibantu dengan
elektrokatalis berbasis Cu/ZnO dalam sebuah
packed bed reactor
• Konversi CO2 mencapai 82% dengan efisiensi
44% metana dan 24% etilena

[1] Green Car Congress. 2008. Mitsui Chemicals to Build Pilot Facility to Study Process for Methanol Synthesis from CO2. Available online : https://www.greencarcongress.com/2008/08/mitsui-chemical.html (Accessed on November 2021)
[2] Sabri, M.A.; Jitan, S.A.; Bahamon, D.; Vega, L.F.; Palmisano, G. 2021. Current and Future Perspective on Catalytic-based Integrated Carbon Capture and Utilization. Science of the Total Environment 790 1408081

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 PROSES CRI 17

Basis : Termokatalisis

• Memanfaatkan CO2 yang ditangkap dengan

absorpsi menggunakan pelarut amine
• Gas H2 diperoleh dari elektrolisis air
• Keuntungan: Profil panas lebih rendah dari
reaksi metanol konvensional, sehingga
penggunaan tube-cooled reactor sudah cukup
• Tube cooled reactor tidak perlu dipasang
secara seri untuk mencapai konveri tinggi
• Menggunakan katalis berbasis CuO dan ZnO

[1] Samiee, L.; Gandzha, S. 2019. Power to Methanol Technologies via CO2 Recovery : CO2 Hydrogenation and Electrocatalytic Routes. Rev Chem Eng. DOI: 10.1515/revce-2019-0012
[2] Sabri, M.A.; Jitan, S.A.; Bahamon, D.; Vega, L.F.; Palmisano, G. 2021. Current and Future Perspective on Catalytic-based Integrated Carbon Capture and Utilization. Science of the Total Environment 790 1408081

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 PROSES CRI 18

Carbon Recycling International (CRI) merupakan perusahaan pertama yang mengindustrialisasi integrated CO2 capture dan proses
konversinya menjadi metanol. Beberapa proyek berikut dikelola oleh CRI yang menghasilkan metanol yang digunakan sebagai bahan
bakar.

[1] Sabri, M.A.; Jitan, S.A.; Bahamon, D.; Vega, L.F.; Palmisano, G. 2021. Current and Future Perspective on Catalytic-based Integrated Carbon Capture and Utilization. Science of the Total Environment 790 1408081

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E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L L Y P R O V E N 19

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 E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L LY P R O V E N 20

✓ Carbon Recycling Internasional adalah sebuah perusahaan yang berkantor pusat di Iceland.
✓ Sejak tahun 2006 CRI telah mempelopori pengembangan teknologi yang diperlukan untuk
menghasilkan renewable e-methanol dari emisi karbon (Emission to Liquid) dan
meluncurkannya untuk membantu mitra mencapai proyek Carbon Capture, Utilization, and
Storage (CCUS) skala industri.
✓ CRI menawarkan desain pabrik Emissions-to-Liquids (ETL) standar dengan kapasitas produksi
metanol nominal 50.000-100.000 ton/tahun.

Pengoptimalan Teknologi Aplikasi Eksekusi Proyek Layanan selama Masa Proyek

❑ Feasibility & Partnerships
❑ Penaksiran CO2 and Aliran Energi
❑ Front end engineering and design
(FEED)
❑ Estimasi CAPEX & OPEX
❑ Lisensi teknologi Emissions-to-LiquidsTM (ETL)
❑ Maintenance and support
❑ Manajemen teknik, pengadaan dan konstruksi
❑ Troubleshooting
(EPCM)
❑ Operator training
❑ Rekayasa dan konstruksi
❑ Pengadaan dan pengadaan peralatan
❑ Pasokan katalis tervalidasi

❑ Final investment decision (FID) ❑ Instalasi

❑ Komisioning

Sumber: https://www.carbonrecycling.is/

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 E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L LY P R O V E N 21

▪ Liquid Wind (sebuah perusahaan asal Swedia)

mengembangkan, membiayai, membangun, dan
mengelola fasilitas untuk mengubah emisi karbon
dioksida dan green hydrogen menjadi bahan bakar
netral karbon yang berharga: e-Methanol, bahan
bakar cair yang efektif akan mendukung transisi ke
carbon neutral fuel, transportasi jalan dan industri
kimia.

