Prereforming

Research I Technology I Catalysts

Leif Storgaard

History
Prereforming was developed back in the 60es especially for towns gas plants The technology disappeared in the 70es when town gas was replaced with natural gas Topse re-invented the technology in the 90es Today more than 100 plants operate with prereformer Topse prereforming catalyst is installed in about 70 % of all prereformers

Typical installation of a prereformer

H2O (optional) Tubular reformer

Prereformer

Waste heat channel Feed from HDS Process steam

Why install a prereformer ?

Increase plant capacity Lower energy consumption No risk for carbon formation in tubular reformer Longer life time of tubes and catalyst in reformer Operate at lower steam to carbon ratio Operate on multiple feedstocks Longer life time of LTS catalyst

Prereforming reactions
CnHm + nH2O nCO +

m (nH2 ) + 2

H 298 (694 kJ/mol for C4H10) (-41 kJ/mol) (-206 kJ/mol)

CO + H2O CO2 + H2 CO + 3H2 H2O + CH4

Temperature profiles in prereformer with different feedstocks

550

Bed temperature, C

500

450

Natur el gas 400 0 20 40 60

LPG

Naphtha

80

100

Distance in bed, %

Temperature profiles in natural gas prereformer using Topse prereforming catalyst

490 480 470 460 450 440 430 0 20 40 60 80 100 D is tance in Bed, %
3 We e ks 1 2 M o n th s 2 2 M o n th s 4 5 M o n th s 5 9 M o n th s

Bed temperature, C

Evaluation of prereformer performance

The prereforming catalyst deactivates mainly due to sulphur poisoning Topse have developed a method to evaluate the deactivation rate of the prereformer (Z90 method) Based on Z90 method the remaining catalyst life time can be estimated Based on Z90 method one get a quick warning if sulphur leakage from HDS should increase

Graphical deactivation plot the Z90 method

510

Temperature [C]

Tmax
490 Measured temperatures

90% of Tmax
470

T 90 = Tin 0.9 Tm ax

T90
450 0 20

Z90

40

60

80

100

Bed volume [%]

Graphical deactivation plot the Z90 method

90 80 70 60 50 40 30 20 10 0 0 10000 20000 30000 40000 50000

Operating Time, Hours

Temperature profile for the prereformer at a naphtha-based plant

495
T90

490

TExit

485

480
TMin

475

470 0 10 20

Z90

30

40

50 Bed height, %

60

70

80

90

100

Excessive sulphur poisoning Z90 plot

Graphical Deactivation Plot - Z90 Method
100 80 60 40 20 0 Time

Z90, %

Operation
The prereforming catalyst should be kept reduced during shut down /start up 1. If the catalyst is oxidized some of the sulphur picked up on the catalyst in the top will be released 2. This sulphur will be picked up by the catalyst further down in the bed 3. The overall catalyst activity will decrease when the sulphur is distributed to a larger part of the bed

Key parameters for prereforming catalysts

Activity Sintering (ageing) Carbon resistance Sulphur tolerance Resistance to gum formation Mechanical stability Pressure drop

New prereforming catalyst AR-401

During development of the new AR-401 catalyst the key parameters have been optimized We have used new techniques to optimize the catalyst Compared to AR-30, the surface area of AR-401 has been increased while maintaining the mechanical strength

Surface area
Total surface area of 10 m3 AR-401 Singapore

Sintering
The sintering rate (ageing) has been investigated in the electronic microscope to find the optimum composition of the catalyst that minimize sintering

Sintering
Particle migration

Sehested et al. J. Catalysis vol. 223 (2004)

From Science to Proven Technology by Brian Munch

AR-401 other features

AR-401is delivered pre-reduced no reduction during start up As delivered AR-401 is stable in air loading do not require inert atmosphere AR-401 can tolerate exposure to condensing steam

Thank you for your attention