Process Integrated Carbon Capture (CC) · AREA II-1/ IK-Gasification slide 2 Overview Carbon Capture (CC) in industrial processes Chemical absorption in amine solutions Mobile test

May 2012

Process Integrated Carbon Capture (CC)

Field Tests And Further Perspectives In Industrial Processes

S. [email protected]

M. Kleinhappl, J. Zeisler

Bioenergy 2020+ GmbH

Speaker: Markus Kleinhappl instead of

AREA II-1/ IK-Gasification

slide 2

Overview

■ Carbon Capture (CC) in industrial processes

■ Chemical absorption in amine solutions

■ Mobile test plant

■ Results of field-tests

■ Gas and Liquid analyses

■ Implementation strategies


slide 3

CC in industrial processesbasic concepts

Source: www.energieblog24.de: Schwarze Pumpe - Oxyfuel

Post combustionCC

OxyfuelCC

Process integratedCC


slide 4

CC in industrial processesbasic concepts

1.53Iron&Steel Production

45 - 230Integrated GasificationCombined Cycle

100 - 300Coal fired Power Plant

794.0Syn Natural Gas, SNG1102.2Fischer-Tropsch Fuel1135.0Methanole, MeOH

782.2Dimethylether, DME

kg CO2/GJ (LHV)

kg CO2reduction/kg product

Gasificationcoal, biomass

CO2-removal

(90%)

Products:

CHPFT-fuelsMeOHDMESNG

Iron making, others…

coal, biomass

Conversionstep

Process gas:

CO, CO2, H2, CH4, N2, H2O

H2S, HCN, NH3, dust

Fermentationbiomass, sewage

UpgradedProcess gas

CO –shift

Source: www.energieblog24.de: Schwarze Pumpe - Oxyfuel


slide 5

CC in industrial processesbasics

Ecological benefits■ Emission reduction and energy recovery■ Saving resources due to CO2 recycling

Procedural benefits■ Increase of calorific value■ Volume flow reduction ■ Decrease of CO2 partial pressure

Benefits in subsequent conversion steps(e.g. Catalytic conversion including complete recovery of sulphur)


slide 6

Chemical absorption in alkanolamine solutionsbasics

•Dissociation and ionization of CO2:

CO2 + H2O HCO3- + H+

•Protonation of alkanolamine:

RNH2 + H+ RNH3+

•Carbamate formation:

RNH2 + CO2 RNHCOO- + H+

-

2.500

5.000

7.500

0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 10,0

CO2 gas out Concentration [vol%]

spec

ific

Hea

t dem

and

[kJ/

kg]

DEA 30%Abs. p: atm.Des. p: 1,8 barDes. T: 116-118 °CGas flowrate: 15 - 17 m³/h, uscL/G ratio: 7.0 - 12.2 l/m³, uscTest duration of point: 3-5 h

Recovery applicationSynthesis gas upgrade

absorber

desorber

T2 T3T4

T5

20-40°C

100-120°C; 0-1bar

gas out: CO2 0-5%vol

CO2

PIRC

10-20°C

gas in: CO2 10-30%vol


slide 7

CO2-separation teststechnology & methods

Key-data of tests

à 200 - 400 h 115 - 300 l/h9 - 30 Nm³/h

Test durationSorbent flowGas flow

■ Redesign of a mobile CO2-separation unit for process gas

■ Reference and long term tests with different absorbent compositionsMonoethanolamine (MEA), Diethanolamine (DEA), MDEA+MEA-solutions, Industrial CO2/ H2S-removal solvents

■ Chemical analysis of gas and liquidsOnline gas analysis (main gas components, CO2 and H2S), additional gas measurement (periodically), CO2-loads (TIC), degradation products (HPLC)

■ Evaluation of chemical effectsDegradation products, capacity, corrosion, long-time behaviour

■ Evaluation and analysis of CC process dataSeparation efficiency, energy demand, sorbent capacity, control strategy


slide 8

CO2-separation testsselected results

75 - 95 %Separation rate, ηCC

Key-data of tests21 - 23 vol%CO2-conc., crude gas

1,8 - 2,5 baraDesorber - pressure200 - 433

175 - 300 h

115 - 300 l/h

9 - 30 Nm³/h

Number of cyclesTest durationSorbent flowGas flow

7 l/Nm³Liq-gas-ratio3.300 kJ/kg CO2

Spec. heat duty, qDes

90% Separation rate, ηCC

MEA 30%Best results

3,000

3,500

4,000

4,500

5,000

5,500

74 76 78 80 82 84 86 88 90 92 94 96

ℵCC, separation efficiency [%]

spec

. hea

t dut

y [k

J/kg

]