▪ Bersama dengan konsorsium ahli teknis mereka,

Liquid Wind sekarang mengembangkan
FlagshipONE eMethanol project skala komersial
pertama mereka di Örnsköldsvik, Swedia dengan
kapasitas produksi e-methanol 50.000 ton/tahun.

Sumber: https://www.liquidwind.se/, https://bioenergyinternational.com/

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 E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L LY P R O V E N 22

▪ Kapsom sebuah perusahaan asal Nanjing, China.

▪ Dengan manajemen proyek Kapsom yang
efisien, klien dapat membangun seluruh pabrik
methanol dalam waktu 12 bulan.

Servis yang ditawarkan:

▪ Flexible Capacity -20,000TPY~1,500,000TPY
▪ High heat transfer coefficient– Heat transfer coefficient 20% ~ 30%
higher than tube type unit
▪ Smart Plant – Fully automatic operation
▪ Superior Equipment – ASME, TEMA standards
▪ Environment Frendly – Green Methanol Production Plant

Sumber: http://kapsom.com/
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 E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L LY P R O V E N 23

❑ Mitsubishi Power, Ltd. adalah penyedia

terkemuka dan inovator teknologi dan solusi
untuk sektor energi global.

❑ Sebuah konsorsium dengan Mitsubishi Power

Europe sebagai integrator sistem telah
membangun pabrik CO2 to metanol.

❑ Mitsubishi Power Europe berkantor pusat di

United Kingdom, Eropa.

Sumber: https://power.mhi.com/regions/emea/products/power-to-x/

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 E X I S T I N G P E N Y E D I A J A S A C O M E R C I A L LY P R O V E N 24

L&T Hydrocarbon Engineering adalah perusahaan rekayasa, fabrikasi pengadaan, konstruksi dan manajemen proyek asal India yang
menyediakan solusi “design to build" terintegrasi untuk seluruh Industri Hidrokarbon. L&T Hydrocarbon Engineering berpengalaman
lebih dari 3 dekade yang telah terbukti memiliki kemampuan yang didukung oleh digitalisasi. Perusahaan mematuhi norma kualitas
global dan standar Kesehatan, Keselamatan dan Lingkungan (K3L), memastikan keandalan dan pengiriman tepat waktu.

Business Verticals

❑ LTHE akan menjadi mitra manajemen rekayasa, pengadaan dan konstruksi untuk membangun pabrik percontohan CO2 ke Methanol
di Pembangkit Listrik NTPC, India. Penandatanganan kontrak telah dilakukan pada 20 Agustus 2020.
❑ Pabrik ini akan terdiri dari tiga sub-unit, yaitu penangkapan CO2 dari Gas Buang, produksi H2 dengan elektrolisis air dan konversi
katalitik CO2 dan H2 menjadi Metanol.

Reference: Wang, dkk. 2017. A Review of Post-combustion CO2 Capture Technologies from Coal-fired Power Plants. Energy Procedia

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 Project with PT Bukit Asam Tbk. 25

TERMOKATALITIK Simulasi dilakukan dengan bantuan piranti lunak ASPEN PLUS V10
dengan basis model fluida Non-Random Two Liquid (NRTL).

katalis Cu/Zn/Al/Zr
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 Project with PT Bukit Asam Tbk. 26

FOTOKATALITIK

Simulasi konversi CO2 menjadi metanol dengan menggunakan teknologi fotokatalitik menggunakan referensi dari Ahadzi, dkk. (2021).
Simulasi dilakukan dengan bantuan piranti lunak ASPEN HYSYS V10 dengan basis model fluida SRK-Twu
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 Project with PT Bukit Asam Tbk. 27

ELEKTROKATALITIK

Elektrolit : larutan KHCO3 20% berat

Katoda : Cu (tembaga), FE: 90%

Aspen Plus V10 digunakan untuk memodelkan dan mensimulasikan

konversi CO2 menjadi metanol melalui teknologi elektrokatalitik.
Metode properti yang digunakan adalah ELECNTRL

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 TERIMA KASIH

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