Hydrogen or Syngas Generation using Plasma Technology · PDF fileHydrogen or Syngas Generation...

Hydrogen or Syngas Generation using Plasma Technology

Topsoe Catalysis Forum 2006Future Hydrogen Generation and Application

Albin Czernichowski, Mieczyslaw Czernichowski, Piotr Czernichowski,

and Krystyna Wesołowska

ECP – GlidArc TechnologiesFrance

www.glidarc-tech.com 2

XIV-XVII

XX- XXI


European Union of X – XI century:

Mieszko I, first historical prince of Poland and Dubravka,Bohemian princess, have given birth to Boleslaw I, king of Polandand his sister Swietoslava (Sygryda or Sigrid or Gunhild).

Swietoslava first married Eric VI of Sweden. They have given birth to Olof III Skötkonung, king of Sweden.

After Eric's death, she married Sweyn I Forkbeard, king of Denmark. From this second marriage she had five children, including Canute the Great, king of England, Denmark and Norway, as well as Harold II of Denmark.


Plasma Reactors (1959-81 and 1987-present)

• Free burning DC arcs (up to 1500 A)

• Wall-stabilized DC arcs (up to 800 A)

• DC plasma torches fed by rare gases , N2 or Steam

• Induction-Coupled High-Frequency (atm. pressure, 25 kW)

• Microwave (3 kW)

• Rotating DC arc

• High current circuit breakers

• Electro-burners (up to 1 MW)

• Controlled Arc

• Gliding arcs (GlidArc I, II and III) @ various configuration


Plasma Chemistry (related to Hydrogen or SynGas)

• CO2 CO + ½ O2

• Water shift of CO

• Steam reforming of CFC

• Upgrading of concentrated H2S

• Natural Gas pyrolysis, steam reforming or POX

• Direct upgrading of biogas (or other CH4 + CO2 mixtures)

• POX of various fossil or renewable liquid fuels


Some other technologies and processes

(related to our plasma chemistry)

• Compact plate reactor for high-pressure catalytic & exothermic processes (like Fischer-Tropsch syntheses or water-shift of CO into Hydrogen)

• Power supplying systems for large GlidArc reactors (multiple discharges)

concept

… several elements are already built and tested:

• single or multiple pipes (also inside the plates) of 14 to 60 mm dia. and of 1.4 to 4.8 m height

• real syngas generation and compression to more than 20 bars, etc …


How GlidArc I operates:


cold electric discharge, 5 – 25 kV, < 5 A, DC or AC, power from 0.05 to 50 kW

0.03 - 12 bar

enhances and stabilises exothermic processes via active catalytic species

bring active energy to endothermic processes

not cooled electrodes

any gas, vapour, droplets or dustaccepted

any initial feed temperature accepted

multiple-discharge/electrode system can be installed for a large scale

GlidArc I features:


GlidArc I reactors

GlidArc

product

Feed


GlidArc II • Mobile central electrode (500 – 10,000 rpm, at the mass potential) and a fixed knife-shape energized electrode

• Discharge does not depend on the gas flow-rate and velocity

• No needs to accelerate gas at the proximity of both electrodes

A CB


• No obligation to push the gas processed between the stages

• No restrictions between the stages for gas acceleration

• Quite compact reactor for large flows

Example:⇒ 3 * 5A * 2kV = 30 kW per stage

⇒ Putting 4 stages 120 kW

⇒ Reactor diameter ~ 0.3 m, height ~ 0.5 m, volume ~ 0.03 m3

⇒ Can process ~ 2400 m3/h of gas


3

1

7

4

2

5

6

GlidArc III

1 Gas A 6 Mass electrode

3 HV electrode 7 HV insulation

4 Gas B

5 Discharge space


Plasma Chemistry related to Hydrogen or SynGas

CO2 CO + ½ O2 Endothermic

and then the water shift: CO + H2O = H2 + CO2

• Futuristic way of CO2 recycling or upgrading

• Some tests in GlidArc I reactors but too high specific energy and too low reaction rate (few %) due to the reverse reaction in the post-plasma space

• Much better results obtained when plasma-generated O* radicals can immediately react with a reductantlike CH4 or H2S (see later)



CFC + H2Ovap → H2 + CO + CO2 + HXaq Exothermic!

