HYDROGEN GENERATORS - TECHNOLOGIES AND PRODUCERS

Hydrogen Production by Steam Reforming

Technologies & Producers

Zoran Jurić, M.Sc. Chem. Eng.

ATA Chemistry
Chemistry
Stevan Ajdinović
Zoran Jurić

HYDROGEN PRODUCTION VIA STEAM METHANE REFORMING

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HYDROGEN GENERATORS - TECHNOLOGIES AND PRODUCERS

How Hydrogen can be produced?

HYDROGEN PRODUCTION VIA STEAM METHANE REFORMING

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What is Steam Reforming?

1. Steam-Reforming Reaction
Methane:
CH4 + H2O (+heat) → CO + 3H2
2. Water-Gas Shift Reaction
CO + H2O → CO2 + H2
(+small amount of heat)
3a. Removal of CO2 by using MEA or KCO3 3b. Pressure Swing Adsorption
Adsorption of CO2 using weak base Adsorption of CO, CO2, CH4
2MEA+CO2 →←MEACOO-+MEAH+ by using molecule sieves
4a. Methanation
Reaction of CO and CO 2 with H2
to remove CO and CO2
CO2 + H2 → CO + H2O
CO + 3H2 → CH4 + H2O

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Hydrogen production through Steam Reforming

Typical synthesis gas composition produced by natural gas steam reforming:

CH4: 2,91%, CO: 12.62%, CO2: 10,40%, H2: 73,98%, N2: 0,09%

Steam reforming of natural gas produces about 7 kg CO 2 per 1 kg of H2 (Princeton University 1997)

HYDROGEN PRODUCTION VIA STEAM METHANE REFORMING

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Steam reforming with CO2 removal

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Steam reforming with PSA unit

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Steam Reforming with PSA-basic processes

Pretreatment of the feed

●The feed is mixed with a small H 2 stream, preheated and sent to the desulphurization reactor.
●After the desulphurization, the feed is mixed with the process steam generated in the steam reboiler.

Reforming and high temperature conversion

●The feed is mixed with steam and it is reformed into a raw hydrogen rich gas.
●Heat for reforming is generated by combustion of fuel gas and purge gas from PSA.
●The heat from the reformed gas is recovered for steam generation.
●The reformed gas is fed to the high temperature CO conversion to produce additional H 2.

Gas cooling by Heat Recovery

●After CO conversion, the converted gas is cooled down in a series of heat exchangers.
●The exchanged heat is used to preheat process streams.

Gas cooling by Heat Recovery

●The H2 rich gas is sent to PSA.

●Impurities are separated to obtain high purity H 2 gas with purities up to 99,999% by volume.
●The purge gas from depressurization and purging during the regeneration of PSA is used as a fuel gas.

HYDROGEN PRODUCTION VIA STEAM METHANE REFORMING

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PSA (Pressure Swing Adsorption)

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Comparison of Conventional and PSA Steam Reforming

PSA units have replaced

conventional units.
The conventional unit may
be preferred when:
•Limited H2 purity is acceptable
•CO2 recovery planned
•The excess steam is
inadequately exploited

CO2 removal

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Major Stream Reformer Hydrogen Plant Producers

1. Foster-Wheeler
2. Haldor Topsoe
3. UHDE
4. Air products
5. UOP
6. Technip
7. Linde (acquisition od Selas America)

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Custom made small scale steam reformers

●Between 50 to 600 Nm3/h range, SMR hydrogen generators compete in

the industrial gas market with hydrogen deliveries and electrolyzers
●Due to their relatively high prices they occupy only a very small fraction
of that market

1. Hydro-Chem/Linde
2. Pan American Enterprises
3. Mahler
4. Caloric
5. CarboTech
6. H2Gen
7. Harvest
8. Hygear
9. HyRadix
10. Osaka Gas

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CO2 Removal - Low CO2 Partial Pressure

