Technologies

Based on renewable resources USA / Asia: Europe:

[email protected] [email protected]

Furfural –from renewable resources

H

CORN COBS SUGAR CANE BAGASSE HEMICELLULOSE

O H

H H

H

OH

HO

OH OH

O

CHO

H

Five carbon sugars

furfural

•

Furfural is produced from agricultural by-products, not food products

•

Lower variance with oil price

•

Historically, all of Penn’s specialty products have been based on furfural

Technology Overview Our chemistry expertise includes…

• Catalytic Processes - Vapor and Liquid Phase Hydrogenation - Hydrogenolysis - Decarbonylation - Reductive Amination - Oxidation Chemistry

• Ring Transformation Processes - Thermolytic Rearrangements - Heterocyclization Reactions

Our product trees are derived from these C4 and C5 building blocks…

• Diels Alder Chemistry

2,3-Dihydrofuran

Furan

• Acylations and Alkylations - Friedel-Crafts Reactions - Hydroxymethylation, Mannich Reaction - Alcohol Etherification

O

O

O Furfural

CHO

O

CH3

2-Methylfuran

Furfural Reduction Chemistry O

Hydrolytic Ring cleavage

O

CO2 H

O

α-Angelica lactone

Levulinic acid

Reduction

Reduction

O

CHO

Hydroxymethylation, Mannich reaction

HO

Dehydration and Isomerization

Hydrogenation

OH

O

CH2 OH

O

DHP

THFA O

OH O

O

Reduction

Isomerization

N

OH

Ether cleavage chemistry OH

Etherification

OH

Hydroxycyclopentenone HO

THFA is a biodegradable solvent for Agrochemical formulations and Cleaning applications

OH

OEt OH

O HO

OH

Furan Tree HO(CH2CH2CH2CH2)nOH O

Decarbonylation

polyTHF

“eco”THF

H3 C

CH3

Alkylation O

O

O

Ditetrahydrofuryl propane (DTHFP)

Friedel-Crafts acylation

Diels Alder reaction

O O

O

Ring Cleavage

RO2C

CO2R

R

O

O

HO2 C

O

Brominationdehydrobromination

O

2-Acyl furans

Br

DTHFP is a catalyst modifier in anionic polymerizations

CO2 H

O

3-Bromofuran

B(OH)2

O

Oxidation Chemistry Furoic acid R R'

O

OH

R2

Tetrahydrofuroates

t-BuOOH VO(acac)2

O

CO2R

O

O2 catalyst

O R1

CO2H

O

H2O2 V2O5

O

CH2 OH

CHO

O

O

O

OH

Hydroxyfuranone

OH H2O2 HCO2H

Pyranone

O

O

Furanone

Highly versatile building blocks from oxidation of furfural and furfuryl alcohol derivatives

2-Methylfuran Tree Cyclization

O OH

Reductive Ring cleavage

O

CH3

Friedel-Crafts acylation

O

Methyldihydrofuran

Acetylpropanol

OH

NH3 CH3

O

N O

2-Ethyl-5-methyl-3-pyridinol HCHO

Hydrogenation CH3

O

CH2 OH

O

Hydrogenolysis CH3

CH3

Oxidation

CH3

2-MethylTHF

O CH3

MethylTHF is becoming increasingly important as a Green solvent of choice

O

O OH

Pyranone

N H

CH3

2,5-Dimethylpyrrole

Dihydrofuran Tree H2O2 MeOH

OH

O

O

OCH3

CH(OMe)3 BF3.OEt2

3-Substituted Furans H3CO

Thermolytic rearrangement

CHO

OCH3

O

CHO

OCH3

O

Hydrolysis

O

O

CH2 OH

CH2 Cl

Cyclopropanes

HO O

N

CN

CH2 Br

O

N R

CHO CHO

CH3

Hydroxyethyl Heterocyclics HO

HO

CH2 OH

CO2H

HO

N HO

N N

R

N R

Facilities • Extensive multi functional facilities – Large scale, efficient Hydrogen generation – Mix of large capacity continuous production units as well as smaller, flexible multi purpose batch production – Batch and continuous distillation units

• Fully equipped R&D resources • Pilot plant capable of kilo to ton quantity production – 6 Reactors varying from 15-400 gallon

• Manufacturing facility (100 – 10,000 MT)

Product List-1 Mono-substituted Furans

O

CO2H

2-Furoic acid: C CAS No. 88-14-2

CO2 CH3

O

Methyl 2-furoate: C CAS No. 611-13-2

N

O

2-Furonitrile: L CAS No. 617-90-3

(CH2 )4 CH3

O

O OAc

Ethyl furfuryl ether: C CAS No. 6270-56-0

Furfuryl diacetate: L CAS No. 613-75-2

2-Pentylfuran: L CAS No. 3777-69-3

2-Furoic hydrazide: L CAS No. 3326-71-4

2-Furanboronic acid: L CAS No. 13331-23-2

3-Bromofuran: C CAS No. 22037-28-1

B(OH)2

O

3-Furanboronic acid: L CAS No. 55552-70-0

O

3-Furaldehyde: L CAS No. 498-60-2

2-Acetylfuran: C CAS No. 1192-62-7

NH2 O

O

Furfurylamine: C CAS No. 617-89-0

Br

2-Bromofuran: L CAS No. 584-12-3 CO2 H

CH2OH

B(OH)2

O

O O

O

CHO

Br O

O

OAc

OCH2 CH3 O

H N NH 2

O

O

3-Furanmethanol: L CAS No. 4412-91-3

3-Furoic acid: L CAS No. 488-93-7

CN

O

O

CH(OEt)2

3-Furonitrile: L Furfural diethyl acetal: L CAS No. 30078-65-0 CAS No. 13529-27-6

