SODIUM BOROHYDRIDE AS HYDROGEN CARRIER

Transcription

SODIUM BOROHYDRIDE AS HYDROGEN CARRIER
Prof. Dr. Bekir Zühtü Uysal
Department of Chemical Engineering & Clean Energy Research and Application Center
D
f Ch i l E i
i & Cl
E
R
h d A li i C
Gazi University, Ankara
Turkish‐German Conference on Energy Technologies, 13‐15 Oct 2014, Ankara
1
CONTENT
Introduction
Global Energy Outlook
Sustainability of Energy Supply
Distributed Energy Supply on Demand and on Spot
Hydrogen as Energy Carrier
Sodium Borohydride (SBH) as Hydrogen Carrier
SBH Production
Hydrogen production with SBH
y g p
Recycling Sodium Metaborate (SMB) to SBH
2
Global Energy Outlook
Fossil fuels have been the primary energy source so far.
BP Statistical Review of World Energy June 2014
•Fossil fuels will continue to be the primary energy source in the coming decades.
•Growth
Growth rate in global primary
rate in global primary energy consumption: +2.3%
energy consumption: +2.3%
•Currently, share of renewables: 5.3%
But, considering the increase in the TOTAL consumption of fuels by 2035, it is anticipated considering the increase in the TOTAL consumption of fuels by 2035, it is anticipated
•But,
that coal’s and oil’s relative shares will decrease and renewables will increase.
4
Sustainability of Energy Supply
LIFE SPAN OF FOSSIL FUELS
Reserves to Production (R/P, Yr)
250
227
200
136
150
YEAR
100
50
65.1
40.6
16
14
0
Crude Oil
Natural Gas
World
Kaynak:
BP Staticical World Review of Energy, June 2006
Türkiye petrol ve doğalgaz rakamları 2003 verisidir.
Turkeyy
Coal
With the fossil fuels
continuing to have the
greatest share in energy
portfolio in the coming
decades global warming
decades,
and
the
associated
challenges should be faced.
Mauna Loa Observatory in Hawaii y
400 ppm is exceeded!
Global CO2 emission values forecasted for 2035 are nearly double the 1990 level.
l d bl h 1990 l l
IEA’s 450 Scenario: The goal is to limit the global increase in temperature to 2°C by limiting
temperature to 2°C by limiting concentration of greenhouse gases in the atmosphere to around 450 parts per million of CO2.
7
ENERGY OUTLOOK ‐ Summary
•Not
Not every country is equally lucky to have enough fossil
fuel.
•Harsh
Harsh and ruthless attack on oil and natural gas
continues towards depletion of their reserves.
•Coal will continue to be one of the major primary source
of energy; though its share will tend to decrease in favor
of renewables.
•Avoidance of global warming requires to increase the
share of renewables in energy generation.
8
STRATEGIC PLANNING FOR FUTURE
1) Rehabilitation and renovation of energy systems using fossil fuels and abatement of the damage to the environment.
‐ Improvement of combustion and gasification systems
‐ Reducing SO2, NOx, Hg and CO2 emissions
2) Development
Development and adaptation of renewable energy systems
and adaptation of renewable energy systems
‐ Hydroelectric
‐ Wind
 Suitable for distributed energy generation (DEG)
‐ Solar
‐ Biomass
3) Energy storage
‐ Use of H2 as energy carrier gy
 Suitable for distributed energy generation (DEG)
Distributed Energy Supply on Demand and on Spot
gy pp y
p
Distributed energy consists of a range of small‐scale and modular devices designed to provide electricity, and
modular devices designed to provide electricity, and sometimes also thermal energy, in locations close to consumers. They include renewable energy technologies (e.g., photovoltaic arrays, wind turbines, microturbines, reciprocating engines, fuel cells, combustion turbines, and steam turbines); energy storage devices (e.g., batteries and flywheels); and combined heat and power systems. Turkish‐German Conference on Energy Technologies, 13‐15 Oct 2014, Ankara
10
H d
Hydrogen as Energy Carrier
E
C i
11
ROAD MAP
E
Energy storage ‐
U
Use of H2 as energy carrier
f H2
i
13
HYDROGEN STORAGE
Physical Storage
Physical
Storage
1) Thick wall tanks (High pressure, very heavy, not very practical)
2) Metal hydride/carbon nanotubes/graphene canisters ( dso pt o capac ty
(Adsorption capacity limitation, difficulties associated with P & T variations)
tat o , d cu t es assoc ated t
& a at o s)
Difficulty involved led to Hydrogen‐on‐demand projects
3) Chemical storage
14
Sodium Borohydride (SBH) as Hydrogen Carrier
SBH can be used to produce i)) electricity (DC) using “Direct Sodium Borohydride Fuel Cell”
y( )
g
y
ii) hydrogen on demand. (Inception by Millenium Cell Inc.)
