Latest Development in Hydrogen programme

at ONGC Energy Centre

D. Parvatalu

ONGC Energy Centre

parvatalu_d@ongc.co.in

IHFC, Mumbai 09.12.2019

Outline of Presentation

Hydrogen programme

OEC strategies

Copper-Chlorine and Iodine-Sulfur Processes

Current status

New Initiatives

Conclusion

ONGC Energy Centre

ONGC Energy Centre set up by ONGC is engaged in RD&D on clean

Energy Technologies

Hydrogen Generation

Uranium, Helium, Rare earths

Solar

Geo-Thermal

Bio-technology

Energy Storage

Energy Recovery

ONGC Energy Centre facilities are located at Delhi, Ahmedabad,

Dehradun and Panvel. Hydrogen facility is being set up at Vadodara

Thermo-chemical Hydrogen Generation

Water

&

Heat Thermochemical

Reactions

Copper – Chlorine Cycle

Iodine – Sulfur Cycle

Hydrogen generation through thermochemical splitting of water is the

focus

– Cu-Cl cycle - Lab scale metallic plant @ 25 lph capacity operational since

2016 based on a new process developed. Both national and international

patents for process granted. Scale up activities @12 MT/Year in progress.

– I-S cycle – Closed-loop in quartz system was established @5LPH Hydrogen

generation and operational since 2018; planning for scale up in metallic

system. Indian Patents granted for catalysts developed

– I-S cycle – Open-loop: Proof of concept in quartz system was established

and Pilot plant setup for H2SO4 production @10-12M.T is planned to be set up

at MRPL.

• Alternate means of Hydrogen generation: Initiated R&D on Sea water

electrolysis, High Temperature Electrolysis, photo-electrolysis, Bio-

hydrogen etc.

OEC Hydrogen programme

• Hydrogen storage: Hydrogen Storage using Colloidal gas Aphrons(CGAs)

and CGAs loaded with Metal hydrides

• Hydrogen applications Initiated activity to join ARCI-CGCRI led

consortium for development of PEM / SOFC technologies and SOEC with

CGCRI

• Development of various support systems:

H.T-H.P corrosion Test facilities for selection of Materials

MoC for reactors, other process gadgets etc.

Molten salt system for Solar thermal storage for high temperature

reactions,

Electrochemical and Ceramic Gas separation membranes

H2S, SO2, H2, Cl2 gas sensors etc.,

Sources of fabrication in progress with collaborative approach

Development of Energy Storage devices, Energy recovery for

application in Oil filed ETP systems in progress

Hydrogen programme

Implementation Strategy

1. Collaborations with Centers of Excellence in India

to establish proof of concept

2. Lab scale Engineering Experiments using

indigenous resources

3. Heat source, Materials, Sensors, Membranes etc.,

development

4. Collaborative Consortium

5. Indigenous Vendor development

6. Scale up decisions

7. Pilot scale demonstration

Work

Execution

Strategy

• Indigenous Technology development for hydrogen generation at

mass scale

All Efforts Leading to

Hydrogen Generation Ecosystem-

Integrated Approach

Studies on integration of Heat

source with Cu-Cl cycle

Studies on alternative approaches

to reduce heat requirement to I-S

cycle

Studies on alternative approaches

to improve separation strategies in

Cu-Cl cycle

Simulation/ Modeling studies on

both cycles to improve process,

separations etc

Development of SOE / SOFC

systems

Development of other processes

and materials for H2 storage

Hydrogen Generation

options

MOC

Membranes

Alternate Electrodes

Heat Integration with CSP

Molten Salts

Pilot demo plants

Fuel Cells

Materials Development

H.T-H.P Corrosion

testing

Electrochem cell operation in continuous

mode

Scale up / Long term performance

of integrated metallic systems

Heat Source development and

integration

Affordable Catalysts

Membranes, electrodes,

development

Process improvement for Energy efficient

separations, Alternate options

etc. ,

Alternative means of Hydrogen generation

Current

focus

Simulations/modeling, Flow sheet development

Activities

Energy storage,

recovery system

development

The ICT-OEC Cu-Cl Cycle

OEC-ICT Closed-Loop metallic Facility: Cu-Cl cycle

H2 generation @25lph: Closed-loop operation in metallic system operational since 2015;

