redefine fcc catalyst testing for advanced technical

Redefine FCC catalyst testing foradvanced technical service

support in new markets

Dr. Marius Kirchmann, Dr. Alfred Haas

10. December 2020

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MDU: an enabling technology to FCC catalyst testing

BBTC MENA & ME-CAT 2020, 8-10 December 2020, Kirchmann et al.

FCC

Introduction

Catalyst

Deactivation

Analytics /

Workflow /

Lab 4.0

Kinetic

Modelling

Catalyst

TestingCase Studies

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Fluid Catalytic Cracking (FCC)Overview

• 500 FCC units worldwide

• Main conversion technology for bottom of the barrel (VGO /

Resid)

• Main products are gasoline, distillates and LPG

• Catalyst market of ~ 3$ billion


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steam

steam

Fluid Catalytic Cracking (FCC)Lab test requirements

Products

Feed

Cat

alys

tTes

ting

Feed Ni, V

Products

Fresh Cat Make-up

ECat

Fresh Cat

DCat

CatalystD

eactivation

~20% steam


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steam

steam

Fluid Catalytic Cracking (FCC)Lab test requirements

Products

Feed

Cat

alys

tTes

ting

Feed Ni, V

Products

Fresh Cat Make-up

ECat

Fresh Cat

DCat

CatalystD

eactivation

~20% steam


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FCC catalyst testingOverview on lab methods

MDU ACECRU

Catalyst

Feed

Cracking count / day

• 3-5 kg

• ~30l / day

• 2-3

• 30-150 g (dep. on C/O)

• <10 ml

• Up to 18

• 7g

• <10 ml

• Up to 18


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FCC catalyst testingOverview on lab methods

MDU ACECRU

• Entrained flow • Entrained flow • Fixed-fluidized bed

N2

N2

N2

Reactor regime


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FCC catalyst testingContact time

MDU ACECRU

Time on feed

Contact time gas

Contact time catalyst

• Continuous

• 1.5-5s

• 1.5-5s + slip factor

• 60s

• 0.5-4s

• 0.5-4s – slip factor

• 30-60s

• 2s

• 30-60s

N2

N2

N2

Contac t

T ime

1.5 -5s

Contac t

T ime

0.5 -4s

O i l Con tac t

T ime

2s


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FCC catalyst testingTemperature

MDU ACECRU

• 700°C → ROT • 700°C → DOT (ROT) • Isothermal

N2

N2

N2

700°C

ROT

530°C

DOT

530°C

700°C

ROT

530°C

Temperature gradient

Implications


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FCC catalyst testingCoke gradient

MDU ACECRU

• Gradient

• Constant (fresh)

• Gradient

• Constant (fresh)

• Fully back-mixed

• Increases during TOS

• Activity changes / averaging

N2

N2

N2

High

High*Low

Reg

Reg

Low

High

Coke

CoC during feed contact


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FCC catalyst testingCoke profiles

MDU ACECRU

• T Gradient • T Gradient

N2

N2

N2

High

HighLowLow

RegReg

Reg

Low

HighK

ine

tic

co

ke

1 .50

1 .25

1 .00

0.75

0 .50

0 .25

010 2 3 4 5 6 7 8

Cata lyst contact t ime

matr ix

zeol i te

En

tra

ine

dfl

ow

En

tra

ine

dfl

ow

• Fully back-mixed

• Increases during TOS


Lucas Doraz io , J i an Sh i , James Fu , Junmei Wei , CP Ke l ka r , Abs t rac t NAM 2018

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Micro Downflow Unit (MDU)Technology


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MDUNew generation

• Up to 18 C/O measurements per day

• Flexible feedstocks:

• VGO / Resid with CRC’s 0-10% (15%)

• Crude Oil

• Lighter feeds (naphtha, gas)

• C/O: 3 to 50 (100)

• Pressure: 0.5 to 3.5 barg

• Reactor temperature: up to 700°C

• Catalyst temperature: up to 900°C

• Variable stripping efficiency

• Cost effective (operation, catalyst, feedstock)

• Fully automated lab system


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MDUSimplified process scheme

Part ic le recovery

• Fast exchange of 6 cata lyst conta iners

Liquid recovery

• Fast exchange of 6 t raps

Par t ic le dosage

• Thermal reservour

• Var iable cato i l

Downf low reactor

• Mult ip le heat ing zones

• Short contact t ime 0.5-4s

Feed dosage

• Precise dosage of broad

range of feedstocks

Gas recovery

• Volume col lect ion

• Onl ine GC

SolidsLiquidsGases


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MDUTemperature control

N2

Temperature (°C)

500 600 700 800 900400

CatT = 700°C

ROT = 530°C

TOS 1s 10s 15-60s

N2


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MDUTemperature control

N2

Temperature (°C)

