LATEST TECNIQUES

ADOPTED IN AMMONIA
PLANT TO IMPROVE
ENERGY
BY
PREM BABOO
SR. MANAGER(PROD)
NATIONAL FERTILIZERS LTD,VIJAIPUR, INDIA
 SIMPLE WAY TO UNDERSTAND
AMMONIA PLANT
 TECHNOLOGY HALDOR TOPSOE

 CAPACITY 1750/1864 TPD

 FEED NG AND NEPTHA

 ENERGY 7.2GCAL/TON OF AMMONIA
ON NG
 7.36 GCAL/TON OFAMMONIA IN
 CASE OF MIXED FEED
INGREDIENT FOR AMMONIA
 TO PRODUCE AMMONIA WE REQUIRE
H2 AND N2
 H2 WE GET FROM NG AND WATER
 N2 WE GET FROM AIR
 NG CONTAINS ABOUT 92%CH4
 NEPTHA CONTAINS HIGHER
HYDROCAREBON
BLOCK DIGRAM OF AMOONIA
PLANT

DESULPHERISATION REFORMING

SHIFT REACTION CO2 REMOVAL AREA

AND METHNATION CO2 TO UREA

COMP HOUSE
SYNTHESIS AMM TO UREA
 DESULPHERISATION
AIM
 TO REMOVE ALL SULPHER
COMING WITH NG AND NEPTHA
 SULPHER IS POISIONOUS FOR THE
DOWNSTREAM CATALAYST
 IT CONSISTS OF TWO STEPS
 HYDROGENATION
 IN THIS VESSLE NG AND NEPTHA ARE
BROUGHT IN CONTACT WITH
HYDROGEN SO THAT ORGANIC
SULPHER GETS CONVERTED INTO
INORGANIC SULPHER WHICH IS
SUBSEQUENTLY REMOVED IN ZNO
ABSORBER
 CATALYST NIMO –FOR NG
 COMO -FOR NAPHTHA
HYDRODE-SULPHERISATION
 ALL ORGANIC SULPHER GETS
CONVERTED IN H2S

NG
HDS
RSH +H2 =RH +H2S
H2
R1SSR2 +H2 = R1H +R2H +H2S
NIMO

OUTLET
 ZnO ABSORBER
 TWO BEDS ARE INSTALLED IN SERIES
 CATALYST USED IS = ZnO
 ZnO+H2S = ZnS + H2O
 SULPHER AT THE OUTLET OF THESE VESSLE ARE
LESS THAN .01PPM
 INCREASING SULPHER CONTENT GIVE THE
INDICATION THAT BEDS ARE GETTING EXHUSTED
AND THEY REQUIRE CHANGE
 FIRST BED CAN BE BYPASSED AND CATALYST CAN
BE CHANGED ON LINE A SPECIAL BED OF Copper
BASEDCATALYST IS INSTALLED AT THE BOTTOM OF
THE FIRST BED TO ADSORB ANY ORGANIC SULPHER
IF IT SLIPS FROM HYDROGEATION BED
 DESULPHERISATION
ZnO +H2S = ZnS +H2
FROM HDS

ZnO ZnO

TO REFORMER
 REFORMING
 AIM
 TO REFORM NG AND NEPTHA IN TO H2
CO AND CO2 REFORMING IS DONE WITH
THE HELP OF STEAM THATIS WHY IT IS
CALLED STEAM REFORMING IT
CONSIST OF THREE STEPS
 STEPS OF REFORMING
 PREREFORMER

 PRIMARY REFORMER

 SECONDRY REFORMER
CONDITION OF REFORMING
 REFORMING IS AN ENDOTHERMIC REACTION
 IT MEANS THAT HEAT WILL HAVE TO BE
SUPPLIED TO MOVE THE REACTION IN
FORWARD DIRECTION
 MAJOR PORTION OF REFORMING IS DONE IN
PRIMARY REFORMER THIS REACTION IS
CARRIED OUT IN A FURNACE OPERATING
CONDITIONS ARE VERY INTENCE
REACTIONS OF REFORMING
 CnH2n+2 +2H20 = Cn-1H2n +CO2 +3H2-
HEAT