planning for 12 M.T / Y set up

30A Electrochemical Stack

• Designed / fabricated 30 A electrochemical stack comprising 4 anodes, Cu cathode and SnowPure® membrane at varying CuCl, HCl concentration and surface area ratio.

• Average cathodic current density of 200 mA/cm2 was achieved with 0.5 N CuCl, 3.5 N HCl, 1.1 V; Further studies are in progress.

Power

Supply

Electrochemical

stack

Pump

Pump

Catholyte

Trap

16

Molten salt circulation

Using vacuum

Using high temperature pump

Molten salt recirculation system

a)

Classical

b)

Electrochemical HI Decomposition 500oC

H2SO4 Decomposition 900oC

1) Reactive

Distillation

2) Extractive

Distillation

3) Electro Electro-

Dialysis

iii) Catalytic

Membrane Reactor

ii) Electrochemical

Iodine-Sulfur Cycle i)Catalytic

Bunsen Reaction 120oC

H2S Incineration

L-L separation

iv) Metal Sulfate

decomposition

I2 + SO2 + 2 H2O → H2SO4 + 2 HI ΔG= -41 KJ / M; ΔH= - 216 KJ / M

2 HI → H2 + I2 ΔG= 24 KJ/M; ΔH= 12 KJ/M

H2SO4 → H2O + SO2 + ½ O2 ΔG=-137 KJ/M; ΔH=271 KJ/M

4) Electrolytic

decomposition

Closed-loop Experimental facilities at IIT-D

H2 generation @5lph: Closed-loop operation in quartz / glass set operational since

2018; planning for scale up in metallic facility

Refinery

H2S production

Conversion to SO2 / SO3

Reduction to S

Sold to H2SO4 manufacturers

H2SO4 to market

2HI I2

2HI H2 + I2

450°C

HEAT

2HI + H2SO4 I2 + SO2 + 2H2O

120°C

WATER

HYDROGEN

HEAT

x

New generation Sulfur recovery process is

a value addition to Refinery

OEC-IIP Open-loop Experimental facility: IIP, Dehradun

Proof of concept in quartz / glass set up completed; planning for scale up in metallic facility to produce

H2SO4 @10-12MT/day at MRPL

H2S incinerator

CSMCRI developed cation-exchange

membrane

Indigenous Cation Exchange Membranes

bear excellent mechanical, thermal,

oxidative and acid-base (20 M H2SO4 or

NaOH) stabilities.

Membrane Water

content (%)

Ion-exchange

capacity (meq./g)

Conductivity

(S cm-1)

Nafion 117 41.6 0.90 9.56×10-2

SCP-13 32.4 1.19 7.35×10-2

Comparative Properties of Nafion and Indigenous CEM

NafionTM and Indigenous Membrane

Polarization Studies performed at BARC

LSV curves for anodic Cu+ oxidation and cathodic hydrogen evolution reaction @ 50

mvs-1 under the experimental conditions described in previous slide

Conclusion: The performance of Nafion-117 and ONGC membrane are almost

equivalent for CuCl/HCl electrolysis

Laboratory setup @ ICT Recently received CGCRI

developed membranes

Permeation cell component:

Membrane –Ceramic, Gasket –Silicone,

Support- Acrylic

Performance evaluation of gas separation membranes

20

Permeation cell component:

MoC: SS Schematic of laboratory setup @ CGCRI

Preliminary results on gas separation are encouraging

Corrosion Testing System

Furnace lid

Furnace

N2 gas inlet

Quartz stand

To scrubbing

Salt level

Si3N4 sample

Different materials screened

Sr.

