An overview of ALKYLATION & BUTAMER UNIT

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Paradip Refinery

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This sulphuric acid Alkylation Unit plant is the first of its kind among all Refineries of IOCL.

Paradip Refinery

A Sunrise Project for A Sunshine Future

UNIT CONFIGURATION

Paradip Refinery

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BRIEF DESCRIPTION OF THE ALKYLATION UNIT

LICENSOR : M/s EXXON MOBILE, USA. LSTK contractor : M/s Punj Lloyd DETAIL ENGG. CAPACITY : M/s Aker power gas Pvt. Ltd : DIOS unit design capacity 442 KTPA i.e. 53.1 MT per hour Alkylation unit design capacity 650 KTPA i.e. 78.1 MT per hour On stream factor: 8320 HRS./YR OBJECTIVE : For maximisation of MS production as well as to improve its quality in line with premium Euro-IV grade, having high RON , low RVP & low benzene (< 0.1 wt%). PROCESS CHEMISTRY : Olefin & isobutane are mixed with the sulfuric acid catalyst in the reactor and chemically combine to form iso-octane rich alkylate.

Paradip Refinery

A Sunrise Project for A Sunshine Future

OBJECTIVE (DIOS SECTION)

To selectively hydrogenate >99% of butadiene (BD) in C4 olefinic stream.

Reduces the butadiene in its feed stream from 2.89 wt% to 200 wppm, since dienes cause high acid consumption in the Alkylation Unit.
The fresh feed is blended with recycled product from the bottom of the stripper to maintain the reactor inlet butadiene concentration at 1.30 wt%.

PROCESS CHEMISTRY :

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PFD OF DIOS SECTION

HYDROGEN GAS Treat gas rate = 968/1290Nm3/hr H2/BD= 1.5/2.0 STATIC MIXER

Reactor EIT= 66.3/92.2 C Pressure=35.2 kg/cm2-g T= 14 C P= 0.95 kg/cm2-g

CWS

FEED HEATER

LP/MP STEAM

DIOS REACTOR Reflux Drum

21

FG

DIOS FEED FROM PRU

FEED RATE= 89.5 m3/hr BUTADIENE = 2.89% SULPHUR= 25 wppm

BD = 1.3 WT%
17

SWS

DIOS STRIPPER
Temp.= 100 C Press.=17.1 kg/cm2-g

FEED SURGE DRUM

SWS CWS LP STEAM

DIOS PRODUCT
To ALKYLATION UNIT

(BUTADIENE <= 200wppm)

Excess DIOS Prod. To LPG Blending

DIOS UNIT RECYCLE

RECYCLE RATIO= 1.25

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FEED STOCK(DIOS)
Feed stock is mostly C4 molecules (97.73 wt %), consisting of 66.20 wt% olefins, 2.89 wt% butadiene (BD).
Feed Composition COMPONENT i-Butane i-Butene Butadiene Butane n-Butene-1 t-Butene-2 c-Butene-2 TOTAL

S. No. 1. 2. 3. 4. 5. 6. 7.

WT % 19.98 22.27 2.89 9.24 14.3 17.33 11.72 100.0

S. No. 1. 2. 3.

Treat Gas Composition (mol %) Contaminants PPMW H2 99.5% Methane By balance Ethylene Nil

Paradip Refinery

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PRODUCT QUALITY(DIOS)
Dienes at out let of DIOS section is 200 PPMW.

S. No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

Product Composition (WT %) COMPONENT Wt%

Propylene Propane 0.49 0.74

i-Butane n-Butane
Isobutylene Butene-1 TR-Butene-2 CIS-Butene-2 Butadiene 2M-Butene-1 Isopentane n-Pentane

19.94 9.31
22.24 11.95 22.28 12.02 0.02 0.07 0.67 0.27

TOTAL
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100.0

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PROCESS VARIABLES (DIOS)

Reactor Temperature : SOR 57 deg. C , EOR 83 deg. C Hydrogen : Butadiene Ratio : Unit is operated between 1.5 at SOR and 2.0 at EOR on molar basis. Space Velocity : Unit is operated at 8.07 hr -1 LHSV Reactor Pressure and Bed Pressure Drop : Reactor operates at 35.2 kg/cm2(g). Catalyst Type / Volume : Pd catalyst-25 m3 Catalyst Activity : Sulfur is the main contaminant expected in the fresh feed that will inhibit the performance of the palladium catalyst.

