catalytic conversions of biosourced raw materials : … · 2011-12-01 · catalytic conversions of...

Confidential A European Project supported within the Seventh Framework Programme for Research and Technological Development

CATALYTIC CONVERSIONS of BIOSOURCED

RAW MATERIALS :

HETEROGENEOUS CATALYSIS

Wolfgang Hoelderich TCHK , RWTH-Aachen

EuroBioRef Summer School Utilization of Biomass for the Production

of Chemicals and Fuels

Castro Marina , Lecce ,Italy

September 18th -24th ,2011,

Wolfgang f F Hoelderich

TCHK , RWTH -Aachen

Confidential

World’s most pressing environmental issues

Global

climate change

Sustainable

energy

production

Food

production

Depletion of

non-renewable

resources

Dissipation of

toxic materials

Green chemistry and engineering

Alternative

Feedstocks

Alternative

Reagents

Alternative

Solvents

Alternative

Products

Alternative

Catalysts

Confidential

Conference in Rio de Janeiro 1992

The sustainable use of renewable

natural resources is one aim in the

Agenda 21 of the Rio de Janeiro

concept for the 21st century

Confidential

Strengths Weaknesses

Petrochemistry

• Known technology

• Existing plants

• Simple chemistry

• Pollution

• Functionalisation

• Depleted resources

Alternative

feedstocks

• Low environmental impact

• Functionalisation

• Non-Toxic

• Biodegradable

• Domestic feedstock

• Natural variability

• Seasonal cost

• Complexity

• Unknown technology

• Technology evaluation

Confidential

However, this field is not as new as it is assumed sometimes:

-10 mio t/a of cellulose and pulp from wood;

-15 mio t/a of fibers from cotton;

-10 mio t/a of fats and oils used in chemical industry e.g for surfactants,

detergents, lubricants;

- X mio t/a of alcohol by fermentation; think of wine and beer

Confidential

Confidential

Renewable Feedstock

Recently, there is the new trend to use renewable sources

for the synthesis of value added chemicals

as well as

for the chemical modification of renewable feedstock

to produce new materials with favorable properties

such as surface activity and biodegradability

as well as

to produce already existing materials in a cheaper and ecologically

safer way than before.

A field of sustainable, green chemistry!

Confidential

• The utilization of renewable feedstock found increasing interest

over recent years due to economic as well as ecological reasons.

• That helps:

- to use the overcapacities of our agricultural economy.

- to save resources such as crude oil and gas as well as energy.

- to produce biodegradable products such as polymers, lubricants.

- to use readily and “cheaply?” available starting materials for the

synthesis of chemicals.

The nature is the architect of the carbon framework !

Confidential

• Renewable raw materials contribute with 10% to the feedstock

consumption of the chemical industry in Germany and the USA.

• Recently, the National Research Council of the USA estimated

for the year 2020 that 25% of the production of organic chemicals

will originate from renewable feedstock. A German politician of the Green

Party spoke about 40% until 2020 .

• At present, approximately 51% of the renewables used in Germany are fats

and oils, 43% based on carbohydrates and 6% based on proteins.

Confidential

Coal

2.2%

Gas

7.6%

Petroleum

82.1%

Renewable Feed

8.0%

Annual total consumptionof

organic raw materials is ca

22.4 mio. tons

8% of renewable feedstock

contribute to approx. 20% of

value of chemicals production

Confidential

Renewable Feed

1.8 Mio. t

Petroleum

18.4 Mio. t

Gas

1.7 Mio. t

Coal

0.5 Mio. t

Annual total consumptionof

organic raw materials is ca.

22.4 mio. tons

8% of renewable feedstock

contribute to about 20% of

value of chemical production

Confidential

The nature is the architect of the carbon framework

One uses readily and “cheaply?” available starting materials found in nature

for the synthesis of chemicals .

Not starting anymore from ethylene / propylene and aromatics to build

up the carbon framework . Starting on a higher synthesis level !!

For example : campholenic aldehyde from pinene epoxide

p-cymene from limonene and pinene

mango fruit aroma from limonene and pinene

grape fruit aroma from limonene and pinene

acrolein and acrylic acid from glycerol as C3 unit

Confidential

p-Cymene is used: as solvent and perfume ingredient,

as intermediate for p-cresol

(antioxidant 2,6-di-tert-butyl-p-cresol)

production route based on petroleum feedstock

H3C

after distillation of the o-isomer m/p-cymene-isomers separation according to

the Cymex-process (UOP) using molecular sieve as an appropriate sorbent and

toluene as desorption media

m/p-cresol isomers separation by partial crystallization of m-cresol under

elevated pressure according to Sumitomo Chemical Corp.