●Most flue gases have very low CO2 partial pressures and near atmospheric
pressure with CO2 concentrations of 3% to 13%.
●Many of acid gas treatment processes operate at 10 barg and cannot remove CO 2
to less than 0,1 barg partial pressure.
●Only commercially absorbents for recovery of dilute CO 2 from atmospheric
pressure gas are monoethanolamine (MEA), including newly developed hindered
amines
●Approximately 0,33 mol of CO2 is absorbed by 1,0 mole of amine at atmospheric
pressure

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CO2 Removal - Medium and Higher CO2 Partial Pressure

●Many commercial processes are handicapped by absorption at atmospheric

pressure (limitation on physical and chemical solvents)
●MDEA, DEA and TEA amines operate at medium CO 2 partial pressures
●Typical applications would be for a CO2 removal unit in syngas production or
natural gas sweetening
●Compression costs to put the flue gas into the operational range are prohibitive
for these absobers

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CO2 Removal - Higher CO2 partial pressure

●Hot KCO3 is effectively used in many ammonia, hydrogen, natural gas plants
●Suitable for bulk removal of CO2 and removal of relatively high concentrations of
CO2 from gas streams
●The most known process with is Benfield process with KCO 3 by UOP with over
675 units worldwide
●There is also well known Catacarb process with KCO 3
●The process with KCO3 is designed for CO2 removal from high pressure streams
and requires an optimal feed CO2 partial pressure of 7 barg (minimum of 2 barg)

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Example:
Econamine FG by Fluor for CO2 removal by using MEA

●The Econamine FG process is today’s premier commercially proven process for

CO2 recovery from flue gasses at low CO2 partial pressures
●The best suited for atmospheric applications
●Recovers 85%-95% of the CO2 in the flue gas and produces a 99,95% pure CO2
●Inhibitor tolerates oxygen and NOx
●Not applicable to reducing gas stream containing large amounts of CO and H 2,
COS and CS2

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Example:
Amine Guard by UOP for CO2 removal by using amines

The absorption and regeneration of acid gases

in the Amine Guard process are based on the
following reactions:

2R2NH + CO2 + H2O = (R2NH2)2CO3 (3)

 (R2NH2)2CO3 + CO2 + H2O = 2R2NH2HCO3 (4)

3,5 barg – 120 barg operating range

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Example:
Benfield by UOP for CO2 removal by using KCO3

The absorption and regeneration of acid gases

in the Benfield Process are based on the
following reactions:

K2CO3 + CO2 + H2O = 2KHCO3 (1)

K2CO3 + H2S = KHS + KHCO3 (2)

10 barg – 120 barg operating range

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MEA and KCO3 vs. PSA

●Many existing hydrogen and ammonia plants world-wide use MEA

(monoethanolamine) or MDEA (methyl diethanolamine) solutions in their CO2
removal processes.
●Others process that have been used is Benfield with KCO3.
●However, it seems that many, if not most, of the newer plants use the Polybed
Pressure Swing Adsorption process (PSA).
●The PSA process does not use any solution or solvent. It uses multiple beds of
a proprietary solid adsorbent.
●The CO2 removal with MEA, MDEA and KCO3 units may be preferred when
limited H2 purity is acceptable and CO2 recovery is planned

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Major producer of CO2 removal processes

1. UOP
2. BASF
3. Dow Chemical
4. Elf Aquitaine
5. Fluoro
6. Texaco
7. Union

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Current Status of Steam Reforming

●Steam Reforming of natural gas is widely used in hydrogen industry today

●Hydrogen is produced by Steam Reforming in large centralized plants for use in
chemical manufacturing and petroleum refining.
●Research and Development programs are investigating the development of
small-scale Steam Reforming technologies to enable the development of small-
scale, distributed hydrogen production and delivery infrastructure.

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Steam Reforming-Advantages

●Steam Reforming of natural gas offers an efficient, economical and widely used
process for hydrogen production, and provides near- and mid-term energy
security and enviroment benefits.
●The efficiency of the Steam Refoming process is about 65% to 75%, among
the highest of currently commercially available production methods.
●Natural gas is available, convenient, easy to handle, hydrogen feedstock with a
high hydrogen-to-carbon ratio.
●The cost of hydrogen produced by Steam refoming is dependant on natural gas
prices and is curently the least expensive among all bulk hydrigen production
technologies.
●A well developed natural gas infrastructure exists and it is a key factor that
makes hydrogen production from natural gas attractive.

