FUNDAMENTALS OF STEAM REFORMING H2 PLANTS

 Typical configuration:
+ Hydrotreating over CoMo at ~600-700 F to convert organic S (Primarily)
mercaptan and Cl into H2S and HCl and saturate any olefins
+ ZNO/ MGO to adsorb H2S and HCL
++ Typically two vessels with appropriate valving so that either could be
changed while the other is operating
++ Typical strategy after S breakthrough at first rxr. Move last to first and
change spent ZNO.
+ Contact with Steam from steam generation section
+ Steam to carbon mole ratio typically between 4 and 8/1
+ Steam Reforming Furnace -
++ Many (sometimes hundreds) of 4 inch id 40 ft long tubes in a fired
furnace
++ Typically 3.5-4 Tubes per MMSCFD H2 capacity
++ Limited by flux at 18 -22 KBTU/HR/Ft2
++ Aggressive Designs go as high as 30 KBTU/Hr/ Ft2 (don’t try
this at home)
++ Many burners could be upfired, downfired or sidefired
++ Usually .75-1 Burner per tube (total in two levels)
++ Other designs may gave as few as 0.2 - 2.0 Burners/tube
++ Steam reforming - CH4 + H20  3H2 + CO
++ Water Gas Shift also occurs: CO + H2O  CO2 +H2
++ Typical Convection section services
 Steam Generation
 Feed Preheat
 Steam Superheat
 Air Preheat
++ Typical Coil Inlet Temperature = 700-1100 F
++ Typical Coil Outlet Temperature = 1400-1500 F
+ Waste Heat Boiler - Generate High P (usually 600#) steam and cool Furnace
effluent quickly to avoid soot formation (CO + CO => C + CO2)

+ High Temperature Shift Reactor ~700 F

++ Performs Bulk Conversion of CO + H20 toCO2 + H2
++ 0.5 - 1.5 % CO in HTS effluent
++ Near Equilibrium
++ Temperature Rise typically 50 - 75 F
+ Low Temperature Shift Reactors ~ 400 F
++ Converts additional CO + H20 to CO2 + H2
++ 0.05 - 0.15 % CO in LTS effluent
++ Near Equilibrium
++ Temperature Rise typically 25-30 F

+ CO2 Removal
 ++ Usually Potassium Carbonate catalyzed by DEA (Catacarb or
Benfield)
++ Typically 0.1% CO2 in scrubbed Gas
++ Often Limits H2 Plant Capacities
+ Methanator - converts leftover CO into CH4 since CO could poison
Hydrotreating Catalyst
++ Reverse of Reforming Reaction
++ CO + 3 H2 => CH4 + H2O
++ Typically 500-600 F
++ High temperature rise from excess CO or CO2 could shut down Unit
+ PSA units often replace LTS, CO2 removal and Methanator in newer designs
++ Pure H2 product ~80-88% recovery from HTS effluent
++ Off gas burned in Low pressure burners at Steam Reforming Furnace
++ Special (larger) furnace design to accommodate Low Pressure/low
BTU fuel
 Reaction Chemistry:
+ Steam Reforming Furnace: CxHy +x H2O => x CO + (x+y/2) H2
+ For Methane: CH4 + H2O => CO + 3 H2
+ Typically Ni based Catalyst designed for high heat transfer
++ Resistance to coking is more important for heavy feeds
+ Typically no hydrocarbon heavier than CH4 in Steam Reformer Product Gas
+ Reactions go essentially to equilibrium for both methane steam reforming and
water gas shift reactions in Steam reforming furnace:

++ Kref = P2(CO)(H2)3 /((CH4)(H20))

++ Kshift = (CO2)(H2)/((CO)(H20)