 CH4 +2H2O = CO2 +4H2 –HEAT

 CO2 + H2 = CO + H20 - HEAT

 HOW OPERATING CONDIONS
ARE DECIDED
 AS PER LE CHATERLIERS PRINCIPLE THE
REACTION OF REFORMING REQUIRES
 HIGH TEMERATUTRE CONDITIONS
 LOW PRESSURE CONDITIONS
 OPTIMUM PRESSURE IS SET ARROUND
34KG\CM2
 PRESSURE BELOW THIS SUITS REFORMIG
REACTION BUT THIS IS NOT SUITABLE FOR
DOWNSREAM REACTIONS
 CATALYST USED IN
REFORMING
 CATALYST USED IS NICKLE
 IN VARIOUS REFORMING STEPS ONLY
THE CONTENT OF NICKLE VARRIES
 BESIDES THIS BASE OF THE CATALYST
ALSO VARRIES
 CONDENSATION OF STEAM IS TO BE
AVOIDED IN CATALYST BED
BECAUUSE IT MAY SPOIL THE ENTIRE
CATALYST
 PRE REFORMER
 PRE REFORMER IS ISTALLED IN AMMONIA
EXPANSION
 ITS PURPOSE IS TO REFORM HIGER HYDROCARBON
TO LOWER HYDROCARBON
 TO BE KEPT IN LINE WHEN NEPTHA IS BEING USED
IN FEED
 WITHOUT PREREFORMER NEPTHA CAN NOT BE
USED IN FEED
 IT CAN BE KEPT IN LINE WITH NG ALSO BUT NOT
WITH GREAT DEAL OF ADVANTAGE
 ITS CATALYST IS ONE OF THE COSLIEST IN
AMMONIA PLANT
 PRE REFORMER

490 ----510

PRE
REFORMER
NG+NEPTHA+STEAM

NI
440----470

REFORMED GAS TO P R
 PRIMARY REFORMER
 IT IS THE MOST IMPORTANT STEP IN
THE REFORMING PROCESS
 IT COSIST OF A FURNACE
 FURNACE IS SIDE FIRED
 IT CONTAINS 288 TUBES AND 576
BURNERS
 CATALYST IS FILLED INSIDE THE TUBE
 FIRING IS DONE ON BOTH THE SIDES OF
THE TUBE
REFORMER FURNACE

TUBES CH4 90%

450---500

NI
765

CH4 11%
 IMPORTANT PARAMETER OF
PRIMARY REFORMER
 FURNACE INSIDE PRESSURE SHOULD BE
SLIHTLY BELOW ATMOSPHERIC PRESSURE
ARROND -5MMWC
 TUBES SKIN TEMP SHOULD NOT EXCEED
905DEGREE CENTRIGADE OTHRWISE TUBE
LIFE WOULD BE SHORTENED
 S/C RATIO IS ONE OF THE MOST IMP
PARAMETE ITS KEPT ARROUND 3.3 LOWER
S/C RATIO MAY RESULT IN CARBON
FORMATION
 SECONDRY REFORMING
 AIM
 TO COMLETE THE REMAINING
REFORMING
 TO INTRODUCE AIR SO THAT WE CAN
GET N2 REQUIRED FOR THE AMMONIA
PRODUCTION
SECONDRY REFORMING
AIR
P REF O/L
765

1200
CH4 11%

SECONDRY REFORMER

S R O/L

940

CH4 .3%
WHAT HAPPENS IN SECONDRY
REFORMER
 PRIMARY REFORMER OUTLET GAS
WHICH CONTAINS ABOUT
11%METHANE AT ATEMP OF ABOUT
765DEGREE IS BROGHT IN CONTACT
WITH AIR AT A TEMP OF 575 DEGREE
 FIRST REACTION IN SR IS EXOTHERMIC
REACTION IN WHICH APART OF GAS
BURNS WITH AIR O2 GETS CONSUMED
WHAT HAPPENS IN SECONDRY
REFORMER
 TEMERATURE OF GAS IN TOP PAERT OF
REFORMER REACHES TO ARROUND
1200 DEGREE
 THIS HEAT IS USED FOR FURTHER
REFORMING
 METHANE AT OUTLET OF SR BECOMES
ABOUT .3%
 SR OUTLET TEMP BECOMES 940
DEGREE
 SHIFT REACTION
 AIM
 GAS AT THE OUTLET OF SR CONTAINS
BOTH CO AND CO2
 CO IS OF NO USE
 CO2 IS REQUIRED FOR THE
PRODUCTION OF UREA
 IN SHIFT REACTORS ALL CO IS
CONVERTED IN TO CO2
 SHIFT REACTION
 SHIFT REACTION IS TWO STEP PROCESS
 FIRST STEP IS CARRIED OUT AT HIGH
TEMP IT IS CALLED HT SHIFT
REACTION TO INCREASE THE RATE OF
REACTION
 SECOND STEP IS CARRIED OUT AT LOW
TEMP CALLED LT SHIFT REACTION IT
IS TO ACHIVE HIGH EQULIBIRIUM
CONVERSION
 HT SHIFT CONVERTOR
 CATALYST USED IRON OXIDE
 INLETTEMP 355 DEGREE
 OUTLET TEMP 423DEGREE
 OUTLET CO 2.8%
 CO+H2O = CO2 +H2
HT SHIFT CONVERTOR