X = F, Cl, (Br, and/or I)

0.85 L glass reactor

vol.% IN

% mineralizationX C

SERkWh/kg

CHCl3 32 37 85 5.4

CF2Cl2 30 41 61 6.8

CFCl3 18 49 58 12

steam plasma + waste CFC

= SynGas + concentrated HX acids!



Upgrading of concentrated H2S

Dissociation energies (per mol of produced H2) for common molecules:

21 kJ for H2S dissociation to H2 + S

37 kJ for CH4 pyrolysis to 2 H2 + C

285 kJ for water electrolysis to H2 + ½ O2

Hydrogen sulphide is present in:• geothermal fluids• natural gases• fluids used for assisted oil recovery• industrial gases (oil desulphurization, coking, rubber pyrolysis, metallurgy, viscose, paper mills, fermentation, etc.)


H2S is therefore an abundant source for potentially the cheapest Hydrogen

but the petroleum industry prefers to produce Hydrogen from other sources … for Sulphur removal from crude oils and refinery products.

This creates > 6 million tons per year of concentrated H2Sin which very weakly bonded Hydrogen is then

stupidly burned to water and cheap Sulphur via 115-years old Claus process!


H2 recovery from H2SThermal processes: no hopeElectrolysis?Non-equilibrium plasma processes: better hope … since 1876' works of Marcelin Berhelot (France).So silent, glow, corona, short pulse, radio-frequency or micro-wave discharges?Interesting laboratory or pilot results … but no industrial applications because of low-pressure necessity and/or nonexistence (or cost) of specific high power electric supplies.

We are proposing a process called SulfArc that is based on our GlidArc devices. We look to upgrade directly almost any H2S-rich mixture into SynGaswithout prior gas separation.


Thermo-ChemistryH2S → H2 + S ΔH° = +20.6 kJ/molH2 + CO2 = H2Ovap + CO ΔH° = +41.1 kJ/molCO + S = COS ΔH° = - 31.5 kJ/mol

H2S + x CO2 = (1-x) H2 + (1-y) S + x H2Ovap + (x-y) CO + y COS

First “Controlled Arc” tests (1987)

1 - Ar plasma torch (2 kW), 2 - power supply, 3 - cathode, 4 - anode of the plasma torch and entry nozzle, 5 - transfer anode and exit nozzle, 6a, 6b, 8 - gas entries, 7 - injection system, 9 - power supply, 10 - reaction chamber, 11 - expansion chamber


Pilot installation of SulfArc for 60 m3/h sour gas processing in Poland (1993)

Acid gas

Treated gas

Nozzle

Reactor

P T P T

Incinerator

Condenser

Air

Acid gas

Sampling

to Stack

I WElemental sulfur

Three-phase 220-380 V

SULFARCUnit

PowerSupply

U

U

Sampling

mesurementValve

Pressure regulator

Mass flow meter


13

5

4

6

7

2

8

9

Schematic view of 1.4-L GlidArc I reformer for H2S or sour gas processing

1- cold gas entry, 2 - preheat chamber, 3 – preheated gas exit, 4 – injector of the preheated gas into the plasma chamber, 5 – exit of the product, 6 – high-voltage connectors to the electrodes, 7 – electrodes (six), 8 – gliding discharges, 9 –observation window


A 60-L SulfArc reactor (based on GlidArc II principle) was built by ECP (and then installed in Texas) for H2S-rich gases processing.

This reactor contains 9 stages, each of them being powered by 3 stationary electrodes so that 36 active electrodes are present (including central electrodes).

H2S conversion rate (all tests for 82-83 vol.% H2S at the input)

0

20

40

60

0,0 1,0 2,0 3,0 4,0

Specific Energy Input in kWh/m3(n)

%

to H2total


SulfArc advantages

• Products do not contain ballast of added reactants• No catalyst• Process does not depend on the chemical composition of effluents• One can process small quantities of H2S or sour gas produced by small industrial units• Energy expense is quite low• No thermal inertia, good resistance to corrosion…

The energy consumptions can be improved…All range of parameters asks for a further fine-tuning…Several further tricks can still be applied like heat recycling…A compromise GlidArc + Claus ?