++ Approach to equilibrium typically used to measure performance -actual

outlet temperature minus equilibrium temperature for effluent (calculate K
from composition and look up temperature for that equilibrium constant)
++ Approach typically 0-5 F for Methane feed
+ + May be as high as 50 F for heavy feeds (Butanes)
++ Approach is usually negative for H2 rich feeds (-20 to -50 F)
++ Theoretically impossible
++ Probably indicates temperature at catalyst surface is much
hotter than measured coil outlet temperature.
++ Other convoluted explanations (i.e. diffusion limitation) are
possible
+ Calculation procedure for approach to equilibrium attached
+ High Temperature Shift Reactors: CO + H20  CO2 + H2
++ Fe based catalyst often promoted by Chromium
++ Very Rugged Insensitive to most catalyst poisons
++ Typically operates at 700 F and 6000 V/H/V (Vapor Hourly Space
Velocity, at Outlet conditions in Hr-1)
++ Must be reduced to activate Fe2O3 + H2 => Fe3O4/FeO + H2O
++ Inlet temperature increases slightly (20-30 F) throughout run to
 maintain equilibrium at outlet.
++ Temperature rise also used as a measure of activity
++ Typically ~1% CO at reactor outlet
++ Monitor approach to equilibrium:
++ Kshift = (CO2)(H2)/((CO)(H20)
++ Should be within 5 - 10 F of theoretical equilibrium temp (table lookup)
+ Low Temperature Shift : CO+ H20  CO2 + H2
++ Usually CuO/ZnO on Alumina base
++ very sensitive to H2S or HCl
++ Will deteriorate if exposed to liquid water
++ Poor activity and high pressure drop
++ Typically operates at 400 F and ~5000 V/H/V
++ Must be reduced to activate CuO + H2 => Cu + H2O
++ Inlet temperature increase slightly (20-30 F) throughout run to
maintain equilibrium at outlet.
++ Temperature rise also used as a measure of activity
++ Typically ~0.1% CO at reactor outlet
++ Monitor approach to equilibrium:
++ Kshift = (CO2)(H2)/((CO)(H20)
++ Should be within 5 - 10 F of theoretical equilibrium temp (table lookup)
+ CO2 removal : K2 CO3 + CO2 + H2O => 2KHCO3
++ Typical solution strength 30% K2 CO3
++ Rich solution 70-80% conversion
++ Lean Solution 25-35% conversion
++ Metallurgy/passivation with V5+ is a major issue maintain .6-.8% V5+
(as KVO3)
++ DEA is the typical catalyst
+ Methanator: CO + 3 H2 => CH4 + H20
++ Reverse of Steam Reforming
++ All H2 actually made because of Shift reactions and CO2 removal
++ Highly exothermic Trise =
135 F/Mole% CO
107 F/Mole% CO2
++ Usually Ni on Alumina Catalyst
++ 450-500 F typical inlet, 4500 V/H/V
++ Usually trips at 825 F
 Monitoring Calculations for H2 Plants

+ Data Required
+ Feed GC Analysis and Rate
+ Steam Rate
+ Steam Reformer Reactor inlet and outlet Temperature, Outlet Pressure and CH4 content
+ For each Shift Reactor effluent CO content inlet and outlet temperature
+ CO2 content after Catacarb/Benfield absorber
+ Methanator Effluent CO and CO2 content, inlet and outlet temperatures
+ For PSA units H2 content of PSA tail gas (to calculate recovery)
+ Steam Reformer Performance Calculations:
+ If detailed analysis of reactor effluent is available calculate Equilibrium constants:
Kref = P2(CO)(H2)3 /((CH4)(H20))
Kshift = (CO2)(H2)/((CO)(H20)

+ If Kshift is better (lower EQ temperature) than equilibrium sample probably

shifted before it was analyzed
++ Adjust composition by shifting back to equilibrium
++ Calculated by solving a quadratic equation to adjust for moles shifted:
Kshift = (CO2-x)(H2-x)/((CO+x)(H20+x)

++ Note x is the only unknown this expand to a simple quadratic equation

++ (CO2-x) is calculated moles of CO2 at reformer outlet at shift equilibrium

++ Similarly (H2-x),(CO+x) and (H20+x) are calculated moles of other components
at shift equilibrium.
++ Calculate Kref using effluent composition adjusted back to shift equilibrium.
++ Calculate temperature corresponding to this equilibrium temperature (table look
up or iterative calculation)
+ If detailed analysis of reactor effluent is not available (or reliable) calculate Equilibrium
constants by matching measured CH4 analysis
++ Iterative calculation required
++ Calculate Moles of C, H and O in feed
++ Guess moles of CH4 at reformer effluent
++ From material balance and shift equilibrium equations calculate effluent
composition
++ Adjust estimate moles of CH4 in effluent to match measure CH4 composition
and satisfy shift equilibrium and material balance equations.
++ Calculate temperature corresponding to this equilibrium temperature (table look
up or iterative calculation) and “approach” to equilibrium.
++ Perform heat balance around reactor radiant section
+ Feed Enthalpy – Product Enthalpy = Radiant duty
+ Calculate Heat flux across tubes Radiant duty/ total tube surface area
++ KBC has several spreadsheet and Fortran programs to perform these
calculations.
+Calculate moles shifted across each shift reactor. From CO composition of effluent.
++ Perform heat balance around reactor radiant section
++ Feed Enthalpy – Product Enthalpy = heat loss should be small

+ If lean and Rich conversions and solution rates are known across Catacarb calculate CO2
absorbed from both absorber and regenerator side. Flag any inconsistency.

