UREA YIELD IN LIQ PHASE & CO2 CONVERSION AS A

FUNCTION OF H2O:CO2 MOL RATIO

0.5 0.5

UREACONCENTRATIO IN LIQ
0.45 0.45

CO2 CONVERSION IN LIQ

PHASE (MASS FRAC)
1 0 0.4 0.4

PHASE(MOLECULE)
0.35 0.35
2 .25
0.3 0.3
3 .50 0.25 0.25
0.2 0.2
4 .75
0.15 0.15
5 1 0.1 0.1
0.05 0.05
0 0
1 2 3 4 5
UREA CONCn. IN LIQ 0.436 0.407 0.373 0.336 0.252
PHASE(MASS FRAC)
CO2 CONVERSION IN LIQ 0.461 0.420 0.377 0.336 0.286
PHASE(MOLECULE)
H2O:CO2 RATIO (MOL/MOL)

UREA CONCn. IN LIQ PHASE(MASS FRAC)

CO2 CONVERSION IN LIQ PHASE(MOLECULE)
•MELAMINE WAS FIRST DESCRIBED BY LIEBIG IN
1834.
•HOWEVER,IT WAS NOT UNTIL 100 YEARS LATER
THAT MELAMINE FOUND INDUSTRIAL INTEREST .
•WHEN IT WAS DISCOVERED THAT BY
CONDENSATION WITH FORMALDEHYDE INSTEAD
OF UREA,CONDENSATION PRODUCTS COULD BE
OBTAINED WHICH WHEN USED IN ADHESIVES ,
RESINS OR PAINT SYSTEMS, SHOWED
CONSIDERABLY BETTER PROPERTIES WITH
REGARD TO THAT PRODUCT PRODUCED FROM
UREA FORMALDEHYDE RESINS.
•e.g. WET STRENGTH OF THE ADHESIVES OR
WEATHER RESISTANCE AND GLOSS OF THE
PAINT.
• UNTIL ABOUT 1960, MELAMINE WAS
MANUFACTURED FROM DICYAN DIAMIDE IN
AUTOCLAVES AT 10 MPA & 400 o C .
• IN 1943, MACKAY FROM AMERICAN
CYANAMIDE CO(ACC) HAD DISCOVERED THAT
MELAMINE WAS OBTAINED BY THERMAL
DECOMPOSITION OF UREA BY REACTION :

6NH2CONH2 3(CH2N2) + 3CO2 + 6 NH3

• ALWAYS CHECK,
(1) UREA IS FOR MELAMINE CAPTIVE USE
OR
(2) UREA IS FOR FERTILIZER & CAPTIVE USES
• UREA 2X106 TONNE PER YEAR IS
REQUIRED FOR 685000 MT PER
YEAR OF MELAMINE PRODUCTION
@ 3.1 MT / MT.
• TOTAL UREA CAPACITY OF WORLD
IS 100X106 TONNE PER YEAR WHERE
2X106 TONNE PER YEAR IS USED
FOR MELAMINE ie 2% OF TOTAL
UREA GOES FOR MELAMINE
• MEDIUM SIZE MELAMINE PLANT REQUIRES
INVESTMENT OF $70~100 MILLION & SKILLED STAFF TO
GUARANTEE A HIGH STREAM FACTOR & CONSTANT
MELAMINE QUALITY .
 MOST OF THE CURRENT MELAMINE
PROCESSES WERE DEVELOPED IN THE EARLY
1960S.
SINCE THAT TIME SUBSTANTIAL PROGRESS
HAS BEEN MADE IN (1) AVOIDING CORROSION
PROBLEMS (2) INCREASING THE ON STREAM
FACTOR (3) FINDING BETTER CATALYSTS &
(4) ACHIEVING BETTER MELAMINE QUALITY.
ON THE OTHER HAND,MELAMINE PRODUCTION
AND DEMAND WORLD WIDE ARE ESSENTIALLY
BALANCED, NEW APPLICATIONS ARE RARELY SEEN
& IN CONRAST TO THE UREA MARKET, THE
MELAMINE MARKET IS COMPLICATED TO SERVE
AS MANY CUSTOMERS NEED TECHNICAL SERVICES
& MELAMINE OF VERY CONSTANT & HIGH PURITY.
 CURRENT MELAMINE PROCESSES