Natural Gas pyrolysis

GlidArc I in CH4 at 1 bar

Two bench scale reactors: glass 0.1 L cold-wall vessel and 1.3 L steel tube.

CH4 flow-rate: up to 2.3 m3(n)/h.

Temperature of the products: < 500°C

Up to 34% of the feed was converted to H2, C2H2, and soot via:

CH4 = C + 2 H2

CH4 = 0.5 C2H2 + 1.5 H2

High selectivity to acetylene (70-90%) and only 30-10% selectivity to soot.

Energy for production of 1 m3(n) H2 + 0.18 m3(n) C2H2 was around 2.6 kWh for that bench scale process


Very dry and light "soot" appears as poorly organized carbon nanoparticles



Partial Oxidation of Natural Gas or Bio-Methane

ECP has a dream: distributed Gas-to-Liquid (GTL) plants providing fuel for local drivers. There are two challenges:

• small Bio-Methane or Natural Gas reforming

• and small Fischer-Tropsch synthesis plant

More than dreams: we already generate our real SynGas by POX of the NG (presently from the town pipe). The POX takes place in our GlidArc I reformers at up to 6 bar and operates with:

air or

O2-enriched air

so that the SynGas compression to higher pressure FT synthesis asks for only one-step operation.

… and our own FT process/reactor is also under development…


0.2 L

0.6 L

Input:

Air 4.4 - 116 L(n)/min

Oxygen 1.7 - 10.5 L(n)/min

O2 content 21 - 44 vol.%

Steam 0 - 9.8 g/min

NG 2.7 - 28 L(n)/min

1.5 - 21 kW LHV

O2/CH4 molar ratio 0.49 - 1.04

Pressure 1.1 - 6.1 bar abs

Generated Syngas (dry, in vol.%):

H2 17 - 49 C2H4 0- 0.02

CO 6.7 - 23 C2H6 0 - 0.4

N2 21 - 65 C3 0 - 0.005

CO2 2.5 - 14 O2, C2H2 absent

CH4 0.2 - 7.3

NG

OX


40

50

60

70

80

90

100

0,45 0,65 0,85 1,05

Input O2/CH4 (mol/mol)

%

2

2,5

3

3,5

4

4,5

5

Thermal Eff iciency (%)CH4 conversion rate (%)(H2+CO) out per CH4 in (mol/mol)H2/CO (mol/mol)

30

40

50

60

70

80

90

100

0,50 0,60 0,70 0,80 0,90

O2 / CH4 ( mol / mol )

1,5

2,0

2,5

3,0

3,5

4,0

4,5

5,0

CH4 conversion rate (%)(H2+CO) out per CH4 in (mol/mol)H2/CO (mol/mol)

Air at atmospheric pressure Air at 4 bar (abs)

Output:

H2+CO up to 89 L(n)/min

Thermal efficiency up to 96 %

L of H2+CO per L of Methane up to 3.3

Conversion rate of CH4 75 – 98 %

Electric power assisting our reforming is less than 1% of the LHV power of produced SynGas stream.



Direct upgrading of biogas (or other CH4 + CO2 mixtures)

EndothermicAnaerobic digestion of any organic matter into biogas is presently available as commercial package. Huge amounts of biogas can also be captured from land fields. Biogas contains: 30-80% of CH4, 80-30% of CO2, up to few % of H2S, and some amount of halogens and siloxanes.

Task:

Partial dry reforming of poor biogas

CO2 + CH4 CO + H2

by direct injection of active electric energy (GlidArc) in order to generate a syngas-enriched biogas @ increased flammability for engines or turbines fueling … or as a source of Hydrogen


010203040506070

400 600 800 1000 1200temperature (K)

vol.%

CH4 COCO2 H2

Equilibrium composition at 1 atm (dry gas) as a function of temperature for poor biogas composed of 65 vol.% CO2 and 35% CH4


13

5

4

6

7

2

8

9

Plasma chamber

1.4-L reactor:

1- cold biogas entry, 2- preheat chamber, 3 – preheated biogas exit, 4– entry of the preheated biogas into the plasma chamber, 5– exit of the upgraded biogas, 6– high-voltage connectors to the electrodes, 7– electrodes (three), 8– gliding discharges, 9–observation window