355

SR OULET GAS

HT SHIFT
CO 12.77
CATALYST GAS TO LT
IRON OXIDE
423
CO 2.8%
 LT CONVERTOR
 CATALEST USED MIANLY CU
 INLET TEMP 195 DEGREE
 OUTLET 212 DEGREE
 OUTLET CO .17%
 CO +H2O = CO2 + H2
 POISON FOR THE CATALYST ARE
 S AND CHLORIDE
LT SHIFT CONVERTOR

HT OUUTLET

CO 2.8%
LT CONVERTOR
LT OUTLET

CO .17%
 CO2 REMOVAL

 TWO MAIN PROCESS FOR THIS ARE

 BENFIELD PROCESS USED IN LINE 1
 GV PROCESS USED IN LINE 2
 GV PROCESS USED IN LINE 2 HAS SOME
ADVANTAGE OVER BENFIELD PROCESS
 GV PROCESS
 AIM
 TO REMOVE ALL CO2 FROM THE
PROCESS GAS BY ABSORBING IN HOT
POTTASIUM CARBONATE SOLUTION
AND THEN REGENERATING THE
SOLUTION
 CO2 PRODUCED IS SENT TO UREA
PLANT
 GV PROCESS

 SOLUTION IS MADE OF POTTASSIUM

CARBONATE
 TWO ACTIVATORS USED ARE
 GLYCENE AND DEA
 COMPOSITION
 K2CO3 27%
 GLYCENE 1.2%
 DEA 1.0%
 VANADIUM .4%
 GV PROCESS
 CHEMISTRY INVOLVED
 ABSORBTION REACTION
 K2CO3+H20+CO2 =2 KHCO3

 REGENERATION REACTION
 2KHCO3 +HEAT = K2CO3 +H20+CO2
TWO STAGE REGENERATION & USE OF FLASH STEAM OF HP IN LP
REGENERATOR & REDUCTION IN LP STEAM
REDUCTION CO2 SLIP by 1000PPM
IMPROVED HEAT RECOVERY
 Heat loss to
atmosphere via
air cooler-12.68
Gcal/h
 BLOCK DIGRAM
 CO2 FREE GAS
CO2
SOLUTION

LOADED SOL

ABSORBER REGENERATOR

GAS
STEAM

LOADED SOL REGENERATED SOL

 METHNATION
 AIM
 TO CONVERT ALL CO AND CO2 TO
METHANE

 OUTLET GAS FROM CO2 REMOVAL

AREA CONTAINS BOTH C0 AND C02
BOTH THESE GAS ARE NOT REQUIRED
AS THESE ARE POISON FOR THE SYN
CATALYST
 METHNATION
 CATALYST USED NICKLE
 C0 + H2 = CH4 + HEAT
 CO2 +H2 =CH4 + HEAT
 METHANE FORMED ACTS AS A INERT
GAS IN SYN REACTION AND IT IS
REMOVED IN PURGE TAKEN OUT FROM
THE SYN LOOP
 METHNATION

GAS FROM GV
290

CO .17% CO2 300 PPM

METHNATOR
NICKLE COANDCO2<1PPM

306

GAS TO COMP
 COMP HOUSE
 COMP HOUSE CONTAINS THREE COMP
 AIR COMP

 REFRIGRATION COMP

 SYNTHESIS COMP
 AIR COMP
 AIM
 AIR COMPRESSOR COMPRESSES AIR UP
TO 34KG\CM2 PRESSURE
 AIR IS USED IN SECONDRY REFORMER
 H2/N2 RATIO DETERMINES FLOW OF
AIR TO SECONDRY REFORMER
 AIR COMP