REACTION LOW PRESSURE <1 MPA HIGH PRESSURE>8MPA

CONDITION 390 ` 400 oC 400 o C
CATALYTIC NONCATALYTIC

MELAMINE WATER GAS WATER GAS

RECOVERY QUENCH QUENCH QUENCH QUENCH

PROCESS DSM / BASF NISSAN MCInc. -II

STAMICA- AGROLINZ
RBON EUROTECNI
AGROLINZ CA
 HIGH PRESSURE PROCESSES
PROCESSES;
IN THE THE HIGH PRESSURE,NON CATALYTIC
THE UREA DECOMPOSITION & MELAMINE
FORMATION TAKES PLACE IN A LIQUID MELAMINE
PHASE AT 410 o C & 8 MPA AND HIGHER.

 AMMONIA IS ADDED TO THE REACTION SECTION

TO GUARANTEE SUFFICIENT HEAT TRANSFER BY
INTERNAL MELAMINE CIRCULATION , AND TO AVOID
MELAMINE DECOMPOSITION TO HIGHER CONDENSED
PRODUCTS LIKE MELAM & MELEM.

CONT’D
 HIGH PRESSURE PROCESSES

 THE PLANT COMPONENTS OF THE REACTION

SECTION ARE MORE COMPACT THAN THOSE OF THE
CATALYTIC PROCESSES BUT THE HIGHLY CORROSIVE
NATURE OF THE MELAMINE MELT REQUIRES THE USE
OF EXPENSIVE CORROSION RESISTANT MATERIALS.

 ONE SPECIFIC ADVANTAGE OF THE HIGH PRESSURE

PROCESSES IS THAT THE OFF GAS CAN BE
ECONOMICALLY REUSED IN A UREA PLANT.
IT CAN DECIDE DESTINATION TO RELEASE AC
LIQUOR WITHOUT HARM TO ENVIRONMENT &
EQUIPMENT AS NO ATMOSPHERIC STORAGE INVOLVES.
NISSAN’S CONSUMPTION FIGURES PER TONNE OF
MELAMINE PRODUCED(HIGH PRESSURE &
NONCATALYTIC PROCESS)
RAW MATERIALS & UTILITIES
UREA(KG) 3040
AMMONIA(KG) 880
CARBON DIOXIDE(KG) 1140
ELECTRICITY(KWH) 400
STEAM,18BAR(KG) 1000
COOLING WATER(M3) 240
PROCESS WATER(M3) 4
FUEL(KJX106) 9.6(=2.286X106 KCAL)
WATER QUENCH (PROS & CONS)

 THE WATER QUENCH HAS THE ADVANTAGE OF

PRODUCING MELAMINE WITH HIGH & CONSTANT
PRODUCT QUALITY ; IMPURITIES ENTRAINED FROM
THE REACTOR SECTION CAN BE REMOVED BY THIS
AFTER TREATMENT.

 ON THE OTHER HAND, SINCE SMALL AMOUNTS

OF MELAMINE ARE HYDROLYSED OXOTRIAZINES
DURING THE QUENCH OPERATION AND THE QUENCH
PROCESS INVOLVES A MULTIPLE STAGE OPERATION
WITH A LARGE QUANTITY OF EQUIPMENT ,
ADDITIONAL WASTE WATER & OFF GAS STREAM
HAVE TO BE HANDLED.THIS CLEARLY INCREASES
BOTH INVESTMENT & OPERATING COSTS.
CONT’D
WATER QUENCH (PROS & CONS)

(MCI)
BECAUSE OF THIS, MELAMINE CHEMICALS INC
DEVELOPED A PROCESS IN WHICH THE
MELAMINE IS QUENCHED BY LIQUID AMMONIA
WITHOUT FURTHER TREATMENT.HERE, BY
ADDING ADDITIONAL VAPORISED AMMONIA TO
THE SEPARATOR THE AMMONIA PARTIAL
PRESSURE IS INCREASED AND THE FORMATION
OF BYPRODUCTS IS SUPPRESSED .