Confidential

- e. g.: catalyst Pd/SiO2 (D-11-10), T = 300°C, WHSV = 3 h-1

in the presence of 1,5 NL H2/h

yield = 98% for a very long service time (> 800h)

W. F. Hoelderich and coworkers

Appl .Catal. A: General 158 (1997), 145

Appl. Catal. A: General 163 (1997), 31



Catal. Lett. 52 (1998), 7

Stud. Surf. Sci. Catal. 121 (1998), 191

Confidential

alpha-limonene

37%

p-cymene

11%

other terpenes

4%

terpinolene

13%

gamma-

terpinene

4%

1,8-cineole

1%

alpha-terpinene

6%

camphene

6%

alpha-pinene

18%

Confidential

crude sulfate terpentine (CST)

cheapest and major source of terpenes

by-product from pulp and paper industry produced during pulp digestion

in Kraft paper mill

15-20 ct / kg compared to 26 ct / kg for toluene and >100 ct / kg for propylene

exact CST composition depending on the geographical origin of the wood

from a Kraft paper mill in La Tuque, Canada, 90% out of -pinene (65%) and

-pinene (25%)

Overall result :

CST conversion/pinene conversion over Pd/SiO2 (D-11-10) is a nice

example for the catalytic bi-functionality

cheap biodegradable resource can replace petrochemical feedstock

double catalyst bed ZnO and Pd/SiO2 (D-11-10) makes the use

S-containing terpenes mixtures manageable

Confidential

limonene 8-alkoxy-1-p-menthene -pinene R = alkyl- 8-alkoxy-1-p-menthenes used as flavours and fragrances, as additives for pharmaceuticals and agricultural chemicals, in food industry and in synthesis of fine chemicals Homogeneous catalysts: HCl, H2SO4, p-toluene sulfonic acids, and Lewis acids such as AlCl3, BF3-etherate Heterogeneous catalysts: acidic cation exchange resins, mordenite, clinopthilolite, ferrierite

CH3

ROH

CH3

CH3

ORCH3

ROH

CH3

H3C CH2

Confidential

OCH3

[RH]

OCH3

CHOH2 / CO

8-methoxy-1-p-menthene 8-methoxy-p-menthane-2-carboxaldehyde

Confidential

R = CH3: mangofruit arom

R = C2H5: green citrous fragrance

R = C3H7: fresh grass flavour

R = C4H9: woody odour

C H O

O R

Confidential

p= normal pressure; T= 25°C; t= 20 h; methanol/limonene= 2:1 (mass ratio);

2g beta zeolite; 10 g limonene; 20 g methanol; batch reactor

0 10 20 30 40 50 60 70 80 90 100

JN H2-B

JN H1-B

HV 92-62

HV 93-23

HV 94-49

selectivity [%] (8-methoxy-1-p-menthene) conversion[%] (limonene)

Confidential

HV94-49

780m2/g

HV93-23

680m2/g

JN-B1-H

640m2/g

Confidential

Sulfurization of limonene and -pinene for the grapefruit arom

limonene 1-p-menthene-8-thioether -pinene

In the case of limonene:

USY-zeolite, 50 °C, 17 bar

conversion: 77%

selectivity: 65 %

CH3

H3C CH2

H2S

CH3

SH

CH3 CH3

H2S

CH3

Confidential

α-pinene epoxide campholenic aldehyde

OOCatalyst ?

Confidential

H

CH3

CH2OH

H

CH3

CH2OH

Natural occuring active fragrance compounds of sandalwoodoil

Synthetically manufactured sandalwood fragrances based on campholenic aldehyde

OH OH OH

Sandacore Brahmanol Bacdanol

OH OH

Polysantol Sandalore

Confidential

α-pinene epoxide campholenic aldehyde

OOCatalyst ?

• USY-zeolite (Si/Al=70) with Lewis acid sites, fine tuned

• 0 °C, 15 g pinene oxide, 2g catalyst, 30 mL toluene

• batch reactor

• 100% conversion, 85% selectivity

W.F. Hoelderich et al. CH 1701 / 95 (Priority 28.04.1995) Firmenich S.A.

Confidential

Biodiesel – Green Fuels

Confidential

O

O

O

C15H31

O

C15H31

O

C15H31

O

CH3OH

O

O

OH

C15H31

O

C15H31

O

CH3OH

OH

O

OH

C15H31

O

CH3OH

C15H31 O

O

C15H31 O

O

C15H31 O

O

OH

OH

OH

glycerol

fatty acid methylesters FAME

triglyceride

Reaction is basic catalyzed using e.g. NaOH or Na-methoxide

Confidential

Transesterification of 200 g rapeseed oil and 50 g methanol with 0.5 g sodium

methoxide as catalyst at reflux temperature

0 2 4 6 8 10 12 14 160

10

20

30

40

50

60

70

80

90

100

Minutes

Triglycerides

Yie

ld %

Diglycerides

Monoglycerides

Glycerol

Methylesters

Confidential

Oil

Methanol

NaOCH3

HCl

HCl

R-1R-2R-3 Crude

Glycerol

Biodiesel

Mixer/Settler II Mixer/Settler I

Biodiesel

Washing

Water

Removal

Methanol

Distillation

R-3

Oil

Biodiesel

Glycerol

Methanol

3

Methanol

Stripper

Glycerol

Separator I

R-3

Reactor I

Glycerol

Separator II

Reactor II

Methanol

Distillation

Confidential

• Homogeneous base catalysts like NaOH or NaOCH3 are of very high

• activity. But the catalyst has to be neutralized with an acid like HCl.