500 600 700 800 900400

CatT = 900°C

TOS 1s 10s 15-60s

ROT = 530°C


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MDUSummary

• „Nothing is constant in FCC“

• Gradients exist in temperature, partial pressure, coke,

…

• Entrained flow reactors (CRU, MDU) resemble the

commercial process

• MDU

• Cost efficient and fast testing in laboratory scale

• Flexibility to access broad parameter space and feeds


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MDUApplications

Classical FCC Petrochemicals Crude Oil to Chemicals Sustainable Processes

• Catalysts / additives

• Process optimization

• Feed testing



• Pyrolysis (CPP)

• Alternative feeds

• Naphtha (Petroriser)

• Resid

• Propane (PDH)

• Methanol



• Pyrolysis

• Biogenic feeds

• Sugar conversion

• Pyrolysis oi l ( i .e co-

processing)

• Circular economy

• Plastics

• Pyrolysis


1 2 3 4

1 picture © Avigator Fortuner/shutterstock

² picture © Aunging /shutterstock

³ picture © Thaiview /shutterstock4 picture © kram-9 /shutterstock

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steam

steam

FCCProcess / test requirements

Products

Feed

Cat

alys

tTes

ting

Feed Ni, V

Products

Fresh Cat Make-up

ECat

Fresh Cat

DCat

CatalystD

eactivation

~20% steam


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steam

steam

FCCProcess / test requirements

Products

Feed

Cat

alys

tTes

ting

Feed Ni, V

Products

Fresh Cat Make-up

ECat

Fresh Cat

DCat

CatalystD

eactivation

~20% steam


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Catalyst deactivationOptions to deactivate fresh FCC catalysts

Hydrothermal Steaming (HT) Cyclic Propylene Steaming (CPS) Cyclic Metals Deactivation (CMD)

• No metals impregnation

• Hydrothermal steaming

• Metals deposition by separate

impregnation step (MM / SI)

• Redox-cycles with SO2 / C3=


• Metals deposition by cracking

spiked VGO on catalyst (crack-on)

• Redox-cycles with Air



1United States Patent Application 201901345892Stockwell, Ind. Eng. Chem. Res. 2015, 54, 22, 5921–5934

3 picture © sandsun/shutterstock4 picture © Przemyslaw Ceynowa /shutterstock

5 picture ©NikolayN/shutterstock

3 4 5

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Catalyst deactivationMarket Survey

„The majority of the oil refining companies are using only CMDU to accurately deactivate catalysts and predict

closer the commercial performance“

MM: Mitchell method (wet impregnation), HT: Hydrothermal (steaming), SI: Spray Impregnation, CMD: Cyclic Metals Deactivation

Worldwide survey by BASF

CMD

60%CPS

35%HT

5%

MethodMetals deposition /

distribution

Deactivation /

conditioningMetals activity

MM + HT

MM + CPS ✓

SI + CPS ✓ ✓

CMD ✓ ✓ (✓)


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Catalyst deactivationLarge scale deactivation unit

• Joint development and construction of multi-purpose deactivation unit with BASF

• Up to 5 kg of catalyst / batch

• Hydrothermal steaming, CPS or CMDU

• Dual-vessel design (patent pending)1

• Continuous age distribution method (CADM)2



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Catalyst deactivation Medium scale deactivation unit

• Scale-down of multi-purpose deactivation unit

• Up to 1 kg of catalyst / batch

• Hydrothermal steaming, CPS or CMDU

• Dual-vessel design (patent pending)1

• Continuous age distribution method (CADM)2

Deact ivation



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Catalyst deactivation Full workflow from catalyst deactivation to catalyst testing

MDU


Deact ivation

Deact ivation

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Catalyst deactivation Full workflow from catalyst deactivation to catalyst testing

MDUDeactivation

• Same process control (hteControl4) with high

flexibility

• Same database (myhte4)

• Deactivation parameters / procedures

• Catalyst characterization data

• Performance data

• Easy calculation and visualization of structure-

performance relationsships


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AnalyticsMethods for FCC product analysis

VGO

Coke

Drygas

Gasol ine

LPG

LCO

HCO

FCC

Products Base AnalysesEduct

Coke analysis

Online GC < C7

SimDist

Add. Analysis

PIANO / RON

2D-GC <600°C

Development

30°C

220°C

350°C

750°CCCR


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Data evaluationIntegrated workflow / Lab 4.0

Spent catalystSyncrudes

<<

<<

wt%

coke

Prozess dataOnline GC

FeedCatalyst

SimDis t

PIANO / RON

SimDis t

SARAMeta ls

BET


<<

<<

<<

<<

<<

<<

<<

<<

1 2

1 p i c t u r e © N i k o l a y N / s h u t t e r s t o c k2 p i c t u r e © F a b l o k / s h u t t e r s t o c k

https://www.shutterstock.com/de/g/NikolayN

https://www.shutterstock.com/de/g/Fablok

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Floor 1: Catalyst testingLab 4.0 for fluid catalyst testing

MDU 3MDU 2 MDU 1

Aging

MDU 4


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P P

APar

Catalytic cracking modelling in MDUKinetic model

• Collaboration with A. Corma, ITQ

• 11 product lumps

• 39 parameters

• Non-isothermal

• Catalytic and thermal cracking

Coke

Gasoline

C1/C2

C3/C4

C2=

C3=

C4=


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Catalytic cracking modelling in MDUParametric studies


