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Norbert Ringer ‐ Clariant16th IMPCA 2013 Asian Methanol Conference

(Syn)Gas to FuelHIGH QUALITY GASOLINE FROM METHANOL

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N. Ringer/ R. RakoczyBusiness Unit Catalysts09.09.2013

Agenda

Public, (Syn)Gas to Fuel – High quality gasoline from methanol2

– Introduction

– MTG: History & Chemistry

– The Catalysts

– CAC’s STF – Process

– Conclusions


Introduction

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N. Ringer/ R. RakoczyBusiness Unit Catalysis and Energy09.09.2013

A Lot Goes on in the Methanol Industry

• Breakthrough in on-purpose Propylene / Olefins from Methanol: successful start-up and operation of MTP / MTO plants in China

• Methanol has arrived in the energy sector:Blending into Gasoline is reality in China

• Feedstock: basically Coal in China and NG elsewhere

Now: Shale gas heralds a new era in North America!


US h l d ti h i th US k t hi h i

Shale Gas Heralds New Era*)

• US shale gas production as a game changer in the US gas market which is now no longer in decline;

• Gas is now available in abundance and can be produced at relatively low cost;• Price is steeply down from 12 $/MM BTU not long ago to ca. 4 $/MM BTU now;

• Shale gas revolution could lead to a major change in the chemical industry:

=> Gas – to – Chemicals and Gas - to - Fuels!

*) ICIS Chemical Business, Issue January 16-22, 2012

Synthetic Fuels - Alternative Route to Energy


Natural gas

Carbonaceous source Fuel

Biomass

Natural gas

Crude oil associates gas

Shale gas

Partial non catalytic oxidation

Catalytic auto thermal

reforming

Syngas to methanol

Methanol to fuel

ASO

LIN

E

Coal

…

Residues

g

Gasification

GA


MTG History & Chemistry

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Methanol to Gasoline - Commercialization


Developed in 1970 by Mobil

Catalyst based on zeolite ZSM-5 (MFI topology)

Process set-up with catalytic DME pre-reactor and catalytic gasoline reactor

Adiabatic pre-reactor inlet 280-320°C, gasoline reactor 400-420°C

Operation close to ambient pressure

Product carbon content maximum C10

Commercialization Oct. 1985 in METHANEX methanol plant in New Zealand

Unit shut down in 1998

Source: John Packer, P. Kooy, C M Kirk, Clare Wrinkes, The production of methanol to gasoline, http://nzic.org.nz/ChemProcesses/energy/7D.pdf


Methanol to Gasoline - Process and Product Issues


– Highly exothermic 1740kJ heat per kg of methanol converted

– Heat removal as inherent issue (pre-reactor and gasoline reactor)

– Coke formation rate calls for a set of reactors

– Significant amounts of traces of methanol in water out of the process

– High formation of 3-6%-wt. of 1,2,4,5 tetra-methyl-benzene (durene) is problematic


Durenes - Evaporation issue


1,2,4,5 tetramethylbenzene 1,2,3,5 tetramethylbenzene

m.p. 79°C m.p. -24°C

The high melting point of 1,2,4,5 tetramethylbenzene causes carburator icing



Methanol to Gasoline - Chemistry


TY in

%-w

t.

SPACE TIME in HOURS

SE

LEC

TIV

IT


Methanol to Gasoline - Product


Hydrocarbon product contentin %-wt.

C1,C2 1.4C3 5.5C3

= 0.2iC4 8.6nC4 3 3C4 3.3C4

= 1.1C5

+ hydrocarbons 79.9



Methanol to Gasoline - Product


Gasoline composition contentin %-wt.

Highly branched alkanes 53Highly branched alkenes 12Naphthenes 7pAromatics 28


The Catalysts

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CLARIANT Catalysts for Synthetic Fuel Production


COD - 900

Catalyst for the conversion of light olefins to distillatesy g

CPA - 100

Catalyst for conversion of paraffins to gasoline (ZEOFORMING)

DME - 100

Catalyst for conversion of methanol to dimethylether

CMG - 100

C l f i f h l li (fi i )Catalyst for conversion of methanol to gasoline (first generation)

SMA-2

Catalyst for gasoline production from methanol tailored for STF process by CAC

FTMax - Series

Catalyst products for Fischer-Tropsch synthesis

CLARIANT Catalysts for Synthetic Fuel Production


COD - 900

Catalyst for the conversion of light olefins to distillates

CPA - 100

Catalyst for conversion of paraffins to gasoline (ZEOFORMING)

DME - 100

Catalyst for conversion of methanol to dimethylether

CMG - 100

Catalyst for conversion of methanol to gasoline (first generation)

SMA-2

Catalyst for gasoline production from methanol tailored for STF process by CAC

FTMax - Series

Catalyst products for Fischer-Tropsch synthesis


CLARIANT’s Experience in Conversion of Methanol

17

CMG - 100

Zeolite MFI (ZSM-5) based catalyst

Optimized hydrothermal stability

Easy to install

High Methanol conversion rate

Easy to regenerate

Low Durene make, less work-up requirement

Patented in 1998

Evaluated and approved at the METHANEX MTG Plant in Plymouth, New Zealand

CMG-100 Chemistry


MeOH molecules flowinto a Reactor filledwith CMG-100 Catalyst.

