catalysis for renewable chemicals - nclinduscap.ncl.res.in/resources/presentations/indus...

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Praj Proprietary and Confidential

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Praj Proprietary and Confidential 1

CATALYSIS FOR RENEWABLE CHEMICALS

Pramod Kumbhar

Ex. Vice President-R&D

Praj Matrix

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Outline

• Renewable chemicals : Basics

• Biomass valorization strategies

• Bio-catalysis

• Chemo-catalysis

• Conclusions

• Praj and Praj Matrix

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Definitions

A renewable resource is a natural resource with the ability to reproduce

through biological or natural processes and replenished with the passage

of time.

http://en.wikipedia.org/wiki/Natural_resource

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• No!!

• Mid to let 1800’s

• Methanol, acetic acid and acetone : Pyrolysis of pine wood

• Ethanol, butanol and acetone : Fermentation of sugar and starches

Renewable chemicals : Is it new?

• Rayon, the first synthetic fabric, and celluloid, the earliest form of film

stock : partially derived from bio-based sources.

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Renewable chemicals : Is it new?

• In 1897 Eduard Buchner began to study the ability of yeast

extracts to ferment sugar despite the absence of living yeast cells.

In a series of experiments at the University of Berlin, he found

that the sugar was fermented even when there were no living

yeast cells in the mixture. He named the enzyme that brought

about the fermentation of sucrose "zymase".In 1907 he received

the Nobel Prize in Chemistry "for his biochemical research and

his discovery of cell-free fermentation".

As recently as the late 1940s, the world depended on bio-based processes

to produce many chemicals

http://en.wikipedia.org/wiki/Eduard_Buchner

http://en.wikipedia.org/wiki/Humboldt_University_of_Berlin

http://en.wikipedia.org/wiki/Zymase

http://en.wikipedia.org/wiki/Nobel_Prize_in_Chemistry

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Motherhood statement!!

Why will chemical industry embrace it??

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Renewable vs. Petroleum raw material prices

Competitive feed stock : key for profitability!

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Non Renewable Renewable

Witnessing Shift in Feed stocks

From hydrocarbons to carbohydrates

19th century 20th century

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Fundamental challenge for catalysis

Opportunity

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Three degrees of Complexities

1st gen Corn

Sugar cane

Cassava

2nd Gen Agriculture biomass

Vegetable oil products

Bio-catalytic Enzymes

Yeast

Bacteria

Chemo-catalytic

Thermochemical

Renewable Drop in replacement

New Molecules

Existing molecules with

Different economics

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Biomass Valorization Strategies

11

• Highly selective

• Low temperature (< 70 °C)

• Aqueous phase

• Primarily batch processes

• Low productivity

• Selective chemistry

• Moderate temperatures

(< 350 °C)

• Various reaction medias

• Batch and continuous

processes

• Non-selective chemistry

• High temperatures (350-600°C)

• Compactification of biomass

• Total decomposition

• Very high T

(>800 °C)

Bio-catalysis Chemo-Catalysis Pyrolysis Gasification

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Possible renewable chemicals

*Source DOE Report

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Top 12 sugar based building blocks

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Bio-catalysis

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Desired molecule

Design of a bio-catalyst :

Traditional Approach

Desired biochemical

• Genes selected rationally

• Trial and error approach

• Amplifying one gene at a time

• Lower productivity

The Ability to Cut and Paste Genes in Microbes Allows Us to Work

Like Never Before!

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Desired molecule


Computational approach

• Strain Engineering

Rapid : Simultaneous testing of pathway diversity

Efficacious : Most productive gene combination selected by the organism!

Combinatorial pathway engineering accelerates the strain development!

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Desired molecule


Computational approach

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Bio Succinic Acid

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Succinic acid : Market data

Total volume : 30000 MTA

Application : Polyester, polyols, coatings

Petrochemical route : Based on Maleic anhydride

Interested companies in Bio succinc acid : BASF/Purac, Bioamber, DSM,

Myriant/PTGC/Mitsubishi

Petrochemical route too expensive

Biochemical route attractive!!