FOLLOW
IN GSFC MELAMINE PLANTS,SHOULD WE
SUCH PRACTICES IN MAIN SCRUBBER &
DRYER
1.IN MS,KEEP U/S VAPNH3 FLOW HIGHER THAN
OBSERVED @ POOR QUALITY PRODUCT
2.** CONT’D
WATER QUENCH (PROS & CONS)
1.**
2.IN DRYER,KEEP FILTER CANDLES CLEAN TO
RELEASE CO2, WATER VAPOUR & INERT GAS SO
THAT NH3 PARTIAL PRESSURE MAY BE
IMPROVED.

PROCESS
THE PURITY OF MELAMINE FROM THE MCI-II
IS ABOUT 97% AND CAN THEREFORE
NOT BE USED FOR ALL APPLICATIONS
GET SPECIFIED APPLICATIONS FROM
MCI-II WHICH CAN GUIDE TO GSFC MELAMINE
PRODUCTS TOO.

CONT’D
WATER QUENCH (PROS & CONS)

MELAM
THESE IMPURITIES CONSIST MAINLY OF
WHICH IS FORMED DURING THE QUENCH
PROCESS. MCI TRIES TO OVERCOME THIS
HANDICAP BY INCREASING THE PRESSURE IN
THE QUENCH PROCESS.

TECHNOLOGY
MELAMINE PRODUCERS WITH PROPRIETARY
HAVE BEEN RELUCTANT TO
LICENSE THEIR TECHNOLOGY. EUROTECNICA IS
THE ONLY ENGINEERING COMPANY WHICH
OFFERS A HIGH PRESSURE PROCESS,ORIGINALLY
BASED ON THE ALLIED TECHNOLOGY.
LOW PRESSURE CATALYTIC PROCESSES

LOW
THE ELECTRIC POWER CONSUMPTION IN THE
PRESSURE PROCESSES IS HIGHER THAN IN
THE HIGH PRESSURE PROCESSES BECAUSE
LARGER QUANTITIES OF GAS PER TONNE OF
MELAMINE HAVE TO BE HANDLED.

UNIT
ON THE OTHER HAND, HIGHER CAPACITIES PER
ARE POSSIBLE FOR HIGH PRESSURE
PROCESSES ARE 90,000 TPA PER UNIT WHILE FOR
NONCATALYTIC PROCESSES A MAXIMUM
CAPACITY OF 50,000 TPA SEEMS TO BE A LIMIT.

FAVOURABLY
THE LOW PRESSURE PROCESSES COMPARE
WITH HIGH PRESSURE PROCESSES
ESPECIALLY AT LARGE CAPACITIES.
CONT’D
LOW PRESSURE CATALYTIC PROCESSES

CATALYSTS
MOST PROGRESS WAS MADE IN FINDING NEW
WITH HIGHER ACTIVITY . THESE
CATALYSTS ALLOWED A CONSIDERABLE INCREASE IN
CAPACITY BY DEBOTTLENECKING ALONE IN STEAD OF
NEW INVESTMENT.

