1

CCUS Status and Potential in the United Arab Emirates

Dr. Mohammad Abu Zahra Associate Professor – Chemical and Environmental Engineering

Coordinator of the Institute CCUS Research

2

Presentation Overview

• Introduction

• Masdar/ADNOC ESI CCUS Project

• Masdar Institute CO2 Capture and Utilization Research Projects

3

HIGH PER CAPITA CO2 EMISSIONS IN UAE

Sunday, April 16, 2017

0

5

10

15

20

25

30

35

40

45

Met

ric

Ton

s p

er

Cap

ita

Per Capita CO2 emissions UAE

• UAE has one of the highest per capita CO2 emissions in the world • This emissions are bound to increase due to expected economic development • Development of CO2 Capture and Utilization Technologies will encourage the

deployment CCS.

Source: United Nations Data

CO

2 E

mis

sio

ns

(Mtp

a)

Source: WWF, United Arab Emirates

Projected CO2 emissions Abu Dhabi

CO2 Gas Emissions in the UAE

4

• CO2 as an EOR agent has been endorsed: – Success of the ESI CCS Project and Rumaitha / Bab Injection are key to future

development.

• Changing landscape in Abu Dhabi with potential CO2 targets for field testing and development: – CO2 capture linked to ADNOC field demand and performance;

• Whilst preliminary, the EAA CCS Value Proposition study forecast a growing CO2 demand in the next 25-30 years, based on ADNOC estimations.

ABU DHABI CCUS: FUTURE POTENTIAL

5

ABU DHABI CCUS: VALUE DRIVERS

Strategic Gas

Demand

& EOR

Environmental

Commitment to

Abu Dhabi 30%

Clean Energy

CCS Global &

Regional

Leadership

This CCUS Project

Will enable future CCS Projects

CCS Projects

ADNOC AD

Government

CO2 capture and transportation

projects at $/MT

CO2 injection for EOR Increased oil

Recovery +

Domestic gas

availability

Gas Liberation

and Enhanced

Oil Recovery

(EOR)

Regulatory Framework

6

AL REYADAH: ADNOC-MASDAR (JV)

• Al Reyadah, a Joint Venture between Masdar (49%) and ADNOC (51%)

– The result of years of on-going collaboration between Masdar and ADNOC sparked by the inspiring vision of Abu Dhabi’s leadership

Al Reyadah is a pioneering initiative and a knowledge hub for Abu Dhabi and the region in CCS technology, and a working platform for future CCS projects

7

Al Reyadah – ESI Project Milestone

• April 2010: FEED completed for the proposed ESI CO2 capture facilities and pipeline.

• Nov 2011: Successfully completed CO2 pilot injection project at Rumaitha field.

• Jan 2012: Abu Dhabi’s 1st CCUS project based at ESI factory was announced.

• Nov 2013: Awarded to Dodsal Group with a EPC contract to build the CO2 compression & dehydration facilities including a 43 km pipeline.

• Jul 2014: Construction of the facilities and pipeline commenced.

• Nov 2014: Formally unveiled Al Reyadah “Abu Dhabi Carbon Capture Company”, middle east first specialized company focused on exploring and developing commercial scale projects for CCUS.

• Nov 2016: Al Reyadah launch, 1st CO2 at ADNOC fields.

8

ESI CCUS PROJECT TECHNICAL

OVERVIEW

9

• CO2 is generated through the Process of Direct Reduced Iron (DRI)

– Methane Gas is reformed to a H2 & CO Syn Gas

– Iron Ore (Fe2O3) is reduced to Iron (Fe) in reactors – producing CO2 and H2O waste

– CO2 is removed via a traditional MEA Amine Absorption System

– CO2 rich waste stream (>99% dry) is available for the CCS Project

CO2 FROM EMIRATES STEEL (ESI)

Fe2O3 + 3H2 → 2Fe + 3H2O

Fe2O3 + 3CO → 2Fe + 3CO2

10

ESI CCUS PROJECT TECHNICAL OVERVIEW

11

• Sized for 800,000 TPA CO2 (98% min purity) = 41.5 MMSCFD • LP Compression:

– Integrally geared 6 Stage Centrifugal Compressor (0 – 41barg)

• Mol Sieve dehydration system – Reduce water content to 20lb/MMSCF

• HP Compression: – Reciprocating 2 Stage Compressor (35 – 238barg)

• Custody Mass Transfer Meter – Coriolis Meter complete with Gas Chromatograph and Multiple

Moisture Analysers

• Utilities: – Electrical Substation transformers/switchgear for 25MW – Control Room & Maintenance Warehouse – Air system

CO2 COMPRESSION AND DEHYDRATION FACILITY

12

Al Reyadah Site

13

CO2 TRANSMISSION PIPELINE - LOCATION

14

Al Reyadah Business Model

15

Carbon Capture Utilization and Storage (CCUS)

CO2 Capture Technologies

• The development of novel capture systems and processes for post-combustion capture, hydrogen production and chemical looping.

• Multiple projects were established in collaboration with Siemens, MIT, Masdar Carbon and RTI.

CO2 storage, injection and monitoring

• Study the interactions between the injected CO2 and the brine saturated rock, geo-chemistry, geo-mechanics, and trapping phenomena during CO2 storage

• CO2 monitoring (GPS and INSAR)

• Collaboration with MIT, ADNOC, ADCO and PI

CCS Policies and Regulations

• Optimal CO2 regulation to Align CCS with EOR and CDM

• Energy Policy and Technology Strategy and scenarios

• Risk analysis, CCS economics and regulations

Importance for Abu Dhabi These activities contribute to the overall vision of Abu Dhabi to reduce GHG emissions. One of the approaches to reduce carbon emission is by the development and deployment of CCS technologies. The current R&D projects will encourage the deployment of CCS technology in UAE. Having the advantage of being an oil producing country, CCS in the UAE will serve to be an excellent candidate to allow for enhanced oil recovery.

Researchers Dr. Mohammad Abu Zahra

Prof. Toufic Mezher Prof. Mohamed Sassi Dr. Enas Nashf Dr. Ahmed Al Hajaj Dr. Khalid Al Ali Prof. Tariq Shamim Dr. Hosni Ghedira

Dr. I-Tsung Tsai Prof. Taha Ouarda

16

DEVELOPMENT OF NEW SORBENTS SYSTEMS FOR CO2 POST-COMBUSTION CAPTURE

• Started in September 2011

• Duration of 30 months

• Total budget: $ 650,000

• Objectives:

- Development and characterization of amine-

based solvents for short term post-combustion

capture application

- Developing CO2-binding organic sorbents for CO2

post combustion capture.

Faculty Dr. Mohammad Abu Zahra; Prof. T. Alan Hatton mabuzahra@masdar.ac.ae; tahatton@mit.edu

17

SOLVENT SCREENING

Name Structure

1 Monoethanolamine (MEA)

2 N-methyldiethanolamine (MDEA)

3 Diethanolamine (DEA)

4 2-amino-1-methyl-2-propanol (AMP)

5 Piperazine (Pz)

6 1-amino-2-propanol (1A2P)

7 2-amino-1-butanol (2A1B)

8 2-(methylamino)ethanol (2MAE)

9 2-(ethylamino)ethanol (2EAE)

10 2-(butylamino)ethanol (2BAE)

11 2-(tert-butylamino)ethanol (2TBAE)

12 2-amino-2-(hydroxymethyl)-1,3-propanediol (AHMPD)

13 2-(dimethylamino)ethanol (2DMAE)

14 1-dimethylamino-2-propanol (1DMA2P)

15 N,N-diethylethanolamine (DEEA)

NH2

OH

OHN

CH3

OH

OHNH

OH

CH3

CH3

NH2 OH

NH NH

CH3

OHNH2

CH3

NH2

OH

CH3NH

OH

CH3 NHOH

CH3 NHOH

CH3

CH3

CH3

NHOH

OH

NH2

OH

OH

CH3

N

CH3

OH

CH3

N

CH3

OHCH3

CH3

N

CH3

OH

16 3-dimethylamino-1-propanol (3DMA1P)