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E.Coli : Mixed acid fermentation

Need to block the undesired pathways!

Myriant did it with strain engineering!!

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Scale-up of Myriants succinic acid

technology

2007 2010 2012 2014

(strain Engineering)

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Bio Adipic Acid

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Adipic acid : Market data

Conventional process

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Verdezyne Bio-catalytic process

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Bio 1,4-Butanediol (BDO)

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Bio 1,4-BDO : Opportunity

• It is a non natural compound

• Not synthesized by any organism

• No complete biosynthetic pathway to harness BDO production

Need a deNovo approach to make in bio-catalytically !!

• Market size : 1 MM MTA

• Produced synthetically from petroleum source

• Used in PBT, polyesters and for making THF

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Strain Engineering for BDO by

Genomatica

Nature Biology. Vol. 7, 445, 22nd May 2011

BDO biosynthetic pathways introduced into E. coli. Enzymes for each numbered step are as follows: (1)

2-oxoglutarate decarboxylase; (2) succinyl-CoA synthetase; (3) CoA-dependent succinate semialdehyde

dehydrogenase; (4) 4-hydroxybutyrate dehydrogenase; (5) 4-hydroxybutyryl- CoA transferase; (6) 4-

hydroxybutyryl-CoA reductase; (7) alcohol dehydrogenase. Steps 2 and 7 occur naturally in E. coli

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1,4-BDO : Genomatica

Catalyst : genetically

engineered E-coli

Higher Titre, rate and yield

The power of strain engineering!!

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Direct gaseous fermentation to Isobutene

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Isobutene : Applications

Diesel

Isooctane

Jet fuel

Tires

Lubricants,

Plastics

pET

Organic glass

Isobutene

http://upload.wikimedia.org/wikipedia/commons/0/02/American_truck_blue.JPG

http://upload.wikimedia.org/wikipedia/commons/4/40/2,2,4-Trimethylpentane.svg

http://upload.wikimedia.org/wikipedia/commons/8/84/A_380_meeting.jpg

http://michelin.az-pneus.fr/produit/pneu-primacy-hp-ete-auto_

http://www.twenga.fr/r.php?tp=8288488158688837372&site_id=2020&pos=10&dir=5

http://upload.wikimedia.org/wikipedia/fr/d/d2/Pmma_fluo_transparent.jpg

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What is the difficulty?

• Microorganisms naturally do not produce light olefins

• Classical bio-process are based on improving existing metabolic pathways

• De novo design of metabolic pathways is necessary to bio-produce light

olefins

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Global Bioernergies, France

• Successfully created an artificial metabolic pathway to Isobutene

Isobutene

Glucose Clostridium

pathway

HMG-CoA synthase

Di-P-mevalonate

decarboxylase Patent EP2304040

Patent WO2011032934

Hydroxyisovalerate

http://upload.wikimedia.org/wikipedia/commons/6/64/Glucose_Haworth.png

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e.g. high purity

Isobutene

Low quality

Glucose

Genetically engineered

micro-organism

Reduced costs and improved environmental impact due to:

- No product toxicity, no feedback-inhibition no back-

flux,

- No distillation or liquid from liquid extraction

Proof of Concept

http://upload.wikimedia.org/wikipedia/commons/6/64/Glucose_Haworth.png

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0.0

100.0

200.0

300.0

400.0

500.0

600.0

0 20 40 60 80 100 120 140 160 180 200

Co

st o

f ra

w s

ug

ar

($/t

on)

PROFIT AREA –

No profit area

Bio-isobutene price = fossile high-purity isobutene price

Price of oil ($/barrel)

No profit area

1998 1997

1996 1995

2010 2011

2009 2008

2007

2006

2005

2005

2004 2003

2002

2001

2010

2009 2008

2007

2006

2004

2003

2002

2001 2000

1994

1993 1992

1991

2011

1999

1999

1998 1997

1996

2000

1995

1994

1993

1992

1991

Sugar cane

Sugar beet

The profitability question

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Edward Buchner : Nobel lecture “Cell free fermentation” 11th Dec. 1907

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Chemo-Catalysis

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Challenges with respect to carbohydrate

chemistry for Chemo-Catalysis

ACTIVATION OF

ALKANES,

OLEFINS etc.