Paradip Refinery

A Sunrise Project for A Sunshine Future

PFD of ALKYLATION UNIT

REFERIGERATION COMPRESSOR M

0.3 kg/cm2-g

6 kg/cm2-g
DP BOTTOMS

Reflux drum
DEPROPANISER

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KO Drum
Receiver economiser
Caustic & Water Wash System

PROPANE
TO STORAGE

LP STEAM

CCR LPG DIOS STRIPPER BOTTOM 40 C

TO TRAIN -2
ISOBUTANE RECYCLE

EXCESS ISOBUTANE
TO LPG BLENDING

FEED CHILLER

FROM TRAIN -2

Reflux Drum

DEISOBUTANISER

Caustic & Water Wash System

4.4 C

18 C

FEED EFFLUENT H.E.

BUTAMER EFFLUENT

REACTOR

SETTLER

Reflux Drum

DEBUTANISER

BUTANE
TO BUTAMER

SPENT ACID TO SARU

FRESH ACID MAKE-UP NSU LPG ALKYLATE PRODUCT TO TANKS RATE = 78.1 MT/hr RON= 96.3 RVP=0.29 Kg/cm2

A Sunrise Project for A Sunshine Future

FEED STOCK (ALKYLATION )

S. No. 1. 2. 3. 4. 5. 6. 7. Components Propane Isobutane n-Butane Isobutylene Butene-1 TR-Butene-2 CIS-Butene-2 Olefins from CCR LPG 42.27 21.39% 32.88 % NSU LPG 1.70% 21.67% 74.97 % Butamer product

DIOS Stripper --19.94%

9.31 % 22.24 % 11.95 % 22.28 % 12.02 %

59.56% SOR, 56.76% EOR 37.81% SOR, 41.27% EOR

Fresh 98% Purity Sulphuric Acid as makeup (2100 MT for initial fill & 160 MT/Day)

Fresh 20% Caustic as makeup (NaOH)

(179 Sm3 for initial fill & 9.51 MT/Day )

Paradip Refinery

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PRODUCT QUALITY(ALKYLATION)
Alkylate properties :S. No. 1. PROPERTIES Rate, m3/hr Value 111.09

2. 3.
4. 5.

Specific Gravity(15/15) RON, clear

MON, clear RVP, kg/cm2

0.704 96.3
93.7 0.29

Paradip Refinery

A Sunrise Project for A Sunshine Future

PROCESS VARIABLES (ALKYLATION )

Reaction Temperature : Operating range is between 2-5.7 Deg C Acid Strength : Best alkylate quality and highest alkylate yields are obtained 92 to 95 wt% acid strengths. Isobutane Concentration : Design isobutane concentration is 62.7 LV% in the reactor product stream. Olefin Space Velocity : Overall olefin space velocity is 0.090 m3/hr olefin/m3 acid inventory. Percent Acid-in-Emulsion (Acid/Hydrocarbon Ratio) : Most desirable range is 60 to 65%. Reactor Mixing : Mixing is important in sulfuric acid alkylation because the isobutane solubility is low and the acid catalyst is viscous at the low operating temperatures employed. Olefin Feed Injection : To minimize the polymerization reactions, the feed is jetted into the reactor emulsion through feed rings , each having 86 feed jets at a high velocity(30 m/s)

Paradip Refinery

A Sunrise Project for A Sunshine Future

MATERIAL BALANCES (ALKYLATION)

Alkylation unit (Butamar yield design case)

SOR Case
OUTPUT S. No. Feed streams MT/HR Products streams MT/HR 1. Alkylation Feed ex DIOS 52.536 Alkylate 78.03 2. CCR LPG 23.027 Propane 11.13 3. SR LPG 16.02 NC4 37.79 4. Butamar product (ic4) 35.6 ASO 0.233 6. Total 127.183 127.183 INPUT

EOR Case
INPUT S. No. Feed streams 1. 2. 3. 4. 6. Alkylation Feed ex DIOS CCR LPG SR LPG Butamar product (ic4) Total MT/HR 52.55 23.03 16.03 37.39 129.00 OUTPUT Products MT/HR streams Alkylate 78.08 Propane 11.04 NC4 39.61 ASO 0.27 129.00

