BITS Pilani

K K Birla Goa Campus

Catalytic Reforming
 Catalytic Reforming - Introduction

• Important process in petroleum and petrochemical industries

• [Petroleum] Conversion of low octane SR naphtha and
cracked naphtha to high octane reformate using catalyst
• [Petrochemical] To produce aromatics (BTX) which are
important for production of synthetic fibre, explosives, dyes,
pharmaceuticals, etc.
• Byproduct: H2 (90% Purity), LPG
• Demand for reforming technology continuously increasing
because
• Strong demand for gasoline (worldwide, especially in India and China)
• Strong demand for petrochemicals worldwide
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 Octane number of fuel

• Advent of I. C. engines of high compression ratio

• Knocking can occur in such cases
• Prevention of knocking can be achieved by high octane value of
the fuel
• Octane number
• Required/desired octane number  86 – 93
• Straight run naphtha (from CDU)  63 – 66
• Increase in octane number
• Using TEL (phasing out) and MTBE (restrictions)
• Achieved by re-orienting or re-forming low octane components
into high octane components (aromatics) using catalyst
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 Reforming reactions
• Dehydrogenation
• Cyclohexane  Benzene + H2
• Isomerization
• N-hexane  2-methyl pentane
• Hydrogenation of un-saturates
• Methyl cyclohexene  methyl cyclohexane
• Paraffin de-hydrocyclisation
• Naphthene isomerisation and dehydrogenation
• Cracking
• Hydrodesulfurisation
• Denitrogenation
• Deoxidation
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 Reforming reaction network
Un-Desired
Reactions

Desired
Reactions

13/03/2018 AMOL DESHPANDE BITS Pilani, K K Birla Goa Campus

 Reaction conditions

• Reaction rates and effect on improvement of octane no

• Isomerization and dehydrogenation are fast reactions whereas
cyclisation is slow and need severe conditions
• Isomerization and cyclisation  best to increase octane no
• Dehydrogenation and cyclisation of n-paraffins  tangible
improvement in octane rating
• Effect of pressure
• Low pressure  encourages dehydrogenation but also leads to
coke formation
• Isomerization  No effect of pressure
• Hydrocracking and elimination reactions  depend on H2 partial
pressure
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 Reaction conditions

• Effect of temperature
• All reactions except hydrogenation are favored at high
temperature
• High temperature  degradation of product and coke deposition
• Typical operating parameters
• Low pressure (10 – 50 atm)
• High temperature ( 450 – 500 C)
• High H2 recirculation
• High catalyst to feed ratio (effects on space velocity)

13/03/2018 AMOL DESHPANDE BITS Pilani, K K Birla Goa Campus

 Catalyst

• Dual function (Metal (Pt) on silica or silica-alumina)

• Acid sites: Isomerization and cyclisation
• Metallic bonds: hydrogenation
• Low Pt catalyst
• 0.3 % (non-regenerative)
• High Pt catalyst
• 0.3 – 0.5% Pt (regenerative)
• Higher percent of Pt : Costly, lead to adverse reactions like ring
opening
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 Catalyst

• Cost of Pt
• Restricts using fluidized bed operation
• Moving bed are in operation
• ZSM – 5 (Zeolite Socony Mobil – 5)
• Alumino-silicate catalyst used especially for isomerization and
disproportionation reactions
• R-132 (UOP) (Pt based)
• Maximum hydrogen production
• Reduction of reformate benzene
• High gasoline yield
• Lower RVP
• Less operating cost
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 Catalyst

• Other catalyst (Cr oxide and Mb oxide on alumina)

• Abrasive resistant
• Can be used in moving beds and fluidized beds
• Bauxite and clay catalysts were used in earlier days
• Clay catalysts  Not much hydrogen produced (compared to Pt)
• Pt combination with other metals are also being use
• Monometallic: Pt
• Bimetallic: Pt and Re; Pt and Sn
• Multimetallic: Pt, Re, Ge; etc.

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 Feedstock

• Suitable for gasoline engines

• Straight run naphtha of low octane no (mostly containing
n-paraffins), Light products obtained in cracking
• Boiling point range : 35 – 180 C
• Feed should be free from impurities like sulfur, nitrogen
and oxygen compounds
• For Pt based catalysts, sulfur and nitrogen content < 5
ppm

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 Overall operation

• Most of the reforming operation conducted in fixed bed

processes using Pt based catalysts
• Pt combinations yield less light ends than conventional Pt
catalysts
• Production from reforming operation
• 5 – 15 % yield of light ends
• 75 – 95 % yield of reformate
• 70 – 350 m3 of H2
• Yield of potential aromatics is a function of naphthenes and
aromatics in feed
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 Catalyst reforming processes

• Semi-regenerative (SR) fixed bed

• Taken off stream after every 3 – 12 or even 24 months (regeneration)

• Cyclic fixed
bed
• Same as semi-
regenerative but
with a swing
reactor
(which undergoes
regeneration after
reforming process)
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 Catalyst reforming processes

• CCR (Continuous Catalyst Regeneration) - Platforming

(UOP)

Ref: UOP website (https://www.uop.com/reforming-ccr-platforming 14

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 Catalyst deactivation reasons

• Coke formation
• Contamination on acid sites
• Agglomeration
• Catalyst poisoning
• Temporary Poisons
• Permanent poisons

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 Catalyst reforming processes –
Licensed technologies
• Platforming (UOP) – 1949
• Rheinforming (Chevron)
• Fixed bed regenerative process
• Rh-Pt combination used in catalyst  good resistant to fouling
• Low P, High SV, Low H2/HC
• Powerforming (Exxon)
• Cyclic or semi-regenerative
• Octane no -> 85 – 100
• 3% yield of H2
• Ultraforming (Amoco)
• Catalyst good for high temperature operation (catalyst posses
longer life)
• Catalytic reforming (Engelhard) 16

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 Products quality – Important
parameters
• C5+ gasoline yied (vol %)
• Research octane number
(RON)
• C4+ gasoline yield
• Dry gas yield
• H2 yield (wt%)

• Coke deposit (for catalyst)

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 Effect of operating parameters
(process variables) on product
• Reactor temperature
• Pressure
• H2/HC ratio
• High ratio or higher H2 partial pressure important for catalyst
stability
• Space velocity
• Paraffinic feed  low SV
• Naphthenic feed  high SV
• Feedstock (N + A content)
• Naphthenic feed give higher reformate yield than paraffins
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 Naptha hydrotreating
• Mainly to remove sulfur (Mercaptans, disulfide and
thiophenes)

• Process Flow Diagram (General)

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 Problem
• Naphtha (80 – 100 C) reformed over a Pt catalyst; RON of reformate  97;
• Reformer capacity  10000 BPSD
• Data:
Feed Product
BP 80 – 110 50 – 110
Avg Mol wt 90 85
K factor 11.59 11.52
API 50.2
Sp gravity 0.782
S (%) 0.01 0.004
SV (h-1) 3

Reactor: P = 20 atm; T = 45 C
Density of catalyst = 0.82 kg/m3
1. Estimate Losses
2. Find Net hydrogen produced
3. Perform complete material balance
4. Find the amount of catalyst in each reactor 20

20/03/2018 AMOL DESHPANDE BITS Pilani, K K Birla Goa Campus