MULTIPLE

FUNCTIONALITIES

COMPETING REACTIONS

– BY PRODUCTS

DOWN STREAM

PROCESS

GAS and LIQUID

PHASE

NONVOLATILE

CONDENSED/LIQUID

PHASE

SURFACE CHEMISTRY

ADSORPTION

/DESORPTION SMALL

MOLECULES

LARGE COMPLEX

MOLECULES

MESOPOROUS

CATALYSTS

ACTIVE SITE &

REACTION SPHERE

CHEMISTRY

NON AQUEOUS

CHEMISTRY

WATER INTEGRAL

PART HYDROTHERMAL

STABILITY

SINGLE

FUNCTIONALITIES

CATALYST POROSITY

LIMITED SOLUBLITY

IN NON-AQUEOUS

SOLVENTS

Conventional Catalysis

Carbohydrate Catalysis

Challenges Possible

remed ies

END PRODUCT

SELECTION

REDESIGN

CATALYSTS

Oxygenated

compounds

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Levulinic acid: A Green platform chemical

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Levulinic acid Ketals by Segetis

ROUGH ESTIMATES SHOW A REPLACEMENT POTENTIAL OF

50 MTPA @ 1USD/KG

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Conversion of Glucose to Levulinic acid

HUMINS

Polymerization

Etherification

Ref.: Rackeman D. W. , Doherty W.O.S, Biofpr. 5:198-214(2011)

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Technology wrap - up

TECHNOLOGIES BASED ON MINERAL ACIDS DUAL SOLVENT FOR ENHANCED SOLUBILITY

Ref.: Rackeman D. W. , Doherty W.O.S, Biofpr. 5:198-214(2011)

TECHNOLOGIES BASED ON SOLID CATALYSTS

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Biofine process for Levulinic acid

Highly capital intensive!

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The “Praj ELA” process

44

C6 sugars

Ethyl levulinate (ELA)

Ethyl Formate

Ligneous char

Ethanol

Heterogeneous

catalyst

• Single step “green” process

• 50% of theoretical yield

achieved

• Process demonstrated on

Lab/semi pilot scale

• Scale-up to pilot in progress

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Gold : thought to be inactive as catalyst

because

• Glitters eternally: chemically inert

• Does not dissociatively adsorb H2 and O2

• Low Melting point : sintering temperature

1063 ℃ vs 1769℃ (Pt)

Catalysis by Gold

Gold : Neglected metal catalyst!

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Prof. Haruta

Tokyo Metropolitan University

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Sugar acids using gold catalyst

Prof. Vorlop, 2012

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Renovia adipic acid process

• Pt and gold based catalysts

• Cash cost below cyclohexane process

US patent application : 20110306790

Pilot plant operating at 1lb/hr

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• Renewable Chemicals: The Future is Now

• Catalysis will be the key to the success

• Interdisciplinary (chemists, bio-chemists, microbiologists

and chemical engineers) team approach essential to make

it happen

• There is no such thing as “Green premium”

Summary

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Praj Industries Limited - Background

Established in 1984

1st Company to avail VC funding in India

Listed on Indian Stock Exchanges

Business Lines

BioEthanol

Breweries

Water and Wastewater

Inputs and Chemicals

Energy Crops Services

Customized Engineering and Manufacturing

Over 450 references in 60 countries

Over 275,000 sq ft of world class

manufacturing facilities meeting global

standards.