INSUFFICIENT
WHEN TEMPORARY OVER SUPPLY OF MELAMINE AND
PRICE TOOK AWAY THE INCENTIVE FOR
REWORKING(BUSINESS PROCESS RE ENGINEERING)-THE
PROCESS TECHNOLOGY, IT WAS MORE ECONOMICAL
TO DEBOTTLENECK.
OFF GAS TREATMENT

DEPENDING ON THE TYPE OF THE MELAMINE PLANT

(ie HIGH PRESSURE OR LOW PRESSURE ) AND TYPE OF
THE UREA PLANT(ie CONVENTIONAL OR STRIPPING ),
THERE ARE SEVERAL ALTERNATIVES FOR
INTRODUCING THE MELAMINE OFF GAS INTO THE
DIFFERENT SECTIONS OF THE UREA PLANT. BUT IN
PRACTICE,SOME RESTRICTIONS HAVE TO BE OBSERVED:

 IN MOST CASES ,THE OFF GAS CAN ONLY BE

RECYCLED TO THE UREA PLANT AS AN AQUEOUS
CARBAMATE SOLUTION . BUT WATER HAS A
DETRIMENTAL EFFECT ON CO2 CONVERSION AND
THUS ON UREA CONCENTRATION IN THE LIQUID
PHASE……… CONT’D
OFF GAS TREATMENT

 IMPORTANT FOR CONVENTIONAL UREA

PROCESSES,WHERE ALL UNREACTED CO2 HAS TO BE
RECYCLED AS CARBAMATE SOLUTION

 GRAPHIC SHOWS THE INFLUENCE OF WATER ON

CO2 COVERSION AND THE UREA YIELD IN THE LIQUID
PHASE AS A FUNCTION OF THE H2O : CO2 RATIO AT THE
REACTOR INLET.

 MOST UREA PROCESS OPERATE IN THE RANGE 0.50

~0.80 , BUT EVEN IN A CONCENTRATED CARBAMATE
SOLUTION (80%) THIS RATIO IS >1.2

CONT’D
OFF GAS TREATMENT

 THE HEAT REQUIRED FOR THE ENDOTHERMIC

CONVERSION OF CARBAMATE TO UREA IS
NORMALLY DELIVERED BY THE HEAT OF REACTION
OF THE AMMONIA & CO2 FED TO THE REACTOR.

 IF THE CARBAMATE STREAM TO REACTOR IS FOR

HIGH COMPARED WITH THE NH3 / CO2 GAS
INTRODUCED,THE NECESSARY REACTION
TEMPERATURE CAN NOT BE HELD, AND THE HEAT
BALANCE IS DISTURBED.

CONT’D
OFF GAS TREATMENT

IN MANY UREA PLANTS, THE CAPACITY OF THE

DECOMPOSER / CONDENSER SECTION IS WELL
MATCHED TO THE CAPACITY AND CONVERSION OF
THE UREA REACTOR , THEY ARE AT THEIR CAPACITY
LIMIT. THUS , DEBOTTLENECKING IS EXPENSIVE.
IT IS OBVIOUS THAT THE IMPORTANCE &
EXTENT OF ABOVE MENTIONED RESTRICTIONS
DEPEND STRONGLY ON THE RELATIONSHIP :
CAPACITY OF THE UREA PLANT COMPARED TO
AMOUNT OF MELAMINE OFFGAS.
 IN MANY CASES ,IT MAY BE MORE ECONOMICAL
TO COMBINE A REVAMPING OF THE UREA PLANT
WITH THE MELAMINE OFFGAS RECYCLING THAN TO
REPLACE EQUIPMENT IN THE UREA PLANT IN ORDER
TO PROCESS THE OFFGAS. A REVAMPED UREA PLANT
OFFERS MUCH MORE FLEXIBILITY & RELIABILITY.

 FOR EXAMPLE, UREA CASALE OFFERS DIFFERENT

APPROACHES FOR REVAMPING UREA PLANTS. FOR
STRIPPING PLANTS, THEY DEVELOPED THE VAPOUR
RECYCLE UREA PROCESS(VRS) . THE CONCEPT IS
BASED ON THE DECOMPOSITION OF RECYCLED
CARBAMATE WITH AN AUXILIARY DECOMPOSITION
SECTION,SOTHAT THE SYNTHESIS SECTION WILL BE
WORKING WITH MUCH LOWER AMOUNT OF WATER.