InputCH4 content in biogas 35 – 50 vol.%Flow rate 15 – 27 L(n)/minThermal power of biogas (LHV) 4.8 – 7.3 kWAdded electric power 0.48 – 0.58Added electric power 6.6 – 12 %

OutputGas temperature 120 – 220 °CFlow rate 17 – 28 L(n)/minThermal power (LHV) 5.0 – 7.4 kWGas composition (dry) CO2 38 – 55

vol.%

CH4 25 – 35H2 6.3 – 14CO 5.3 – 11

(H2 + CO) (12 – 25)C2H6 1.5 – 2.0C2H2 0.07 – 1.4C2H4 0.11 – 0.22

C3 0.24 – 0.33Electric energy expense to produce 1 m3(n) H2 + CO 2.1 – 2.5 kWh

Efficiency 27 – 43 %

@ such temperatures one can not obtain such product composition even using a highly active catalyst!


0

2

4

6

8

10

0,25 0,35 0,45 0,55 0,65

SEI kWh/m3(n)

% o

f LH

V ad

ded

0

5

10

15

20

25

% v

ol.

% LHVH2+COC2H2

SynGas and C2H2 content in upgraded poor biogases (35-50 % CH4) as a function of Standard Energy Input as well as the % of added LHV with respect to the LHV of initial biogas


2,0

2,1

2,2

2,3

2,4

2,5

0,25 0,35 0,45 0,55 0,65SEI kWh/m3(n)

SER

kW

h/m

3 (n) o

f Syn

Gas

Standard Energy Requirement (SER) to produce the pure SynGas from poor biogases as a function of Standard Energy Input (SEI); cumulated tests on biogases containing 35-50% of CH4



POX of various fossil or renewable liquid fuels

We electrically assist the POX (with air) of any carbonaceous feed accepting a very small (< 1%) electric energy addition to generate very active and simple GlidArc discharges that:– ignite the partial oxidation– catalyse it in the plasma zone, and– stabilise a post-plasma polishing zone of the

reformer

allowing safe POX process:any liquid fuel + air CO + H2

(+ N2 + CO2 + H2O)


Task/Example #1JP-8 aviation fuel reforming

air input: 1.4 – 2.5 m3(n)/hJP-8 input: 0.25 - 0.48 kg/h

aromatics: 15 vol.%Sulfur: 433 ppm wt.

SynGas production after < 15 min (cold start) or after only 1 min when the reformer is kept hot. Reformate contents:

H2 10 – 16 vol.%, dry

CO 15 – 19

H2+CO 25 – 35

N2 58 – 67

CO2 2.8 – 4.8

CH4 0.7 – 2.8


Output LHV power of the SynGas (Reformate Gas)and Energetic Efficiency of the process

0

1

2

3

4

5

4 6 8input JP-8 (g/min)

kW LHV

outp

ut

0

20

40

60

80

100

%

output power (kW)

thermal efficiency (%)


Task/Example #2Road Diesel Oil reforming

air input: 2.9 – 8.8 m3(n)/hfuel input: 0.66 – 1.8 kg/h

Sulphur: 310 ppm wt.preheat: 240°C

1.8-L

Carbon Number Distribution

02468

1012

7 9 11 13 15 17 19 21 23 25

Carbon Number

% w

t


Diesel fuel conversion: totalCoke, soot, tar: absent Reformate LHV power (all combustibles): 7 - 22 kWReformate gas (vol.%, dry basis) : H2 16 – 20

CO 19 – 22CO2 2.4 – 4.8CH4 0.8 – 3.3C2H4 0.0 – 2.1

0

5

10

15

20

25

10 20 30 40

g/min DO input

kW o

tput


Task #3

Vegetable oils + air (+ GlidArc) = H2 + COExample: Rapeseed Oil

Ideal reforming:

C18.1H34.1O2 + 8.05 O2 = 18.1 CO + 17.05 H2O/C = 0.89 (added oxygen)

Full combustion:

C18.1H34.1O2 + 25.63 O2 = 18.1 CO2 + 17.05 H2OO/C = 2.83 (added oxygen)

CompromiseC18.1H34.1O2 + 10.53 O2 =

15.09 CO + 12.54 H2+ 2.31 CO2 + 0.47 CH4 + 0.11 C2H4 + 3.35 H2O

O/C = 1.16 (added oxygen)


010203040506070

3000 3200 3400 3600 3800 4000

air/oil L(n)/L

vol.%

CO2H2N2CO

Concentration of main products (dry basis) as a function of air/oil ratio for all successful runs. Other gases are at minor concentrations: CH4 0.5–1.0, C2H4 0.1–0.5, C2H6 0.01–0.03, and C2H2 0.001–0.005 vol.%.


