axens state of the art solutions for base chemical purification · 2019-11-15 · mercury removal...

Axens State of the Art

Solutions for Base Chemical

Purification

Dinesh KHOSLA

Axens’ State of the Art Solutions for Base Chemical

Purification

Indian Petrochem 2019, 14-15 November, Mumbai | 2

Petrochemical & Polyolefins Market

Fulfill the market demands for very

performing products

New technologies

Purification systems more sophisticate

Valuables Monomers are

available but comes with impurities

Very performant catalysts =

Very dependant of impurities presence


POLYMERIZATION

Petrochemicals

AROMATICS

MERCURY

REMOVAL

OTHER OLEFINS SOURCES

ETHANE

LPG

CONDENSATES

NAPHTHA

OTHERS

NAPHTHA

RAFFINATE PYGAS

AROMATICS

OLEFINS

BASE CHEMICALS

GASOLINE POOL ETHERS

PYGAS

POLYOLEFINS

From Pygas

Hydrodealkyl.

Complex

ALTERNATIVE CHEMICALS

BIOMASS OLEFINS

STEAM CRACK

ER

GAS

PURIFICATION

BENZENE

TOLUENE

XYLENES

MERCURY

REMOVAL

C2 & C3

C4

C5 & C5+

OLEFINS / PYGAS

PROCESSING &

PURIFICATION


C3 Propylene

LD 265, LD 273, LD 275: liquid phase LT 279: vapor phase

C3 Selective Hydrogenation Gas/Liquid Phase Purification

AxSorb (regenerative) AxTrap (sacrificial)

Pd: LD 485, LD 465 Ni: LD 551, LD 541, LD 341, LD 241


Steam Cracker Environment

LD 485, LD 465

C4/C5 Total Hydrogenation Saturated C4/C5

(co-cracking)

Max butenes

Butadiene C4

BD extraction

C4 BD Rich Selective

Hydrogenation

LD 265, LD 277 LD 267 R, LD 269, LD 271,

LD 2773

Residual BD Hydrogenation

Or Hydroisomerization

Max butene-2

Max butene-1

C2

Ethylene C2 Selective Hydrogenation

LT 279, LD 153

Gas Phase Purification


Liquid Phase

Purification

Aromatics

Gasoline pool

C5+

LD 145 + HR 606

Pygas 2nd Stage

Pygas 1st Stage

C5

Ste

am

Cra

ck

er

Fu

rna

ce

s &

Dis

tilla

tio

ns


Cracked gas Compressors

Caustic W

ash

Ethylene

Heavy Pygas

Gasoline

1st to 3hd STG

Acethylene converter

MAPD Hydro

Propylene

H20

BD extraction

Butadiene

Ethane to steam Cracker

Propane

Quench Oil

Tower

Quench water

Tower

Fuel gas

water

Distillate stripper

Condensed water

AsH3 Condensats

PE unit

PP unit

H2, CO …

Hydrogen

Fuel gas (CH4, CO …) Cracked-gas

dryers

KO drum

AsH3

H2

H2

MAPD

VAC

C4+

C3+

BD Hydro Butenes

C5+

1st stage Pygas Hydro

H2

BTX

H2

2nd stage Pygas Hydro

Gasoline

Ethane / Naphta

C2+

H2 PSA

H20

Steam Cracker and Contaminants Methanator

Chilling Cold box

H2


Axens Product Offer for Monomers Purification

Products Type Benefits

AxSorb 537 3A Molecular Sieve

(extrudates)

For drying: Excellent adsorption kinetics

Very low olefin coadsorption

Superior coking tolerance

Good mechanical properties

AxSorb 913 13X Molecular Sieve For Polar molecules removal < 10Å diameter (Methanol, H2S, CO2, RSH,

DMS, DMDS, Ketones, Nitriles, Ethers, olefins)

AxSorb 900/902 Hybrid (beads)

High performance polar molecules removal

Low adsorption heat release

Simplified operation

AxSorb 980/984 Promoted Alumina

(beads)

For CO2 & COS removal: Higher capacity products with high stability, lower

coking

No adsorption heat release

AxTrap 100 serie Metal Oxide (beads)

High Arsine/Phosphine/S pickup capacity

Loading/Unloading under air

No pre/post-treatment

AxTrap 200 serie (beads) Mercury removal

Loading/Unloading under air


Axens Catalysts & Adsorbents Offer:

Principles and Overview


■ Depends on the specific impurities to be removed, the feedstock composition, the impurity and the outlet specifications:

Typical Impurities & Adsorbent Selection

A large Adsorbents

product range is needed

Cracked-gas: H2O, NH3, Hg

Ethylene: H2O, O2, CO/CO2, H2S, NH3, NOx, N2, Alcohols (mainly methanol), Aldehydes, Ketones, Peroxides, Amines, Chlorides, Phosphine (PH3)

Propylene: H2O, O2, CO/CO2, Sulfurs (H2S, Mercaptans, COS, DMDS), NH3, Alcohols (mainly methanol), Aldehydes, Ketones, Peroxides, Amines, Arsine (AsH3)

Molecular Sieves (zeolites)

Activated and Promoted Aluminas

Hybrid or composite Material

Metal Oxides

Feed & Impurities ? Adsorbent ?