Desorption pressure: 1,8 barabs

CO2-concentration, crude gas: 21 -23 vol%

MEA 20%

MDEA/MEA 30%/20%

DEA 30%

MEA 30%

Constant gas conditions:■ No oxygen■ Dust < 1 mg/m³, usc■ H2S < 80 mg/m³, usc■ System overpressure 65 mbar


slide 9

Gas and liquid characterisationSampling procedure

PIFI

PIFI

cooling unit

pump activatedchar coal

flow rate display

silica gel

flow rate measurement

ball valve

control valve collection drain

impinger for inorganicparameters

safety flask

cooled double jacket flasksfor organic parameters

probe

heated filter

heated tube

ball valve

PIPIFIFI

PIPIFIFI

cooling unit

pump activatedchar coal

flow rate display

silica gel

flow rate measurement

ball valve

control valve collection drain

impinger for inorganicparameters

safety flask

cooled double jacket flasksfor organic parameters

probe

heated filter

heated tube

ball valve

Gas-sampling Liquid-analysis

CO2-Analyzer:• Total Inorganic Carbon (TIC)• Principle: stripping out CO2 with

phosphoric acid for infrared detection

Conductivity:• via conductivity cell

Degradation products:• HPLC


slide 10

CO2-separation testsAbsorption of H2S/HCN

Hydrogencyanide (HCN) MEA20%

0

2

4

6

8

10

12

S_1 S_2 S_3 S_1 S_2 S_3

[mg

HC

N/m

Hydrogensulfur (H2S) MEA20%

0,00

20,00

40,00

60,00

80,00

100,00

120,00

S_1 S_2 S_3 S_1 S_2 S_3

[mg

H2S

/m

before absorber before absorber

after absorber

after absorber

Hydrogencyanide (HCN) DEA20/30%

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

S_1 S_2 S_3 S_1 S_2 S_3

[mg

HC

N/m

20%

30% 30%

20% 30% 30%

Hydrogensulfur (H2S) DEA20/30%

0

10

20

30

40

50

60

70

S_1 S_2 S_3 S_1 S_2 S_3

[mg

HC

N/m

20% 30% 30%

before absorber

after absorber after absorber

before absorber

20%

30% 30%

MEA20% DEA30%

Complete removal of H2S and HCN with all tested solvents(MEA, DEA and MEA+MDEA-solutions)

Complete stripping of H2S in the desorption unit


slide 11

CO2-separation testsliquid analysis

32 - 470,15 – 0,1637,6 – 40,70,30 – 0,3172 - 75MEA20/MDEA30

18 - 260,06 – 0,158,5 – 18,70,27 – 0,3534 – 44,2DEA 30

38 - 550,28 – 0,3859 – 81,50,53 – 0,62115 - 132MEA 30

23 - 350,36 – 0,3952 - 570,55 – 0,6180 - 89MEA 20

[g/l]α [mol/mol Amin]c [g/l]α [mol/mol Amin]c [g/l]

ΔcCO2-lean sorbent – CO2-loadCO2-rich sorbent – CO2-load

■ Up to 400 h of operation no depletion in performance (spec. heat duty, efficiency)

■ Gas analyses via standardised methods CO2, CO, H2, CH4, impurities

■ Liquid analysis via HPLC-UVOxazolidone, HEIA, HEEDA, DI-UREA detection limit of 1 ppm

almost no degradation products found

CO2 load in used solvent solution:

min2.5 2.75 3 3.25 3.5 3.75 4 4.25 4.5

mAU

0

10

20

30

40

50

MWD1 A, Sig=195,4 Ref=400,100 (AMIN\SPIKE_PROBE_100%H2O_20111108_4WL 2011-11-08 13-38-21\039-0901.D)

2.6

72

2.8

58

3.1

38

3.9

98

4.2

54

MWD1 A, Sig=195,4 Ref=400,100 (AMIN\SPIKE_PROBE_100%H2O_20111108_4WL 2011-11-08 13-38-21\036-0601.D)

2.8

58

3.1

41

3.3

83

4.0

01

4.2

56

sample (blue line); sample + standard (red line)

e.g.: oxazolidoneEvaluation of degradation effects:


slide 12

Appendix –Blast furnace + CC + GuD-// CC combined cycle

Exhaust gas

ore, coke

Gas-turbine

Air

Gas-cooling

Gas treatment

steem150°C

; 4 bar

M

G

heat

G

Steem-turbine

CO2

CO2-lean process gas = fuel gas

Blast furnacegas

CC-plant

HRSG

from:

HRSGslagfurnaces…

e.g. to blast furnace

example:

Crude iron: 2,7 Mt/yCO2 separated: 0,75 Mt/yCC steam demand 160 MW

e.g. from air compressor


slide 13

Installation of the mobile plant


slide 14

Looking for further collaborations…….

■ For initiatives of plant manufacturers to realised these technology in industrial scal for production and energy (IGCC)

■ In general for material testing absorbent mixtures

■ Specific interests of gas characterisation and degradivecomponents; analyses can be performed

Thank You for Your kind attention!

May 2012

Process Integrated Carbon Capture (CC)

Field Tests And Further Perspectives In Industrial Processes

S. [email protected]

M. Kleinhappl, J. Zeisler

Bioenergy 2020+ GmbH

Documents

Process Integrated Carbon Capture (CC) · AREA II-1/ IK-Gasification slide 2 Overview Carbon Capture (CC) in industrial processes Chemical absorption in amine solutions Mobile test