CONT’D
 IN FACT , IF SENDING THE OFFGAS STREAM TO
THIS NEW SECTION, THE SYNTHESIS WILL
PRACTICALLY RECEIVE ONLY AMMONIA & CO2
FROM THE MELAMINE OFFGAS AND NO WATER.

 IF FOR ANY REASON, A COMBINATION OF OFFGAS

TREATMENT WITH A UREA OR FERTILIZER PLANT IS
NOT POSSIBLE OR DESIRED, THE OFFGAS MIXTURE
CAN BE SEPARATED INTO ITS COMPONENTS NH3 &
CO2 BY SEVERAL METHODS.eg.

 (1)USE OF MEA SCRUBBING PROCESS (NO DETAILS

AVAILABLE)(2)AS CO2 PARTIAL PRESSURE IN
OFFGASES FROM LOW PRESSURE MELAMINE
PROCESSES IS TOO LOW TO APPLY PHYSICAL
ABSORPTION, SOLVENTS WITH CHEMICAL
CHARECTERISTICS LIKE MEA OR MDEA ARE
REQUIRED. (MDEA IS MORE EFFICIENT THAN MEA)
 THE SOLUBILITY OF DISSOLVED NH3 WILL
NEGATIVELY IMPACT THE EFFICIENCY OF THOSE
SYSTEMS OF MDEA & MEA, BASF HAS DEVELOPED
SPECIAL SEPARATION PROCESS FOR ITS MELAMINE
PROCESSES WHICH USES THE DIFFERENT
VELOCITIES OF ABSORPTION BETWEEN NH3 & CO2
FOR SEPARATION OF COMPONENTS.

 ie THE OFFGAS FROM MELAMINE PLANT

CONTACTS A DILUTE NH3 / CO2 SOLUTION IN TWO
ABSORBERS ARRANGED IN SERIES HAVING SHORT
CONTACT TIME, THUS STRIPPED NH3 IS COMPRESSED
& LIQUIFIED WHILE NH3 CONTAMINATED IS WATER
WASHED TO REMOVE NH3.
THE MELAMINE SHOULD ALSO HAVE A CONSTANT
& HOMOGENOUS PARTICLE SIZE TO GUARANTEE A
REGULAR VELOCITY OF SOLUTION ,AND IT SHOULD
BE FREE OF UREA BECAUSE THIS CAN CAUSE
COLOR CHANGES DURING FURTHER
PROCESSING.FOR THESE REASONS ,IT IS QUITE
CLEAR THAT MELAMINE MUST HAVE PURITY OF
ATLEAST 99.9% FOR FOLLOWING USES.
PAPER & TEXTILES, COATINGS , ADHESIVES,
LAMINATES, MOULDING COMPONENTS & OTHERS.
SEPARATION PROCESS WAS DEVELOPED BY
AGROLINZ.
IT WORKS ON THE BASIS OF DISTILLATION &
ABSORPTION AND IT MAKES USE OF AMMONIA &
CO2 OVER CARBAMATE SOLUTIONS AT DIFFERENT
PRESSURES.THE OFF GAS IS FED TO A CO2 SCRUBBER
AND SURPLUS AMMONIA LEAVES THE SCRUBBER AT
THE TOP.
THE DISSOLVED AMMONIA IS STRIPPED OFF FROM
THE RESULTING AMMONIA /AmCm SOLUTION IN A
STRIPPER.THE CARBAMATE SOLUTION FROM THE
BOTTOM OF THE STRIPPER IS COMPRESSED TO
ABOUT 20 Bar,AND THEN THERMALLY DECOMPOSED
IN THE SOCALLED ‘CO2 STRIPPER’.
AFTER A WATER WASH, CO2 FROM THE TOP OF CO2
STRIPPER CAN BE REUSED.
THE SOLUTION AT THE BOTTOM OF THE STRIPPER
,POOR IN CO2, IS AFTER HEAT EXCHANGE,REUSED IN
THE CO2 WASHER.