17 Isobutylamine (IBA)

18 Sec-butylamine (SBA)

19 Butylamine (BA)

20 N,N,N′,N′-Tetramethyl-1,3-propanediamine

(TMPAD)

21 3-(dimethylamino)propylamine (3DMAPA)

22 1,3-diaminopropane (DAP)

23 Hexamethylenediamine (HMD)

24 Diethylamine (DA)

25 Triethylamine (TA)

26 Hexylamine (HA)

27 Triethanolamine (TEA)

28 Isopropylamine (IPA)

29 Tert-butylamine (TBA)

30 Benzylamine (BA)

CH3

NCH3

OH

CH3

CH3NH2

CH3NH2

CH3NH2CH3

CH3

NCH3

NCH3

CH3

NH2NCH3

CH3

NH2NH2NH2 NH2

CH3NHCH3

CH3NCH3

CH3

CH3NH2

OH

N

OH

OH

CH3

CH3

NH2

CH3

CH3

NH2

CH3

NH2

18

HEAT OF ABSORPTION VS CO2 LOADING

50

60

70

80

90

100

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

-D

H (

kJ

/mo

l o

f C

O2

)

CO2 loading

tertiary amines

● primary/secondary amines

MEA

AMP Pz

DEA

MDEA

2EAE

TMPDA

3DMA1P

1DMA2P

2DMAE

2-ethylaminoethanol (2EAE)1-dimethylamino-2-propanol (1DMA2P)3-dimethylamino-1-propanol (3DMA1P)2-dimethylaminoethanol (2DMEAE) N,N,N′,N′-Tetramethyl-1,3-propanediamine (TMPDA)

50

60

70

80

90

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

-D

H (

kJ

/mo

l o

f C

O2

)

CO2 loading

MEA

MDEA

Pz

DEA

AMP

2EAE

2-ethylaminoethanol + MDEA ( : 5wt%/25wt%, : 10wt%/20wt%, :15wt%/15wt%)

2-ethylaminoethanol + 1-dimethylamino-2-propanol (1DMA2P)

(■: 5wt%/25wt%, ♦: 10wt%/20wt%, ●:15wt%/15wt%) 2-ethylaminoethanol + 3-dimethylamino-1-propanol (3DMA1P)

(■: 5wt%/25wt%, ♦: 10wt%/20wt%, ●:15wt%/15wt%) 2-ethylaminoethanol + 2-dimethylaminoethanol (2DMEAE)

(■: 5wt%/25wt%, ♦: 10wt%/20wt%, ●:15wt%/15wt%) 2-ethylaminoethanol + TMPDA

(■: 5wt%/25wt%, ♦: 10wt%/20wt%, ●:15wt%/15wt%)

TMPDA

3DMA1P

1DMA2P

2DMAE

19

ADVANCED SOLID SORBENT MATERIAL FOR POST-COMBUSTION CO2 CAPTURE

• Project Partners:

• Kick off in October 2011

• Duration of 48 months

• Total budget: $ 4,100,000

• Overall Objectives:

- Optimization and production scale-up of advanced MBS

materials in fluidizable form and development of

associated fluidized-bed process technology.

- Collection of critical process engineering data using

single-stage testing equipment to allow for a detailed

design of a bench-scale CO2 capture prototype based on

MBS materials.

- Demonstrate technical and economic feasibility of a

commercial embodiement of the MBS-based CO2 capture

process

• Masdar Institute tasks:

- Techno-Economic Evaluation of the advanced solid

material for the natural gas combined cycle power plant

case

- Evaluation of scale-up challenges and issues related to

the application for NG case

- Sorbent single-stage and bench scale long term testing

using flue gas from NGCC power plant

University of North Carolina

Pennsylvania State University

Sud-Chemie Inc

Unitel Technologies

Foster Wheelers USA

Faculty Dr. Mohammad Abu Zahra mabuzahra@masdar.ac.ae

20

Project Overview

Solid Sorbent technologies are being developed

as general replacements for amine-based CO2

capture as well as for niche applications that

can leverage specific advantages of these

technologies.