0

2

4

6

8

10

12

10 15 20 25 30

oil mL/min

outp

ut L

HV

pow

er

(kW

) of S

ynG

as

0

12

24

36

48

60

72

L(n)

/min

of S

ynG

askWL(n)/min

Output flow rate of H2+CO in L(n)/min and in kW for all runs


5

5,5

6

6,5

7

3000 3200 3400 3600 3800 4000

L(n) air per L oil

kWh

(LH

V) o

f Syn

Gas

fr

om 1

L o

f oil

LHV of the Syngas produced from 1 liter of the Rapeseed oil as a function of applied air/oil ratio. The data originate from allnon-sooting tests


Task/Example #4

Prove that our GlidArc-assisted conversion of biodiesel into the Synthesis Gas (H2 + CO) can be used:

A. as a part of a de-NOx process for which a very frequent catalyst regeneration is required,

B. to feed (or only boost) classical spark engines for decentralized power generation.

We have accepted both challenges, have built and tested in France three prototypes of reformers of 100% biodiesel. Two prototypes were then installed and successfully tested in Tennessee and Colorado in 2005.

www.glidarc-tech.com 445-L test reformer

SynGas

preheated air

sampling

hot SynGas exit

Air(cold) from blower

entry

connectors to two GlidArc electrodes

double-wall(heat exchanger)

Fuel + water entry (cold)

control burner


Soybean biodiesel B100Specific gravity 883 kg/m3 (at 15°C)Lower Heating Value (LHV) 10.4 kWh/kgCarbon content 77 wt.%Hydrogen content 12Oxygen content 11Av. chemical formula (CH1.87O0.11)n

Air input flow-rate 8.2 – 28 m3(n)/hBiodiesel flow-rate 1.7 – 9.0 kg/hWater flow rate 1.3 – 4.5 kg/hInput power (LHV) of fuel 18 - 94 kW

SynGas generation starts after < 20 min (cold start) or after 1 min when the reformer is kept hot.


SynGas quality (dry, vol.%):

H2 19 – 23 av. 22

CO 10 – 20 av. 15

H2+CO 29 – 43 av. 37

N2+Ar 48 – 60 av. 53

CO2 6.7 – 11 av. 8.5

CH4 0.5 – 1.5 av. 0.9

C2H4 0.05- 0.25 av. 0.18

C2H6 0.02 - 0.05 av. 0.04

C3 0 - 0.003

O2, C2H2 absent


Output LHV power of the SynGas and H2 mass flow rate

0

20

40

60

80

100

0 40 80 120 160

g/min biodiesel

kW

0

0,2

0,4

0,6

0,8

1

0 40 80 120 160

g/min biodiesel

kg/h

H2

Energetic efficiency =

74%


5-L GlidArc-assisted biodiesel reformer for continuous production of 22 m3/h SynGas

=> 1 kg H2 per hour

Tennessee, July 2005

de-NOx catalytic reactor (>96% cleaning of whole exhaust from 4 MW biodiesel engine)


GlidArc reformer de-NOx catalytic reactor

www.glidarc-tech.com 51Colorado, November 2005

Our 5-L reformer


0.5 m

25-hrs run without any

problem

www.glidarc-tech.com 53Output LHV power of the SynGas for 90° Ethanol

0

10

20

30

0 20 40 60Ethanol IN (g/min)

kW (L

HV)

SynGas

Energetic Efficiency

= 76%

… and what about ECP’s links to Poland in the liquid fuels domain?

Task/Example #5

Ethanol


Other ongoing developments

Diluted waste/dirty alcoholsOther vegetable oils Waste GlycerolWater diluted Sugar or molassesBio-oils from biomass pyrolysisLarger reformer (0.4-0.7 MW)Fischer-Tropsch catalysts…

www.glidarc-tech.com

Thank you!

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