CN

CO2H O

(2-Furyl)acrylic acid: L CAS No. 539-47-9

O

(2-Furyl)acrylonitrile: L CAS No. 7187-01-1

C: Commercial scale, P: Pilot scale, L: Laboratory scale

Product List-2 Di- and tri-Substituted Furans

CH3

O

CH3

2,5-Dimethylfuran: C CAS No. 625-86-5

CH3

CH3

CH2OH

O

5-Methyl furfuryl alcohol: C CAS No. 3857-25-8

O

CHO

CH3

O O

5-Methyl furfural: P CAS No. 620-02-0

2-Acetyl-5-methylfuran: L CAS No. 1193-79-9 Br

Br

HOCH2

O

CH2 OH

O

2,5-Furandimethanol: L CAS No. 1883-75-6

Br

Br

2,3-Dibromofuran: L CAS No. 30544-34-4

O

Br

2,5-Dibromofuran: L CAS No. 32460-00-7

CHO

O

3-Bromofurfural: L CAS No. 14757-78-9 O

Br Br

O

CO2 H

5-Bromo-2-furoic acid: L CAS No. 585-70-6

Br

O

CH3

CO2H

O O

4,5-Dibromo2-furoic acid: L CAS No. 2434-03-9

2-Methyl-5-propionylfuran: C CAS No. 10599-69-6

CH3

O

CH3

3-Acetyl-2,5-dimethylfuran: L CAS No10599-70-9

C: Commercial scale, P: Pilot scale, L: Laboratory scale

Product List-3 Dihydro- and Tetrahydrofuran Derivatives OH O

CO2H

O

Tetrahydrofurfuryl alcohol: C CAS No. 97-99-4

CO2 CH3

O

Tetrahydrofuroic acid: C CAS No. 16874-33-2

Methyl tetrahydrofuroate: C CAS No. 37443-42-8

O

2-MethylTHF: C CAS No. 96-47-9

O

O

O

O O

O

O O

2,3-Dihydrofuran: P CAS No. 1191-99-7

2,3-Dihydro-5-methylfuran: L CAS No. 1487-15-6

O

O

2-Methyl-tetrahydro3-furanone: L CAS No. 3188-00-9

exo-3,6-Epoxy-1,2,3,6-Tetrahydrophthalic Anhydride: C CAS No. 6118-51-0 OH

OH

O

OCH3

O

3-Hydroxy-2-methoxytetrahydrofuran: P CAS No. 33691-67-7

3-Hydroxy-tetrahydrofuran: L CAS No. 453-20-3

Tetrahydro-3-furanone: L CAS No. 22929-52-8

H3 C

O

CH3

O

2,2-Ditetrahydrofuryl propane: C CAS No. 89686-69-1

C: Commercial scale, P: Pilot scale, L: Laboratory scale

Product List-4 Non-furan compounds derived from furan precursors OH CH3

N H

N

2-Ethyl-6-methyl-3-pyridinol: C CAS No. 2364-75-2

H N

CH3

2,5-Dimethylpyrrole: C CAS No. 625-84-3

3,4-Dihydro-2H-pyran: C CAS No. 110-87-2

HO

OH

OH

CHO

Acetopropanol: P CAS No. 1071-73-4 O

OH

1,2-Pentanediol: P CAS No. 5343-92-0

HO

OH

1,5-Pentanediol: P CAS No. 111-29-5

O

OH

CO2 H

O

1,2,4-Butanetriol: P CAS No. 3068-00-6

2-(1H-Pyrazol-4-yl)-ethanol: L CAS No. 180207-57-2

OH

O

Cyclopropane carboxaldehyde: P CAS No. 1489-69-6

OH

N

O

Acetonyl acetone: C CAS No. 110-13-4

Levulinic acid: P CAS No. 123-76-2

O

O

α-Angelica lactone: P CAS No. 591-12-8

C: Commercial scale, P: Pilot scale, L: Laboratory scale

Contact United States & Asia Steve Prescott

Europe Bogdan Comanita

Sales Division Penn A Kem, LLC 3324 Chelsea Avenue Memphis, TN 38108

Sales Division Penn A Kem, LLC 805 McKnight Park Drive Pittsburgh, PA 15237

Phone: (901) 320-4091 Cell: (901) 832-2929 Fax: (901) 320-4006 Email: [email protected]

Phone: (647) 344-4645 Cell: (647) 924-7298 Email: [email protected]

Customer Service and Samples Ms. Jennifer Saylor Toll Free: (877) 895-PENN (7366) Phone: (901) 320-4018 Fax: (901) 320-4002 Email: [email protected]