21

AMINO-FUNCTIONALIZED SILICA

Amine impregnation

Amines are filled into the pores of silica

Amine impregnation

(PEI, AMP, DEA...)

Silica substrates Solid adsorbent

Aminopropyltriethoxysilane (APTES)

22

AMINO-FUNCTIONALIZED SILICA

Amine grafting using

Aminopropyltriethoxysilane(APTES)

Amino functional groups are chemically attached to

silica substrate

23

ADSORPTION PERFORMANCE

Effect of temperature on the CO2 loading capacity: (A) PEI impregnated

precipitated silica (B) APTES-PS-70

0 20 40 60 80 100 120

0

20

40

60

80

100

120

140

160

180

200

CO

2 l

oad

ing (

mg/g

)

Temperature (o

C)

Pure CO2 at ambient pressure and heat equilibrium

Pure CO2 at 1 bar for 24 h

0

10

20

30

40

50

60

70

80

90

100

40 60 80 100 120C

O2 l

oad

ing (

mg/g

)

Adsorption temprature (oC)

24

TESTING AND EVALUATION OF CO2 CAPTURE AND UTILIZATION

• Overall Objectives:

• To evaluate the possible application of fly ash

and modified fly ash for capture and utilization

of CO2 from flue gas. The possible combination

of fly ash with rejected brine from desalination

plant for CO2 sequestration will also be

investigated.

• To carry out a detailed techno-economic

evaluation of the proposed ZCF based CO2

capture technology.

• Support ENGSL in the testing and evaluation of

use of caustic soda and sodium silicate

solution for capture and utilization of CO2 from

flue gas to produce soda ash and Amorphous

Precipitated Silica (APS).

Faculty Dr. Mohammad Abu Zahra Dr. Ahmed Al Hajaj

Total project budget: $ 900,000 Project Duration: 30 months Kick off: January 2015

25

DESALINATION AND REJECT BRINE

• 11 million m3/day of desalinated water

• Translating to approximately 22 million m3/day of

reject brine. (Ahmed et al, 2012)

• A large percentage of this is usually dumped into

the sea. (Ahmed et al, 2012)

Effects of Reject Brine

• Increases sea water salinity

– Harm to marine ecosystem

– Ultimately higher costs for operators

• Increases sea water temperature

– Reduced level of dissolved O2

Sunday, April 16, 2017

500

600

700

800

900

1000

1100

1200

1300

2005 2010 2015 2020 2025 2030 2035

Pe

ak M

IGD

Year

Water Supply and Demand in Abu Dhabi

Supply Capacity Demand

UAE Water Demand and Desalination Reject Brine

26

• Over 44 Mtpa of CO2 can be sequestered through baking soda

which is about 32% of UAE’s CO2 emissions of 167.6 Mtpa

Sunday, April 16, 2017

Incentives • Reduction of the High Per Capita CO2 Emissions1 • Possibility of Lower overall cost for treating brine and capturing CO2 • Proximity of Power Plants and Desalination Plants reduces logistic burden.

CO2 Utilization using Desalination Reject Brine: Potential

Brine(Na+) + CO2 + Catalyst NaHCO3 ( Baking Soda)

Brine & Amine

CaCO3 NaHCO3

Filtrate

Alkaline Solid Wastes Flue gas

CO2 Absorption Filtration Recovery

Clean gas

Amine

27

Sunday, April 16, 2017

PRECIPITATE YIELD AND SODIUM CONVERSION

• This observation is due to the amine reaction mechanism with CO2. • Precipitates observed only for the Tertiary and Sterically hindered amines

which react via the bicarbonate route • The amines without precipitate all react via the carbamate route

60%

21%

0%

10%

20%

30%

40%

50%

60%

70%

MEA DEA AMP MDEA PZ

Co

nve

rsio

n

Amine

Na Conversion at 0.6M NaCl and 30wt% amine

2.9

1.2

0

0.5

1

1.5

2

2.5

3

3.5

MEA DEA PZ AMP MDEA

Solid

Qu

anti

ty (

g/1

00

g So

lve

nt)

Amine

Precipitate Yield at 0.6M NaCl and 30wt% amine

SOLVENT SELECTION

28

CO2 ABSORPTION CAPACITY

Sunday, April 16, 2017

• Piperazine has the highest CO2 Capacity but is unsuitable for the process since it gives no precipitate.