AIR COMP

AIR TO SECONDRY REFORMER

ATMOS AIR 34KG /CM2 170

REFRIGRATION COMPRESSOR
 AIM
 IT IS USED TO COMPRESS AMMONIA
WHICH IS USED AS A REFRIGRENT IN
SYNTHESIS LOOP
 REFIGRATION IS DONE AT THREE
PRESSURE LEVEL
 ITS FINAL DISCHARGE PRESSURE IS
14KG \CM2
 SYNTHESIS COMP
 AIM
 AMMONIA SYNTHESIS REACTION IS
CARRIED OUT AT HIGH PRESSURE
CONDITIONS AT ABOUT 180KG\CM2
 SYN COMP IS USED TO COMPRESS GAS
UP TO THAT PRESSURE
 Syn compressor

Gas to comp Gas from loop

Gas to loop 180kg/cm2

26kg/cm2 172kg/cm2
175 Gas to conv
 AMMONIA SYNTHESIS
 AIM
 TO PRODUCE AMMONIA WITH THE
HELP OF SYN GAS COMING FROM
METHNATOR
 SYN GAS CONTAINS MAINLY H2 AND N2
 AMMONIA SYN REACTION

 3H2 +N2 = 2NH3 +HEAT

 CATALYST USED IRON
 REACTION CONDITION
 HIGH PRESSURE AND LOW TEMP
 AMMONA SYN REACTION
 AMMONIA SYN REACTION IS A REVERSIBILE
REACTION AND EQULIBIRIUM CONDITION IS
DETERMINED BY TEMP AND PRESSURE
CONDITIONS
 IN ONE PASS THROUGH THE CONVERTOR
ONLY 30% OF THE REACTANTS GETS
CONVERTED TO THE PRODUCT SO
REMAINING GAS KEEPS ON CIRCULATING
 BLOCK DIGRAM

GAS TO CONV

H2 AND N2

H2 N2 AND NH3

OUT LET GAS

 BLOCK DIGRAM OF SYN
SECTION

SYN GAS STEAM

AMM CONVERTOR LOOP BOILER BFW HEATER

GAS GAS EX WATER COOLER GAS GAS EX

PRI CHIL SEC CHILL AMM SEP LET DOWNVESSLETO

PURGE GAS STORAGE
AMM TO UREA
 What is purge
 AS AMMONIA SYN REACTION IS NOT
COMPLETED IN ONE STEP AND GAS IS KEPT
ON CIRCULATING INERTS BUILDS UP IN THE
LOOP
 INERT MEANS CH4, Ar NH3 AT INLET OF
CONV THEIR CONCENTRATION SHALL NOT
INCREASE BEYOND 14%
 SO A SMALL AMMOUNT OF GAS IS
CONTTIOUSLY WITHDRAWN FROM THE
LOOP THIS STREAM OF THE GAS IS CALLED
PUGE GAS
 PURGE GAS RECOVERY
 PURGE GAS CONTAINS H2, CH4 AND
AMMONIA
 AMMONIA IS RECOVERED BY
WASHING THE GAS WITH WATER AND
REMAINING GAS WHICH CONTAINS CH4
AND H2 IS USED IN REFORMER FIRING
SYSTEM
 PURGE GAS RECOVERY