Largest Resource Base for Bio Ethanol Industry

Diverse Global Feedstock Experience

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Praj Matrix – The Innovation Center

US$ 20+ Mn investment

80,000 sq ft of Labs, PP, and

Offices

14 Well Equipped Labs

125 technologists and growing

30 PhDs, 80 Masters

Pilot Plants

2 TPD Cellulosic Ethanol pilot plant

Two 750 kg/d Chemical pilot plants

500 sq ft Open Raceway Pond for

Algal Cultivation

IP - 11 granted patents

Bench and Pilot scale facilities to enable validation of

scientific assumptions and rapid commercialization

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Praj Proprietary and Confidential 54 54

Emerging Value Chain

Technology Engineering

Plant & Machinary

Customers Feed Stock

Agri- Processing Companies

• BIOFUEL • CHEMICAL • BIOCHEMICAL • FOOD • FEED • PHARMA

Technology Partners

Partnerships Across Value Chain

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The Biorefinery approach by Praj

55

Mechanical and

Hydrothermal

pretreatment

C5 and C6 sugars

Enzymatic

hydrolysis

Ethanol,

i-Butanol,

Isopropanol

2,3-BDO

1.4-BDO

Propanediol

Fermentation/Bio

catalysis

Chemo-Catalysis

LA/ELA, Furfural,

HMF, polyols Ethylene, iso butylene,

Butadiene, MEK, Acrylic acid

Lignin and residues

Power and

phenolics

Lignocellulosic biomass

Asia’s first 2nd Generation ethanol plant in India

Will be converted to a biorefinery in phase II

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Copyright 2011 Praj Industries Ltd. 56

Thank You

http://www.vivergofuels.com/

http://www.novozymes.com/

http://www.google.ca/imgres?imgurl=http://src.fabinet.up.ac.za/cams/img/CSIR logo 2006 trans.gif&imgrefurl=http://src.fabinet.up.ac.za/cams/img/&h=515&w=737&sz=17&tbnid=fcQiXoZBMmjqsM:&tbnh=99&tbnw=141&prev=/search?q=csir+logo&tbm=isch&tbo=u&zoom=1&q=csir+logo&hl=en&usg=__N0P0PmtodL9qsPP2pbBrvSrSgVs=&sa=X&ei=ZeTGTfbnIMfIgQe6wqnMBA&ved=0CB8Q9QEwAg

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Nexant's analysis shows several clear trends:

The dominant chemicals in terms of announced capacities are methanol/DME, metathesis oils, and

ethylene.

In terms of chemical classification, bio-based alcohols, olefins and oils are the areas with the most

planned commercialization.

Fungible (i.e. drop-in) chemicals are the main focus of chemical development and represent roughly

75% of the projects examined by Nexant. If metathesis oils are not included, fungible chemicals

constitute over 90%.

There is roughly an even split between projects that use first- and second-generation feedstocks.

Some 58% of projects examined use corn, cane sugar, dextrose or plant oil as a feedstock. The

remaining 42% use cellulose, lignocellulosic biomass, or other exotic feedstocks.

But the strength of the technology alone will not determine the success or failure of these ventures. It is

unlikely that all of these projects will reach fruition.

As well as the perennial risks associated with new ventures and biotechnology, projects have to

contend with the overall economic climate. Feedstock price changes may also doom infant

technologies.

More than any other factor, this may alter whether or not bio-based routes to chemicals will be

competitive.

Although some bio-based feedstock prices have shown increased volatility - particularly corn and

sugarcane - the primary source of risk is in hydrocarbon prices.

Despite these risks, Nexant believes that nearly two-thirds of announced capacity - some 4m

tonnes/year of production by 2015 - is likely to reach completion, putting the growth at 1m tonnes/year.

Bio-based chemical producers have the potential to build extensive alternative supply chains for a

variety of chemicals. While risks in the sector remain high, newly commercializing players have the

potential to become strong competitors.

http://www.icis.com/chemicals/methanol/

http://www.nexant.com/

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