+ Perform heat and mass balance around Methanator:

++ Feed Enthalpy – Product Enthalpy = heat loss should be small
 Overall Energy Balance and Economic for H2 Plants

+ H2 plants are heat integrated to preheat feed and produce Steam (or preheat Boiler feed
water) from waste heat.
++ Reformer Effluent Cooling
++ Reforming Furnace convection section
++ HT Shift Effluent cooling

+ Heat balance will claculate Stema production.

+ Heat available for steam = Convection Duty + Effluent cooling duty (WHB + Shift
effluent cooler) – Process Steam production + Superheat – Feed preheat to Radiant inlet
Temperature.
+ Radiant Efficiency can be estimated from fuel gas composition excess air and furnace
Bridgewall Temmperature
++ Usually need to adjust 2 – 4% to account for radiation into convection section
+ Overall Furnace Efficency can be calculated from fuel gas composition excess air and
furnace stack Temperature

+ Heat recovered in effluent heat exchange can be calculated from composition and
temperature.

+ Heat required for feed preheat can be calculated based on Feed composition and battery
limit temperature and furnace inlet temperature.

+ Heat required for process steam generation can be calculated from BFW temperature and
process steam pressure and temperature.

+ Heat available for export steam calculated by difference.

+ Adjust heat loss and radiant duty (if necessary) to match observed duty in base case.

+ Calculate Steam production for subsequent cases assuming constant heat loss.

+ Perform economic analysis based on individual feed costs and cost of producing steam
by alternate mechanism (Boilers)
 Overall Material Balance Equations for a Steam Reforming
H2 Plant With CO2 Removal/Methanation

Assumptions:

• Hydrotreated Feed is mixture of Paraffins and H2

• Overall Reaction Stoichiometry :

CNH2n+2 + 2(N - X)H2O => (3N+1-4X) H2 + (N-X) CO + X CH4

• Product Contains only H2 and CH4 thus:

H2/CH4 = P/(1-P) = (3N+1-4X)/X (Eqn 1)

Where:

P = Purity, mole fraction H2 in Product

N = Moles of carbon per mole of Feed
X = Moles of methane product per mole of feed

• Solving Eqn 1 for X as follows:

PX = (1-P) (3N+1-4X) = -4X + 4PX + (1-P) (3N+1)

Rearranging:

4X - 3PX = (1-P) (3N+1) (Eqn 2)

X (4-3P) = (1-P) (3N+1) (Eqn 3)

XCH4 = (1-P)(3N+1)/(4-3P) (Eqn 4)

•Moles of H2 product / mole of feed can be calculated by:

XH2 = 3N+1-4X= (3N + 1) - 4(1-P)(3N+1)/(4-3P) (Eqn 5)

which Reduces to:

XH2 = P(3N+1)/(4-3P) (Eqn 6)

• Similarly Moles of CO2 per mole of feed can be calculated by:

XCO2 = N-X = N - (1-P)(3N+1)/(4-3P) (Eqn 7)

which Reduces to:

XCO2 = (N-1+P)/(4-3P) (Eqn 8)

• For feeds that contain N2 assume all N2 in the feed goes to product and use
equations 4, 6 equations 4, 6 and 8 for the hydrocarbon portion.

• N can be calculated from the detailed Lab analysis or from feed gravity as
follows:

MW = 28.98 Gravity (Eqn 9)

N = (MW - 2.016)/14.026 (Eqn 10)

•To calculate mass rates of each product rates from feed rates multiply by the ratio
of
molecular weights of the feed and the product as follows:

WCH4 = XCH4 Wfeed MWCH4/MWfeed

WH2 = XH2 Wfeed MWH2/MWfeed
WCO2 = XCO2 Wfeed MWCO2/MWfeed