• The presence of brine in the solvent resulted in higher CO2 capacities as a result of

• Precipitation effect in Tertiary and Sterically Hindered amines

• Carbamate Hydrolysis into Bicarbonate in the Primary and Secondary amines

SOLVENT SELECTION

0

0.2

0.4

0.6

0.8

1

1.2

MEA DEA AMP MDEA PZ

Mo

l CO

2/M

ol a

min

e

0 M NaCl

0.6 M NaCl

29

SOLVENT SELECTION SUMMARY

Amine Precipitate Yield CO2 Capacity Sodium

Conversion

MEA Low Medium Low

DEA Low High Low

AMP High High High

MDEA Medium Poor Medium

PZ Low High Low

Sunday, April 16, 2017

AMP is selected as the best solvent to replace ammonia in the Solvay Process due to its performance in all of the three criteria

SOLVENT SELECTION

30

Sunday, April 16, 2017

EFFECT OF BRINE CONCENTRATION ON NA CONVERSION

2.9

11.9

0

2

4

6

8

10

12

14

0.6M 1.8 M

g So

lid/1

00

g So

luti

on

Brine Concentration

Yield

0.88

0.94

0.5

0.55

0.6

0.65

0.7

0.75

0.8

0.85

0.9

0.95

1

0.6M 1.8 M

Mo

l CO

2/M

ol A

min

e

Brine Concentration

CO2 Capacity

60%

92%

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0.6M 1.8 M

Pe

rce

nta

ge

Brine Concentration

Sodium Conversion

• Higher Brine concentrations is beneficial for the process as it leads to higher

yields, CO2 capacity and Conversion

SENSITIVITY ANALYSIS

31

Friedel Salt

AMINE RECOVERY 2 – ULTRA HIGH LIME WITH ALUMINIUM PROCESS (UHLA)

• Recovers the amine by removing species bonded to it such as HCO3- and Cl-

• HCO3- is removed by Thermal desorption and Cl- removed by UHLA process

• In UHLA process,

4𝐶𝑎2+ + 2𝐴𝑙 𝑂𝐻 4−

+ 2𝐶𝑙− + 4 𝑂𝐻 −

→ 𝐶𝑎4𝐴𝑙2𝐶𝑙2(𝑂𝐻)12 ↓

• Friedel Salt is used as Anion Exchange in High Temperature environments

Brine/Amine

NaHCO3

CO2 H2O

Flue gas

Carbonation Filtration Heat

Clean gas

Amine/Water/Na+

Flash

UHLA Process

NaAlO2 + CaO

Friedel Salt

CO2 H2O

AMINE RECOVERY

32

DESORPTION RESULTS

Sunday, April 16, 2017

Temperature 80 C 100 C 120 C

CO2 Loading (Before) 0.89 0.86 0.85

CO2 Loading (After) 0.56 0.18 0.15

Cyclic loading 0.33 0.68 0.70

% CO2 Desorbed 37% 79% 82%

• The optimum desorption temperature is 100oC since increasing the temperature does not give any added advantage.

• Typical Regeneration Temperature is at 120oC and this has been reduced by 20oC resulting in energy savings for conventional Carbon Capture Process

𝐿𝑜𝑎𝑑𝑖𝑛𝑔 =𝑀𝑜𝑙 𝐶𝑂2

𝑀𝑜𝑙 𝐴𝑚𝑖𝑛𝑒

AMINE RECOVERY

0%

20%

40%

60%

80%

100%

0 10 20 30 40 50 60 70

% C

O2

Re

mo

ved

Time (Hours)

100 C

80 C

120 C

33

RESEARCH SPONSORS AND COLLABORATORS

Wednesday, February 18th, 2015

Collaborators:

Sponsors

34

Thank you Dr. Mohammad Abu Zahra

Associate Professor

Chemical Engineering

mabuzahra@masdar.ac.ae

+971 2 810 9181