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Steam Reforming-Challenges
●During the production of H2, CO2 is produced.
●The Steam reforming process emission: CO2 produced ≥ H2 produced
●To avoid emission of CO2, CO2 can be captured and sequestered
●Possible near or mid term shortages of natural gas
●Significant R&D is required to bring the cost of H2 using Steam Reforming down
and to make the process more efficient
●American DOE's target is to reduce the cost of distributed H2 production from
$3/kg H2 to $1,5/kg H2 by 2010, and improve efficiency from 68% to 75%.

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Hydrogen Trends

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Hydrogen Production Future

In the near- to mid-term, hydrogen will likely be produced by:

• steam reforming of natural gas
• water electrolysis using electricity from conventional energy
resources.

In the mid- to long-term, the hydrogen production technologies

currently under development:
• renewables via electrolysis
• direct renewables (photobiological, photoelectrochemical, etc.)
• high temperature nuclear chemical cycles
• clean coal and natural gas--will become more cost effective and
contribute to a diversification of domestic hydrogen production.

One of hydrogen’s great strengths is its ability to be produced from a

wide variety of resources

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Mahler - Hydrogen Generators Producer

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Mahler 400 m3/h Hydrogen Generator - Economics

MAHLER AGS GmbH
E C O NO MIC AL E VALUAT IO N
P r o j e c t N o. :
C u s t o m e r : Me s s e r Te hno g as AD

Type of plant : Hydrogen Plant (based on Natural Gas)

HYDROFORM-C
Plant data
Design data i.N. = 0°C, 1013 mbar
plant capacity 400 m3/h (i.N.) Hydrogen
Hydrogen concentration 99,999 % by vol.
product pressure 13 bar abs
Consumption figures
Natural gas 181,0 Nm3/h
Electric power 39,0 kW
Process/demin water 0,54 m3/h
Cooling water 15,0 m3/h

Investment
price of plant (incl. demin water unit) 1.900.000 EURO
Erection/Commissioning (assumption) 510.000 EURO
others 0 EURO
Total investment costs 2.410.000 EURO

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Mahler 400 m3/h Hydrogen Generator - Economics

Operating data
operating hours/day 24 h/d
operating days/week 7 d/w
operating weeks/year 51 w/a
operating hours/year 8.568 h/a

Generated productgas quantity/year 3.427.200 m3/a (i.N.)

Financial figures
Depreciation 10 years
Interest rate 8,5 %
Natural gas 0,350 EURO/m3
Electric power 0,100 EURO/kWh
Process/demin water 5,000 EURO/m³
Cooling water 0,060 EURO/m³

Generated product gas quantity/year=400 m3/h • 99,999% • 8568 h/a = 3.427.166,00 m3/a

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Mahler 400 m3/h Hydrogen Generator - Economics

3
Total costs per year Total costs per Nm
Capital Costs per year 367.303 Euro / a 0,107 Euro/Nm3
Maintenace/repair 72.300 Euro / a 0,021 Euro/Nm3
Capital costs per year 439.603 Euro / a 0,128 Euro/Nm3

Natural gas per year 542.783 Euro / a 0,158 Euro/Nm3

Electric power 33.415 Euro / a 0,010 Euro/Nm3
Process/demin water 23.134 Euro / a 0,007 Euro/Nm3
Cooling water 7.711 Euro / a 0,002 Euro/Nm3
Operating costs per year 607.043 Euro / a 0,177 Euro/Nm3

To tal c o s ts pe r ye ar 1.046.645 Euro / a 0,305 Euro/Nm3

Specific product costs

including investment: 0,305 Euro / Nm3 H2
without investment: 0,198 Euro / Nm3 H2

1.046.645 euro/a (total cost per year) / 3.427.166,00 m 3/a (total H2 produced per year) = 0,305 euro/m 3

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