~6s

~2s

3 .5s Ref

~6s

~2s

3 .5s

Prediction by kinetic modelExperimental data / DoE

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Catalytic cracking modelling in MDUParametric studies @ constant catoil


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Catalytic cracking modelling in MDUSummary

• 11 lump kinetic model for detailed yield

calculation

• MDU to determine and validate kinetic

constants and activation energies by well

defined and flexible parameter space

• Kinetic model to optimize yield distribution

• Potential: kinetic input for computational

particle fluid dynamic (CPFD) or reactor

modelling


Peter Blaser, CPFD, BASF FCC Conference 2019, Lisbon

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Case studies

Case 1 Case 2 Case 3

MDU vs. ACE vs. CRU

ECat

Standard VGO / low CCR

MDU vs. DCR

ECat / Additives


MDU vs. Commercial RFCC

ECat

Resid / CCR = 4 wt%

NA


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Case studies

MDU vs. ACE vs. CRU

ECat


• Parameter space

CRU

~6s

~2s

3 .5s


Case 1

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Case 1Results vs. conversion

H i g h e r C / O

Yield distr ibution of

CRU and MDU match

well


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Case 1Results vs. conversion

Yield distr ibution of

CRU and MDU match

well at constant conv

Best condit ion

identif ied by paramter

variat ion


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Case 1Summary

• Yield distribution of CRU at constant

conversion / coke closely resembled by MDU

• Same conditions as in CRU directly obtained

the same yield pattern

• Broad C/O, conversion and coke range

accessible

• Kinetic model by Corma describes the yields

and parameter variations quite well

• Parameter space

CRU

~6s

~2s

3 .5s


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Case studies

MDU vs. ACE vs. CRU

ECat


MDU vs. DCR

ECat / Additives



ECat

Resid / CCR = 4 wt%

NA



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Case 2 w/ Phillips 66MDU vs. DCR

De

lta

Co

nv

ers

ion

(%)

Base Feed change Cata l ys t change

• Delta conversion @ constant catoil = 7.5

2

0

-2

-4

-6

-8

-10

DCR MDU

• Delta yields @ constant conversion = 73%

De

lta

Yie

lds

(%)

3

2

1

0

-1

-2

-3Coke H 2 DryGas LPG Naphtha LCO Slur ry

DCR MDU

• Comparison of MDU / DCR at same conditions → no optimization of MDU


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Case 2 w/ Phillips 66Overview

• „MDU tends to match pilot plant

cracking conversions at higher CTO“

• „MDU yields closely resemble those of

the DCR unit for the step changes in

this study“


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Case studies

MDU vs. ACE vs. CRU

ECat


MDU vs. DCR

ECat / Additives



ECat

Resid / CCR = 4 wt%

NA



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Case 3Overview

• Target

• Achieve same yield distribution as RFCCU @

constant coke

• Feed

• Atmospheric resid

• 4 wt% CCR

• 0.5 wt% sulfur

• 13 wt% with BP > 745°C

• Catalyst

• eCat

RFCCU

• Parameter space

~6s

~2s

3 .5s


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Case 3Yield distribution RFCCU

Yield distr ibution

provided by customer

at constant coke of

7.94 wt%


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Case 3Yield distribution RFCCU and MDU results

MDU

MDU

MDU MDUMDU

MDU

MDU

MDUMDU

Accessible yield

distr ibution in MDU

by changing:

Catalyst T

Reactor T

Pressure

Residence t ime

Di lut ion

98±2%


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Case 3Yield distribution RFCCU and MDU results

Closest yield

distr ibution

Catalyst T: 700°C

Reactor T: 560°C

Pressure: 1.86 bar

Residence t ime: 3.5 s


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Case 3Interpolation @ constant conversion / coke

@ Conversion = 68.2% @ Coke = 7.94wt%

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U

MD

U

RF

CC

U MD

U

RF

CC

U

MD

U

RF

CC

U


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Case 3Summary

• Yield distribution of commercial RFCCU at

constant conversion / coke closely resembled

by variation of parameter space in MDU

• Higher reactor temperature needed to reach

reaction progress to LPG at shorter reactor

length

• Close reaction kinetics of bottoms to gasoline

to LPG

• Thermal cracking / wall effects increase

drygas yields

RFCCU

• Parameter space

~6s

~2s

3 .5s

MDU


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SummaryMDU

• Provides laboratory test at reasonable costs

• Enables tech service support and supports R&D in multiple

areas by offering:

• Broad accessible parameter space

• Flexible feed supply

• Detailed product analysis

• Operates in a digital lab 4.0 environment

• Delivers input for kinetic modelling

• Simulates commercial yield distributions


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PeopleFCC team

FCC Team


hte

hte GmbH | Kurpfalzring 104 69123 Heidelberg, Germany T +49 6221 7497 0 info@hte -company.com www.hte -company.com

THANK YOU.

redefine fcc catalyst testing for advanced technical

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