PRESENTATION ON

CATALYTIC REFORMING UNIT

UNIT
NSU HTU

SCOPE OF THE UNIT

Feed preparation for HTU Removal of Sulphur, Nitrogen, Oxygen from feed of CRU . For production of high octane reformate (MS component) For burning coke from CRU catalyst. To produce pure N2 for units. To improve Hydrogen purity of recycle gas.

CRU
CCRU N2 Ammonia Refrigeration

HYDROTREATER UNIT( UNIT-14)

Catalysts used in hydrotreater :
LD-145 1.9 M3 HR 348 19.1 M3 TO PROTECT THE REFORMER CATALYST THE FEED HAS TO BE PRETREATED IN ORDER TO ELEMINATE THE FOLLOWING POISONS: S, N2, H20 , DIOLEFIN, ARSENIC AND METALS BY HYDROREFINING REACTIONS WHERE MERCEPTANS, SULPHIDES AND DISULPHIDES EASILY REACT LEADING TO CORRESPONDING SATURATED AND AROMATIC COMPOUND R-SH + R-S-R + R-NH2 + H2 2H2 H2 -----> ------> -----> RH +H2S, RH +RH +H2S R-H + NH3

Sulfur combined into cycles of aromatic structure, like thiophene, is more difficult to eliminate.

+ S Thiophene

4H2

C4 H10 + H2S

De-NITRIFICATION: Nitrogen compounds inhibit considerably the acidic function of the reforming catalyst. They are eliminated by production of ammonia. The nitrogen compounds of SR naphtha are methylpyrol and quinoline. HC CH + 4H2 C5H12 + NH3 HC C-CH3 N

Methyl pyrrol

n-Pentane

Ammonia

HC HC

HC

CH

CH
+ 5H2

HC

CH
+C3H8+NH3

HC HC

CH

HC CH

CH

CH

Quinoline

Benzene

Propane

Nitrogen elimination is practically complete. The total Nitrogen content in the product is less than 0.5 PPM

HYDRO-DEOXYGENATION: Oxygen or oxygen compounds modify the acidic function of the reforming catalyst. They are eliminated by production of water. The oxygen compounds of straight-run are peroxides and phenols. Oxygen is almost completely transformed into water.
HC HC OH HC CH CH + H2O HC CH CH

+ H2
HC HC CH

Phenol

Benzene

HYDROTREAER UNIT( UNIT-14)

HYDROGENATION REACTION CONVERTS THE DIOLEFINS, OLEFINS TO SATURATED COMPOUNDS

THE ARSENIC AND METAL COMPOUNDS ARE ABSORBED ON THE CATALYST ( NICKEL AND MOLYBDENUM CATALYST)

Operating conditions
NHTU :
ATTRIBUTES Pretreater Feed Reactor inlet tempearture Delta T Stripper bottom sulphur Moisture UNITS MT/hr 0 C 0 C ppm ppm

49 291 2.1 0.25 5-6

OBEJECTIVE OF CRU
To produce lead free Motor Sprit from Mathura Refinery. The purpose of CCRU type or Reforming Unit is to produce High Octane reformate as component of lead free Motor Spirit.
Design Capacity:
Over Design Factor Turn Down Capacity

0.466 MMT/Year based on 8000 hrs/y

120% of Design 60% of Design

CATALYTIC REFORMING
BY PRODUCTS

H2 RICH CRU GAS USED AS MAKE-UP FOR HYDROTREATING, AND TO PRODUCE H2 THROUGH PSA -140 MAKING MORE ECONOMIC VIABLE PROCESS.

LPG

(NOT GENERATED AT PRESENT)

CATALYST (CR 201) CHARACTERISTICS

THE OCTANENISING CATALYST CR-201 IS MULTIMETALLIC CATALYST CONSISTING OF PLATINUM PLUS METAL PROMOTORS TIN ON AN ALUMINA SUPPORT HIGH PURITY ALUMINA SUPPORT HAVING STRONG RESISTANCE TO ATTRITION HIGH STABILITY AND SELECTIVITY DUE TO Pt AND Sn HIGH REGENERABILITY IDEALY SUITED FOR CCRU HIGH REFORMATE YIELD HIGH HYDROGEN YIELD HIGH STREAM FACTOR LOW CATALYST INVENTORY