... inside the pores of the CMG-100 catalyst carbon atoms join up in complex strings with hydrogen to form hydrocarbons (Gasoline).

The zeolitic CMG-100 catalystcauses MeOH to rearrange.Two hydrogen atoms joinonto one oxygen atom toform water while ...


CMG-100 Commercially Proven


CMG-100

STF – The Technology

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STF Process Concept by Chemieanlagenbau Chemnitz


STF Process - Unique advantages (I)


easy and optimal process control

high product yield and product selectivity with lowest unwanted by-products levelsg p y p y y p

due to

-isothermal reaction process

-optimized recycling of non-used components

-isothermal reactors allowing stable process control and optimal reaction conditions

-tailor-made SMA-2 catalyst by CLARIANT

substantial reduction of the recycling gas quantity due to use of isothermal reactors compared to adiabatic reactors


STF Process - Unique Advantages (II)


increase of catalyst lifetime and cycle length of the synthesis catalyst due to isothermal reaction process

use of the reaction heat of the exothermic gasoline synthesis for HP steam generation

use of the generated steam as energy source in the process and for generation of electrical energy

process water is fully cleaned of methanol and other oxygenated components

a biological purification of waste water is not required

product gasoline complies DIN EN 228 and European emission standard EURO 5 and does notproduct gasoline complies DIN EN 228 and European emission standard EURO 5 and does not require any further refining

STF Process - Demonstration Plant



STF Process - Gasoline Properties


STF fuel DIN EN 228:2004-03gasoline, regular

Density (15°C) 750 – 760 720 – 775 kg/m³Density (15 C) 750 760 720 775 kg/m

Molecular mass 95 – 96 kg/kmol

Paraffins 30 – 40 %-wt.

Olefins 4 – 6 max. 18 %-wt.

Naphthenes 7 – 9 %-wt.

Aromatic compounds 34 – 36 max. 35 %-wt.

Benzene 0,2 – 0,4 max. 1 %-vol.

Durene1 2 4 5 Trimethylbenzene

max. 3 %-vol.1,2,4,5-Trimethylbenzene

Research octane number 93 – 95 min. 91

Motor octane number 84 – 85 min. 82,5

Vapor pressure 66,7 max. 100 kPa

Boiling range 40 – 186 - °C

STF Gasoline - Applicability tests


First results of „full load“ mode:

• tests with a modern fuel injection motor (Downsizing Concept)

e [ba

r]

1820222426

STF Benzin Charge 2 Basis Benzin ROZ95

• Comparative fuel: Gasoline RON 95 („Super E10“ with 5.1% Ethanol)

Valuation of Results:

• With STF gasoline nearly same results under full load at constant charging pressure

• Ignition angle with STF gasoline minimal later (ca. 1°KW), this means knocking behavior slightly higher

375400

p me

12141618

Zünd

win

kel [

-]

-12-8-40481216

Ign

itio

n A

ng

le [

-]

• Specific fuel demand Beff until 4000 1/min for both fuels identical, at higher speed (number of revolutions) slightly higher

in cooperation with:

Drehzahl [1/min]1000 2000 3000 4000 5000 6000

Bef

f [g/

kWh]

250275300325350375

Speed [1/min]


STF commercial scale plant - Capacities


Balance for 50.000 t/a final product gasoline plant capacity

Raw material Products

t/a kg/h % t/a kg/h %

methanolwater

134.99114.999

16.0701.786

9010

gasolinefuel gasLPGheavy gasolinewater

50.0005.3732.4891.19790.931

5.952640296143

10.825

33,33,61,70,8

60,6

149.990 17.856 100 149.990 17.856 100

electrical energy excess

2,4 MW

Conclusions

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(Syn)Gas to Fuel - Summary


A new process for the production of high-octane gasoline from methanol has been developed.

Th ti l t t i th d l t h bThe essential targets in the process development have been:

Achievement of high product yields and selectivity at low capital and energy costs.

Generation of a product, which does not need further refining but is in compliance with a high-octane gasoline as per DIN EN 228 standard.

Development of an almost effluent free technology

PLANT CAPACITY: 50 000 t/a product gasolinePLANT CAPACITY: 50.000 t/a product gasoline

Based on SMA-2 catalyst made by Clariant

THANK YOU FOR YOUR KIND ATTENTION!

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N. Ringer/ R. RakoczyBusiness Unit Catalysts09.09.2013

(syn)gas to fuel · synthetic fuels - alternative route to energy 6 public, (syn)gas to fuel –...

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