No.

Suggested materials for

corrosion study

Status Other materials tested

Bare Materials Coating candidates

1. Hastelloy C-276 √ Monel 400 SiC Alumina/C-276

2. Inconel 600 √ Nickel 200 Haynes-214 YSZ/C-276

3. Inconel 690 √ Nickel 201 Hastelloy B Yttria/C-276

4. Inconel 625 √ Inconel 718 Ti alloys

(Ti-Gr-2, 5 and 7)

Chromium Titania/

C-276

5. 18Cr-8Ni √ Inconel 800 Zr alloys

(Zr-702, Zr-705)

Chromium oxide/

C-276

6. Alloy 400 X Inconel 825 Nichrome C-2000/C-276

7. Alloy 600 √ Tantalum Hastelloy C-22 Alumina+YSZ/C-276

8. 9Cr-1Mo √ Ti6Al4V Hastelloy C-2000

9. C22 √ Titanium (99%) Si3N4

10. Alloy 405 X Nimonic 80A NbSiC

Nilcra-Zirconia

Conditions: Reactant: Solid CuCl, Temperature: 530°C, Static condition, Exposure Time: 100 h, Inert atmosphere

Evaluation of non-metallic materials

Sr.

No.

Weight loss

(g)

Corrosion

rate

mm/y

Visual

Observation

1 <0.0001 Insignificant

Smooth, even,

shiny surface;

undamaged 2 <0.0001 Insignificant

Sr.

No. sample Weight loss

(g)

Corrosion rate

mm/y

Visual

Observation

1 NbSiC <0.0001 Insignificant Presence of absorbed

salt after drying

2 N-Zr <0.0001 Insignificant Smooth, even, shiny

surface; undamaged

Si3N4

Conditions: Reactant: Solid CuCl, Temperature: 530°C, Static condition, Reaction Time: 100 h, Inert atmosphere

OEC and BITS-Goa are working on Electrochemical decomposition of HI an

alternate route to HI section in I-S cycle

New Approach: Electrochemical Decomposition of HI

From elementary cell …

Cell : tri layer ceramic 200-300mm, where electrochemical reactions occur

Interconnector : metal distributing electrons and mechanical support occur

Cathode

Électrolyte

Anode

Demi-

interconnecteur H2O H2

O2

O2-

e-

e-

e-

Demi-

interconnecteur e-

H2O H2

O2

+

-

2 main difficulties : Ceramic metal assembly Leak tightness

to a stack

OEC and CGCRI have initiated

work on “LSCF-based novel

composite cathode, Fabrication of

SOFC short stack using single cells

to try on 3kV cell”

New Initiatives: Development of SOFC / SOEC

Sensors Development:

• OEC in association with BARC has initiated development of sensors

for H2S, SO2 for application in various ONGC Assets

• Preliminary studies at ONGC, Uran plant gases are encouraging

• OEC is in the process to develop H2 and Cl2 sensors developed by

IGCAR

New Initiatives: Development of Sensors

H2S sensor based on SnO2: CuO thin films H2 sensor based on Pd films on Pt-100

Conclusions

Indigenous Cu-Cl closed loop process has been developed and patented in

India and 6 other countries viz., USA, Canada, Japan, UK, Korea and China

Cu-Cl process has been demonstrated at engineering lab scale and in the

process of scaling up to 12 MT / Y

I-S closed loop process has been developed, demonstrated and patented

(applied); in the process of scale up

I-S open-loop process has been established; in the process of scaling up. A

10-12 MT / day capacity H2SO4 plant is planned to be set up at MRPL

Indigenously designed and developed reactors, intermediate processes,

membranes, catalysts, test facilities etc., during the process.

Several Engineering / Material challenges are being addressed to make it

reliable and cost competitive.

Initiated R&D activity on hydrogen storage, application of Hydrogen using PEM

/ SOFC concepts

Thank You

all for kind attention

&

our collaborators for support