CATALYST CONTAMINANTS
TEMPORARY POISONS ARE THOSE WHICH CAN BE REMOVED FROM CATALYST WITHOUT SHUTDOWN. THEY ARE SULFUR, ORGANIC NITROGEN, WATER AND OXYGENATED ORGANICS AND HALOGEN. PERMANENT POISONS ARE THOSE WHICH INDUCE A LOSS OF CATALYST ACTIVITY WHICH CAN NOT BE RECOVERED EVEN WITH THE REGENERATION AND MAY BE SO SEVERE THAT THE CATALYST MAY BE REPLACED. THE MAIN PERMANENT POISONS ARE ARSENIC, LEAD , COPPER , IRON , NICKEL AND CHROMIUM

OCTANE NUMBER OF HYDROCARBONS

OCTANE NUMBER IS A MEASUREMENT OF ANTI-KNOCK CHARACTERISTICS OF FUELS. AMONG THE SAME CARBON NUMBER COMPOUNDS THE ORDER OF RON (RESEARCH OCTANE NUMBER) IS PARAFFINS < NAPHTHENES < AROMATICS. BRANCHED PARAFFINS ALSO HAVE HIGH OCTANE. IT INCREASES WITH DEGREE OF BRANCHING. THEREFORE OCTANE NUMBER OF NAPHTHA CAN BE IMPROVED BY REFORMING THE HYDROCARBON MOLECULE (MOLECULAR REARRANGEMENT). SUCH REARRANGEMENT TAKES PLACE IN REFORMING REACTORS IN PRESENCE OF CATALYST BY WAY OF NUMBEREOUS COMPLEX REACTIONS.

OCTANE NUMBER OF VARIOUS HYDROCARBONS n I n l n l Butane Butane Pentane Pentane Heptane octane Toluene 94.0 102.0 61.8 93.0 0.0 100.0 120

INDEX = A+0.85N
THE HIGHER THIS INDEX, THE LOWER THE SEVERITY OF OPERATION TO MEET THE SAME PRODUCT SPECIFICATION. THE LOWER THIS INDEX (I.E. HIGHER THE PARAFFINS) THE HIGHER THE SEVERITY OF OPERATION TO MEET THE SAME PRODUCT SPECIFICATIONS, AS THE DEHYDROCYCLIZATION OF PARAFFINS BECOMES IMPORTANT.

REACTIONS IN CATALYTIC REFORMING

FOLLOWING ARE THE MOST PREVALENT REACTIONS IN CATALYTIC REFORMING MAIN

DEHYDROGENATION
AROMATICS.

OF

NAPHTHENES

TO

ISOMERISATION OF PARAFFINS AND NAPHTHENES.

DEHYDROCYCLISATION
AROMATICS.

OF

PARAFFINS
TO

TO

HYDROCRACKING

OF PARAFFINS MOLECULAR WEIGHT COMPOUNDS.

LOWER

HYDROCRACKING
RUPTURE OF CARBON TO CARBON BOND WITH REVERSIBLE FORMATION OF LOWER MOLECULAR WEIGHT PARAFFINS. RCH2 CH2 C H3 + H2 ----> RH + CH3 CH2 CH3 N PARAFFIN PARAFFIN HYDROCRACKING IS EXOTHERMIC. THESE REACTIONS ARE UNDESIRABLE DUE TO DECREASE IN REFORMATE YIELD. FAVOURED BY INCREASE IN TEMPERATURE AND PRESSURE. HYDROCRACKING PRODUCE COKE PRECURSOR AND REDUCE THE CATALYST ACTIVITY. REACTIVITY OF PARAFFINS HYDROCRACKING INCREASE WITH CARBON CHAIN.

MAIN OCTANIZING REACTIONS

THE MAIN OCTANIZING REACTIONS TAKE PLACE IN THE VARIOUS REACTORS IN THE FOLLOWING ORDER, 1ST REACTOR 2ND REACTOR 3RD REACTOR CRACKING DEHYDROCYCLIZATION

DEHYDROGENATION DEHYDROGENATION ISOMERIZATION ISOMERIZATION CRACKING DEHYDROCYCLIZATION