Hydrogen can then be used in
Hydrogen
can then be used in
1. fuel cells to generate electricity (DC)
2. internal combustion engines for power
3. combined heat and power systems
b dh
d
15
Why NaBH4 ?
Why NaBH
High hydrogen storage capacity
10.6 wt‐% H2
Storage &
shipping
Safely,
Solid (powder or pellet)
Alkaline solutions  pH 9
H2 production
Controllable catalytic hydrolysis
Hydrolysis energy
evolution
210 kJ/mol
Relatively less than those for other hydrides
Recycling or use of the hydrolysis product
NaBO2 can be recycled or used for the production of other valuable chemicals. Turkish‐German Conference on Energy Technologies, 13‐15 Oct 2014, Ankara
16/73
BORON
Türkiye has about 73% of world’s reserves.
Tincal ( Na2B4O7.10H2O )
Colemanite (2CaO.3B2O3.5H2O )
Ulexite (Na2O.2CaO.5B2O3.16H2O )
NaBH4 can be produced using these raw materials.
•
•
•
•
•
•
•
Ankara
A
k
İstanbul
Bandirma
Kestelek
Bigadic
Emet
İzmir
17/73
Hydrogen can be generated by hydrolysis of sodium borohydride. Turkish‐German Conference on Energy Technologies, 13‐15 Oct 2014, Ankara
18
SBH Production
Commonly used INDUSTRIAL
Commonly
used INDUSTRIAL sodium borohydride
sodium borohydride production production
processes;
1 Rohm&Haas Process,
1.
Process
4NaH + B(OCH3)3 → NaBH4 + 3NaOCH3
2. Bayer Process,
4MgH2 + Na
+ Na2B4O7 → 2NaBH4 + 4MgO + B
+ 4MgO + B2O3
19
OUR
R RELA
ATED W
WORK
ALTERNATIVE METHODS FOR SBH PRODUCTION
PRODUCTION OF SODIUM BOROHYDRIDE BY
HYDROGENATION OF ANHYDROUS BORAX AT HIGH
TEMPERATURE AND PRESSURE IN THE PRESENCE OF
MAGNESIUM
4 Mg+ 4 H2 + Na2B4O7  2 NaBH4 + 4 MgO + B2O3
Go = -307 kJ/mol NaBH4
The highest yield was obtained as 93 % in the h h h
ld
b
d
h
experiment performed at a reactor temperature of 550oC, reaction time of 4 hours, the hydrogen oC and ggas given to the reactor at 25 bar and 400
g
using a stoichiometric mixture of anhydrous borax with 200 % excess amount Mg. Turkish‐German Conference on Energy Technologies, 13‐15 Oct 2014, Ankara
20
Hydrogen production from Sodium Borohydride
OUR
WORK
R RELA
ATED W
HYDROLYSIS
HYDROLYSIS rxn
Sodium borohydride should be kept in
alkaline medium (e.g. NaOH solution) in order
to be stable for a long time.