ARTICLE FOCUSES ON VRS (VAPOR, NH3&CO2,

RECOVERY SYSTEM) FOR OFFGASES FROM
MELAMINE PRODUCTION .
AT UREA-MELAMINE UNITS OF GSFC,
CRS(CONDENSATE RECOVERY SYSTEM) IS BEING
TRIED AS AN R&D IN COMMERCIAL MELAMINE
UNITS.
 SUCTION TO RELIQUIFICATION (PCV-619 OF MEL-1)
ENSURES SUCTION TO BHEL & FINALLY OVERALL
CLOSED LOOP .
 BACKPRESSURE OF AC TREATMENT & OFFGAS
TREATMENT IN MEL-1 WILL BE MONITORED.
 SIMILARLY,PCV-421 ENSURES SUCTION TO DEMAG
NH3 COMPRESSOR & OVERALL LOOP ACCORDINGLY.
 INCREASE OF SUCTION WILL BRING TOWER
PRESSURE MORE CORRESPONDINGLY & RESULTING
HIGHER PARTIAL PRESSURE OF NH3 & CO2
REACTION TO COALESCE WITH NH3,H2O OR
CONDENSATION OF CO2 BY WAY OF AmCm
FORMATION IN TOWER ITSELF.
 NC = RELATIVE VOLATILITY OF NH3 OVER CO2
= (VP)N /(VP)C

 MEL-1 PCV-619 ACTUAL SET= 0.1 KG/CM2(G)

 MEL-2 PCV-421 ACTUAL SET = 0.05 KG/CM2(G)
 THIS SET DIFFERENCE AFFECTS CO2
SEPARATION EFFICIENCY ADVERSELY AT MEL-2
MELAMINE APPLICATIONS BY REGIONS(in %)
EUROPE USA JAPAN ASIA
PAPER&TEXTILES 3 5 3 0
COATINGS 6 19 14 0
ADHESIVES 25 24 62 80
LAMINATES 56 35 10 5
MOLDING COMPS 4 9 5 10
OTHER 6 8 6 5
TOTAL 100 100 100 100

PAT C A L M OTHER
∮ IN THE PAST FIVE YEARS (REVIEWED IN 1997
BY BASF) THE ANNUAL GROWTH RATE FOR
MELAMINE CONSUMPTION WORLDWIDE HAS
BEEN ESTIMATED AT 4 ~ 5% . A SIMILAR GROWTH
RATE IS EXPECTED FOR THE FORSEEABLE
FUTURE.WORLDWIDE ANNUAL PRODUCTION
CAPACITY IS ESTIMATED AT 685000 TONS AND
THIS CAPACITY CORRESPONDS WELL WITH
EXPECTED DEMAND FOR THE YEARS TO COME
COUNTRY COMPANY CAPACITY
EUROPE 282000
Austria Agrolinz 50000
France ELF atochem 16000
Germany BASF 48000
Italy Agrolinz 40000
Netherlands DSM melamine 90000
Poland Pulawy 30000
Romania Azoures 8000
COUNTRY COMPANY CAPACITY

UNITED STATES 108000

United states Melamine 48000

chemicals inc.

American 60000
melamine
chemicals
COUNTRY COMPANY CAPACITY
Japan 116000
Japan Mitsubishi 30000
petroleum co.
Mitsui toatsu 40000
chemic.

Nissan chemic. 46000

COUNTRY COMPANY CAPACITY
Asia 179000+10000
China Sichuan general 12000
chemic.works
India Gujarat state 5000+10000
fertilizer
Indonesia DSM kaltim 50000
Sri melamine rejeki 20000

Korea Namhae chem. 20000

Samsung fine 16000
chemicals
Iran Orumiyeh petr. 3000
Saudi arabia SAFCO 20000