AM TO STORAGE
GAS TO REF WATER

ABSORBER LOADED SOL REGENERATIONR

STEAM
PUURGE
 Installation of Plate type Combustion air
preheater
 Facilitate reduction in reformer stack temperature to
125°C
 Energy saving: 0.055 Gcal /MT NH3
 Energy saving due to
 a) NG saving due to increase in combustion air
temperature
 B) Reduction in steam consumption in ID Fan
 Conversion of Benfield process to GV
process
 To increase capacity and improve energy
effciency
 GV 2 stage process has a lower specific
regeneration heat requirement and hence
reduction in low pressure steam consumption by
utilizing flash steam of HP regenerator &
utilization heat by LP steam reboiler instead of
loosing to atmosphere through air cooler
 Energy savings: 0.18 Gcal/MT NH3
 Existing Amm-II is based on GV Process
New equipment in conversion from Benfield to GV
section
 Separator OH 2nd regenerator (B-1307)
 LP steam boiler (E-1301)
 DMW pre-heater (E-1305 A/B)
 Condenser OH 2nd regenerator (E-1309)
 2nd Regenerator (F-1303)
 Steam Ejector (X-1301)
 Aeration Injection tank (T-1305)
 Sealing water heater (E-1315)
 Cooler for Aeration tank (E-1324)
 Activated carbon filter and 2nd Mechanical filter
New machinery in conversion from Benfield to GV
section
 CO2 blower (K-1301)
 Semi-lean solution pump (P-1301D)
 Lean solution pump (P-1302 A/B)
 2nd condensate pump (P-1308 A/B)
 Aeration Injection pump (P-1309 A/B)
 Sealing water pump (P-1310 A/B)
 Modifications in 1st regenerator
 New take off trays are installed below bed 2
and above bed 3
 New liquid re-distributors above bed 1 and 3
 Bed limiters over beds 1 and 3
 1st bed height reduced by 2195 mm
 Demister
 New nozzles and instrumentation for new take-
off trays
 Modification in CO2 absorber
 Liquid distributor over Bed 2 and 4
 Liquid redistributor over beds 1,2,3 & 4
 Gas distributor under bed 1
 Packing : Bed 1: IMTP 50 Bed 4: IMTP25
 Installation of S-50 converter
 To increase the energy efficiency of the ammonia
synthesis loop, an S-50 converter R-1502 is installed
downstream of the existing converter.
 The increase in ammonia concentration exit the new
converter results in a decrease in loop pressure and a
lower circulation rate, which gives savings on the
synthesis gas compressor and the refrigeration
compressor.
 Energy saving: 0.18 Gcal/MT NH3
 Advantages of addition of S-50 Loop
 Ammonia concentration at the outlet of S-50 =
24.35% as compared to 20.02% in S-200
 Higher conversion 35.5 % as compared to 28.3% in S-200
 Lower circulation rate as compared to S-200 for same
load
 Higher steam generation 82 T/hr as compared to 70 T/hr in S-
200
 Lower synthesis loop pressure
 Lower compressor power due to less circulation and low
pressure
 Possible to achieve higher plant load with same equipments
S-50 Integration in synthesis loop
 Parallel Air compressor
 Addition of Parallel air compressor
(reciprocating type) to meet the additional
process air requirement
 Process air from Existing PAC: 59152
Nm3/hr
 Process air from New Compressor: 6030
Nm3/hr
 Total air requirement for 1750 MTPD
ammonia as per PFD: 65181 Nm3/hr
 Ammonia-II CEP: Process air
 As per PFD of Ammonia-II CEP, the total
requirement of process air from PAC of
Ammonia-II shall be 75683 Nm3/hr with
distribution as follows:
 Process air for Ammonia-II CEP : 69234
Nm3/hr
 Instrument air : 3924 Nm3/hr
 Export to Ammonia-I : 2525 Nm3/hr
69
 Ammonia-II CEP: HTAS report & OEM review

 The capacity of existing PAC in Ammonia-II is : Normal:

59275 Nm³/h , Rated : 64900 Nm³/h
 Based on overall performance curve of PAC, HTAS has
confirmed that the desired load shall remain within the
operating range of the compressor.
 OEM of PAC of Ammonia-II has confirmed that it should
be possible to operate the machine with 75372 Nm³/h
without modifications.
 It was practically observed that the machine is in position
to deliver the desired load with no limitation on driver
side.
70
LINE1 AND LINE2 DIFFERENCE
 LINE 1 DOES NOT HAVE MIXED FEED
CAPABILITY ONLY NG CAN BE USED AS
FEED

 IN LINE1 AIR COMP IS RUN BY STEAM

TURBINE IN LINE 2 GT IS USED FOR
RUNNING AIR COMP
LINE1 AND LINE2 DIFFERENCE
 IN LINE 1 STRIPPING OF CONDENSATE
IS DONE BY LOW PREESURE STEAM
AND ALL THE STEAM IS VENTED TO
ATMOSPHERE
 IN LINE 2 STRIIPING IS DONE BY MP
STEAM AND STEAM IS REUSED IN
REFORMER THUS SAVING THE ENERGY
LINE1 AND LINE2 DIFFERENCE
 IN LINE 1 BENFIELD PROCESS IS USED
FOR CO2 STRIPPING

 IN LINE 2 GV PROCESS IS USED FOR CO2

REMOVAL

 LINE 1 DOES NOT HAVE PRE REFORMER

LINE1 AND LINE2 DIFFERENCE
 IN LINE 1 BENFIELD PROCESS IS USED
FOR CO2 STRIPPING

 IN LINE 2 GV PROCESS IS USED FOR CO2

REMOVAL

 LINE 1 DOES NOT HAVE PRE REFORMER