NOTE : ASO (acid soluble oil ) purged along with spent H2SO4

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A Sunrise Project for A Sunshine Future

BRIEF DESCRIPTION OF BUTAMER UNIT

LICENSOR LSTK contractor DETAIL ENGG . CAPACITY On stream factor : M/s UOP, USA. : M/s Punj Lloyd : M/s Aker power gas Pvt. Ltd : 35621 kg/hr (iC4 = 59.60 mol%) of isomerate at SOR and 37382 kg/hr of isomerate (iC4 = 56.90 mol%) at EOR . : 8320 HRS./YR

OBJECTIVE

The unit purpose is to produce isobutane from n-butane ex-alkylation unit to balance the requirement of isobutane within the Alkylation unit. PROCESS CHEMISTRY :

CH3
CH3-CH2-CH2-CH3
Pt
Acid/PERC

CH3-CH-CH3

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PFD of BUTAMER UNIT

BUTAMER FEED
FROM ALKYLATION UNIT COALESCER

CHLORIDE INJECTION CHARGE HEATER

ISOMERISATION REACTORS

Feed Surge Drum

LIQUID FEED DRIERS

HP STEAM

FLOW= 35453 / 37389 kg/hr (iC4 = 1.45 %,nC4= 97.7 %)

HCFE CCFE

LEAD

LAG

METHANATOR REACTOR
Temp.= 232 C Press.= 41 kg/cm2g

(CO+CO2= 10w ppm CO = 1wppm)

H2/HC = 0.03

Temp.= 93-174/120.156 C Press.= 31.8 kg/cm2g LHSV = 4

NET GAS PREHEATER

FG
Wash water circulation pump

NET GAS CHILLER

NET GAS SCRUBBER

Stabiliser

Reflux Drum

HP steam MAKE UP GAS DRIERS

LP STEAM

Caustic circulation pump

FRESH CAUSTIC MAKE-UP

MUG K.O. Drum cws H2 MAKE-UP GAS

ISOMERATE
TO DIB AT ALKYLATION UNIT

FLOW= 35621 / 37382 kg/hr (iC4 = 56.90 %,nC4= 41.37 %)

FLOW=45 kg/hr (CO+CO2= 20 ppm)

Paradip Refinery

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Feed Composition Components Isobutane n-butane Isopentane Total

FEEDSTOCK (BUTAMER )
Composition, mole% 1.45 97.69 0.86 100.0

Hydrogen Makeup Gas Composition Stream composition units Hydrogen Volume% Methane Mole% sulfur Mole ppm Nitrogen (excluding Mole ppm N2) HCl Mole ppm CO+CO2 Volume ppm Total
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value 99.5 Balance Nil 0.00

1 20 100.0

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PRODUCT QUALITY (BUTAMER)

S.No.
1. 2. 3. 4. 5. 6.

Components
Propane Iso butane n-butane i-pentane n-pentane C6+(n-hexane) Total

Composition mole% SOR EOR 0.85 0.40 59.89 56.90 37.57 41.37
1.25 0.37 0.07 100.0 0.96 0.32 0.05 100.0

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PROCESS VARIABLES(BUTAMER)

REACTOR TEMPERATURE Minimum inlet temperature=105oC Maximum bed temperature=205oC LIQUID HOURLY SPACE VELOCITY : Units are operated at 4 1/hr LHSV HYDROGEN TO HYDROCARBON RATIO : Units are designed to operate at a 0.03 H2 mole ratio at the reactor outlet. PRESSURE :Typical operating pressure is 31.6 kg/cm2 g.

Paradip Refinery

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MATERIAL BALANCE (BUTAMER)

Feed Stream Feed ex Alkylation Make up Hydrogen Total Product Stream Isomerate Fuel Gas Water Total UOM kg/hr kg/hr kg/hr kg/hr Start of Run 35621 360 12 35993 End of Run 37382 294 12 37688 UOM kg/hr kg/hr kg/hr Start of Run 35948 45 35993 End of Run 37643 45 37688

Paradip Refinery

A Sunrise Project for A Sunshine Future

THANK YOU

Paradip Refinery

A Sunrise Project for A Sunshine Future