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A Novel Piperazine‐based Amine Solvent
for Flue Gas CO2 CapturePiperazine + 4-Hydroxy-1-methylpiperidine
YANG DU AND GARY T. ROCHELLE PAPER 3A, 3RD POST COMBUSTION CAPTURE CONFERENCE
SEP. 2015
1
Outline Background Find a blend good as Pz, but without solid precipitation
PZ/HMPD (4 Hydroxy 1 methylpiperidine) PZ/HMPD (4‐Hydroxy‐1‐methylpiperidine)
Thermal Degradation and Oxidationg
CO2 solubility, capacity, and solid solubility
CO2 rate
Amine volatility and synthesis
Conclusions2
Conclusions
Capacity & Rate of Aminesp y
3
Capacity & Rate of Aminesp y
αlean@PCO2* 0.5kPa αrich@PCO2* 5kPa
4
Common PZ blends offer good rate & capacity
B t th l t bilitBut poor thermal stability
5
HMPD is Best of 38 AminesClass Best Cons
Imidazoles (8) NH
N
CH3
Capacity
Piperidines (8) N
OH
Volatility2nd best
Morpholines (4) NO
OH
Capacity
Piperazines (4) N
N Stability
Acyclic amines (14)NH
CH3
OH
O
NH
CH3
Volatility
8
CH3O CH3
N CH3OH (pKa=9.1)
Solvent EvaluationPiperazine/Hydroxy-methyl-piperidine
(PZ/HMPD)(PZ/HMPD)
7
Thermal degradation at 175 °C, CO2 loadedg , 2
PZ/HMPD/1MPZ/HPD
8 10
Degradation of 2 m PZ/3 m HMPD @ 175 °CNHNHN CH3OH NH OH NNH CH3↔+ +
HMPD PZ HPD 1MPZ
NN CH3CH31,4‐DMPZ
9 11
HMPD resistant to Oxidation 70 °C, 98% O2+2% CO2, 2 2
10 14
CO2 Solubility in 2 m PZ/3 m HMPD805.E+6
158 C
70
75
5 E+4
5.E+5
e (Pa)
100 C (WWC)96 C
65
70
5.E+3
5.E+4
kj/m
ol)
pressure
40 C
20 C
Habs@1500 Pa is 68.5 kJ/mol
60
65
5.E+2
5.E+3
H abs(k
partial p
20 C
555.E+1CO2p
Open points: high P VLE
505.E+00 5 1 1 5 2 2 5 3
Solid points: WWCLines: semi‐empirical equation
11
0.5 1 1.5 2 2.5 3
CO2 (mol/kg H2O+Amine)
CO2 Capacity in 2 m PZ/3 m HMPD
25600 40 C
6400
12800
e (Pa)
1600
3200
pressure
400
800
1600
partial p
Capacity = 1.9 – 1.3
200
400
CO2p
Open points: high P VLE
p y= 0.6 mol CO2 kg
50
100
0 5 1 1 5 2 2 5 3
Solid points: WWCLines: semi‐empirical equation
12
0.5 1 1.5 2 2.5 3
CO2 (mol/kg H2O+Amine)
2 m PZ/3 m HMPD Solid Solubilitygood to 4oC
Solution
5 m PZ/5 m HMPD
5 m PZPZ 6H O ( )PZ.6H2O (s)
15
CO2 Absorption Rate in 2 m PZ/3 m HMPD by WWC
2 m PZ/3 m HMPD @40 C20
s) 80
6020
2.E‐6
/Pa m
2 s 80
5 m PZ @40 C
g' (m
ol/ 100
k g
2.E‐7100 1000 10000
14
PCO2* 40C (Pa)
Capacity & Rate of Amines
(μ=4.2 cP)
(μ=5 cP)
(μ=18 cP)
15
Volatility of PZ/HMPD, CO2 loaded
6.4 5 m PZ/2.3 m AMP
3.2 7 m MEA5 m PZ/5 m HMPD
1.6Pa)
2 m PZ/3 m HMPD
0.8P am(P
8 PZ
0.4 5 m PZ/5 m MDEA
8 m PZ
0.2
5 m PZ/5 m MDEA
50 500 5000CO2 partial pressure @40 °C 16
R
Slide 16
RGT6 make amine fonts largerRochelle, Gary T, 29/08/2015
Synthesis route to HMPD
Application: Pharmaceutical intermediate
y
Ethyl Acrylate (1)
Michael addition+2Methylaminey y y
DecarboxylationDieckmann condensation
(2) (3)
(4)
17
Synthesis route to HMPDy
$(1)
Michael addition+2
$2/kg
DecarboxylationDieckmann condensation
(2) (3)
(4)
HMPD: $20/kg
18
MEA: $2/kgPZ: $6/kg
Summary of amine propertiesSummary of amine properties
Amine 7 mMEA 2 m PZ/3 m HMPD 5 m PZ
kg’avg 4 4 10 1 12 1kg avg(mol/Pa m2 s * 10‐7)
4.4 10.1 12.1
Normalized 0 63 0 92 0 77Capacity (mol/kg)0.63 0.92 0.77
Tmax(C) 122 149 164max
Tmelting (C)(PCO2 = 100 Pa)
—— 4 18( CO2 00 a)Volatility (ppm)
(40 C, PCO2 = 500 Pa)30 16 5
19
Texas Carbon Management Program R h ll G M bRochelle Group Members
Yang DuYang Du [email protected]
20