■ Target: Olefin Purification

■ Reactions to promote:

Diolefins & Acetylenics Hydrogenation

Olefins Isomerization (if required)

■ Other reactions are undesirable because:

Loss of desired products (ethylene and propylene)

Higher production of lower value products

Higher hydrogen consumption

Higher gums formation leading to reduce cycle

Catalyst - Selective Hydrogenation

Specific catalyst is required depending on the application

to be Selective


Base Chemical Purification: Ethylene


Polymer

Grade

Ethylene

Acetylene

Converter

Impurities

removed

ppm ppb

From

furnaces

H2O

NH3

Methanol

CO2

H2S

RSH

COS

Arsine

Phosphine

Typical Gas Phase Purification

AxSorb

533/537

AxTrap

191

LT 279

LD 153

AxSorb

900/902

AxSorb

980/984

Purification


■ LT 279: Former Generation

Many references in vapor phase and more particulary in FE hydrogenation

(excl. repeat orders and spare reactor)

■ LD 153: New Generation

Differences between LD 153 and LT 279:

› Higher selectivity to maximise ethylene yield ➨ multi promoted

› Higher stability during CO fluctuations to avoid runaways

› Low pressure drop ➨ 5mm beads

› Improved resistance to contaminants (arsine, phosphine)

C2 Front-end Hydrogenation Catalysts


Base Chemical Purification: Propylene


Polymer

Grade

Propylene

MAPD

Converter

Impurities

removed

ppm

H2O

NH3

Methanol

RSH/RSSR’

COS

Arsine

Phosphine

COS

Typical Liquid Phase Purification

Product

Propane

ppb

LD 265

LD 273

LD 275

AxSorb

900/913

AxSorb

980/984

AxSorb

537

AxTrap

191 or

192/194

C3/C3= Splitter Purification


■ Selectivity: key to maximize profits

■ LD 265 reference option: many references in C3 hydrogenation

Standard design upstream PP Splitter, ideal for 1 stage scheme

■ LD 273 high performance – bi-metallic noble metal

many references in C3 hydrogenation

■ LD 275 new formulation: new catalyst for C3 hydrogenation

C3 Cut: Catalyst Selection

Low Pd content ➨ Cost control

Propylene yield improvement

› 1% gain at 10 ppm MAPD

Industrial experience at 1 ppm MAPD

Long cycles > 3 years


Base Chemical Purification: Butene


C4 Cut: Catalysts for Butenes Maximization

C4

feed

H2

make-up Product

butadiene

<10 ppm

Catalyst type

depends on targeted

butene isomer

Butadiene ~0.5 wt%

Many references to date

LD 265

or other

LD

LD 265

LD 271

LD 269

LD 267R

AxSorb

913

From ~50%

butadiene down to

ppm level

2 stages

scheme


■ Butene-1: high value co-monomer for polyethylene

Sustained growth (LLDPE and HDPE demand)

■ LD 271 catalyst for Butene-1 maximization

High performance

› Butadiene removal

› High butene-1 yield

› Low Pd content ➨ Cost control

› Long operating cycles

C4 Value Chain: Maximizing Butene-1

Butadiene

Butene-1

Butene-2

n-Butane


■ Butene-2: Intermediate for different applications

High purity isobutylene separation

Oligomerization, HF alkylation feedstocks

Propylene synthesis via metathesis, …

› Butene-2 is the only reactive C4 isomer

C4 Value Chain: Maximizing Butene-2

butadiene

Butene-1

Butene-2

n-butane

Hydroisomerization Optimal Solution

Hydroisomerization towards butene-2:

The solution: LD 267 R or LD 269 catalyst


Base Chemical Purification: C5+


Pygas 1st Stage: Palladium or Nickel Catalyst

Catalyst Type Palladium based catalyst Nickel based catalyst

Targets Cost to fill Maximum

activity Cost to fill

Maximum

activity

Feeds

LD 465 LD 485 LD 341 LD 541 & LD 551

Clean

feed

Contamined feed

Benzene

Toluene

Mixed Xylenes

C5+

C5

Gasoline

Pygas Value Chain (Typical)

Pygas 1st Stage Hydrogenation

(GHU-1)

Pygas 2nd Stage Hydrogenation

(GHU-2)

Aromatics Production /

Recovery

Stabilize unstable diolefins

& alkenyl aromatics Prepare feed to Pygas

2nd Stage Main duty:


Pygas 2nd Stage Dual Catalytic System

Neutral NiMo LD 145

Many references

Neutral NiMo benchmark

Prevent gum formation in

downstream HDT catalyst

Low P feature (2-4 mm

spherical)

LD 145 HR 606 1.6

Diolefins & styrenics

saturation

Olefins complete

saturation, S removal

Feed On-spec product: S, B.I.

Main duty:

HDT CoMo HR 606

Many references

High activity

Aromatics selectivity

Evolution of former HR 306 & HR 406

many references

Multilobe extrudate


■ A complete and large Catalyst and Adsorbent portfolio:

efficient and industrially proven

■ Deep Knowledge

■ New successful catalysts and adsorbents perfectly oriented towards

petrochemicals market demand

■ Technical Services: Axens’ regional forces handle:

follow-up

troubleshooting (processes, catalysts and adsorbents)

Conclusion

A single source for multiple technologies & products to

meet all olefins purification requirements


Thank www.axens-solutions.net you!

axens state of the art solutions for base chemical purification · 2019-11-15 · mercury removal...

Documents