EFFECTS OF CATALYST (Pt R Rd)
•CATALYST, (Pt, Ru, Rd)
•NaOH CONCENTRATION, •TEMPERATURE, Çözelti
Çözelti Kabı
Manyetik Karıştırıcılı Isıtıcı
Peristaltik Pompa
Reaktör
Hidrojen Toplama Kabı
Pt-%0,5
T=20 oC
NaOH : 10 wt
%
wt-%
Efficiency  64-85%
21
Recycling SMB to SBH
22
OUR
R RELA
ATED W
WORK
RECOVERY OF SODIUM BOROHYDRIDE FROM SODIUM METABORATE at HIGH TEMPERATURE AND HIGH HYDROGEN PRESSURE
N BO2 + 2Mg
NaBO
2M + 2H2 → NaBH
N BH4 + 2MgO
2M O
∆G = -342,02
342 02 kJ
Effect of additional Na sources:
2NaBO2+4Mg+NaOH+4H2→2NaBH4+4MgO+Na2O2
NaBO2+Mg + Na2CO3 + 2H2 → NaBH4 + MgO + CO2 + Na2O2
At 650ºC, 28 atm hydrogen pressure and with hydrogen fed to the
reactor at 400ºC, 43,1 % product yield was achieved by using a
stoichiometric mixture of NaBO2 and Mg,
Mg 34 % yield was achived by
using 100 % excess Mg, 46 % yield was achieved by using 100 %
excess Mg and carbon coated platinum and
53,3 % yield of sodium
borohydride was achieved by using 200 % excess Mg and 100 %
excess NaOH.
23
OUR
R RELA
ATED W
WORK
Recycling
Sodium Metaborate Via Boric Acid
Recycling Sodium Metaborate Via Boric Acid
XRD analysis of the solid product
Purity achieved : 100%
Purity achieved : 100%
24
CONCLUSIONS
Sodium borohydride is a suitable chemical for hydrogen on demand and thus for distributed
hydrogen on demand and thus for distributed energy generation on demand and on spot.
Though, efforts should continue to lower its cost.
25
SOLAR‐‐HYDROGEN
SOLAR
HYDROGEN‐‐ELECTR
ELECTRIICITY ENERGY CYCLE
TY ENERGY CYCLE
SOME O
OF OUR RELATED
D WORK
K
Bekir Zühtü UYSAL
Bekir Zühtü UYSAL*, *, Mecit
Mecit SIVRIO
SIVRIOĞLU
ĞLU, , Ufuk GÜNDÜZ ZAFER
Ufuk GÜNDÜZ ZAFER, , Ö. Murat DOĞAN
Ö. Murat DOĞAN, , İbrahim ATILGAN
İbrahim ATILGAN, , Timur AYDEMİR
Timur AYDEMİR, , Atilla BIYIKOĞLU
Atilla BIYIKOĞLU
26
SUPPORT OF STUDEN
NTS
INTERUNIVERSITY SOLAR CAR COMPETITION Gazi University’s team
INTERUNIVERSITY SOLAR CAR COMPETITION –
G iU i
it ’ t
27
II LIKE TO THANK TO MY COLLEAGUES IN CHEMICAL, MECHANICAL AND LIKE TO THANK TO MY COLLEAGUES IN CHEMICAL MECHANICAL AND
ELECTRICAL ENGINEERING DEPARTMENTS, AND OUR STUDENTS
WHO HAVE CONTRIBUTED TO THESE RESEARCHES. Prof. Dr. Ö. Murat Doğan
Ö
Prof. Dr. Ufuk Gündüz
Prof. Dr. Atilla Bıyıkoğlu
Prof. Dr. Mecit Sivrioğlu
Prof. Dr. Mecit Sivrioğlu
Prof. Dr. Levent Aksu
Assoc. Prof. Dr. Timur Aydemir
Assoc. Prof. Dr. Hüseyin Çelikkan
A t P f D İb hi At l
Asst. Prof. Dr. İbrahim Atılgan
Asst. Prof. Dr. A. Elif Sanlı
Dr. İlknur Kayacan
Fethiye Bideci (B.Sc., M.Sc.)
y
(
)
Ece Olgun (B.Sc., M.Sc.)
Şafak Doğu (B.Sc., M.Sc.)
28
THANK YOU
[email protected]
TEMENAR’s web page: www.temenar.gazi.edu.tr
29

SODIUM BOROHYDRIDE AS HYDROGEN CARRIER

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