• The formed salts end up in the crude glycerol. The glycerol is of low

quality or a costly purification by distillation is necessary.

• A high triglyceride quality is required,i.e. without a high content of fatty

acid which is always in competition with food uses.

• Low quality fats and oils contain large amounts of free fatty acids. The

• formation of soaps causes severe separation problems due to

• emulsification of the two liquid phase reaction mixture.

• Low quality triglycerides can be only used after refining or preesterification.

• There is a need for process intensification and simplification.

• The application of heterogeneous catalysis is a powerful tool.

Confidential

To overcome these problems we have chosen

various rare earth oxides as heterogeneous catalysts

- first batchwise in an autoclave

- second in a continuous flow fixed bed reactor

Confidential

16:0 18:0 18:1 18:2 18:3 other

Rapeseed oil 4.4 1.5 62.7 18.6 9.7 3.1

Refined palm oil 44.6 4.1 38.7 9.7 0.1 3.4

Crude palm oil 48.4 4.6 36.2 8.2 0.2 2.4

Brown grease 27.7 17.4 39.0 9.6 0.7 5.6

TG DG MG FFA

Rapeseed oil 99.3 0.7 0 0

Refined palm oil 91.0 9.0 0 0

Crude palm oil 87.7 6.7 0.5 5.0

Brown grease 74.8 11.7 1.5 12.0

Confidential

• Experiments in 75 ml autoclaves with glass inlet and magnetic stirring.

• For example 12.5 g refined or crude palm oil, 12.5 g methanol and

1.25 g of each powdery rare earth oxide are used.

• The reaction mixture is heated up to 200°C, kept 2 h at the same

• temperature and cooled on ice thereafter.

• A maximum pressure of 33 bar is reached due to methanol

Confidential

0 20 40 60 80 100

Blank

Product Composition (%)

Refined Palm Oil

0 20 40 60 80 100

Y2O

3

Sm2O

3

Nd2O

3

Pr6O

11

CeO2

La2O

3


Crude Palm 0il

Triglycerides

Diglycerides

Monoglycerides

Free fatty acids

Methylesters

Confidential

• In the presence of free fatty acids in the feed rare earth metal soaps are

formed. That causes leaching.

• These rare earth metal soaps serve as homogeneous base catalysts.

Therefore, for the crude palm oil with a somewhat higher FFA content

always higher conversion is obtained in comparison with FFA free oil

• These effects are disadvantageous because of poor long term

catalyst stability and the contamination of products by heavy metal ions

• For the blank tests free fatty acids accelerate the conversion speed

autocatalytically.

Confidential

• Therefore we have to avoid soap formation. This can be done

by immobilization of rare earth oxides on different supports.

• In particular tetragonal ZrO2 serves as a suitable support.

• In the first step of its preparation 10% La2O3 as dopant on Zr(OH)4

stabilizes the tetragonal ZrO2 modification after calcination at 700°C.

• In the second step by subsequent impregnation of the support with

La(NO3)3 and calcination at 700°C a total loading of 20% La2O3 can

be achieved.

• In this manner highly dispersed and immobilized La2O3 on tetragonal

ZrO2 is prepared. Leaching is not observed anymore.

• In comparison to neat La2O3 a much higher BET surface is obtained.

• Furthermore a high partition of mesopores of great diameter reduces

diffusion problems.

Confidential

12.5 g refined palm oil, 12.5 g methanol, 1.25 g catalyst as designated, 2h at 200°C

0 10 20 30 40 50 60 70 80 90 100

20% La2O

3/ZrO

2

(tetragonal)

10% La2O

3/ZrO

2

(tetragonal)

ZrO2

(monoclinic)


Triglycerides

Diglycerides

Monoglycerides

Free fatty acids

Methylesters

Confidential

V6

P2

PIC

P1

PI

OilMethanol

TIC

TIC

TIC

C1

V1 V2

V3 V4

V5

V7

B1 B2

B4

B3

W1

A1 A2

A3

A1, A2, A3 scales:

0-5 kg

P1, P2 piston pumps:

0-2.4 l/h

C1 fixed bed reactor:

125 cm3

TIC temperature control:

RT-300°C

PIC Pressure control:

1-100 bar

Confidential

Confidential

146.25 g 20% La2O3/ZrO2, temperature as given above, 250 ml/h methanol,

250 ml/h rapeseed oil, LHSV = 4 h-1

0 50 100 150 200 250 300 350 40040

50

60

70

80

90

100

Temperature Yield 6.5 h

225°C 98.2%

200°C 96.5%

175°C 87.8%

Meth

yle

ste

r Y

ield

(%

)

Minutes

Confidential

146.25 g 20% La2O3/ZrO2, temperature as given above, 250 ml/h methanol,

250 ml/h rapeseed oil, LHSV = 4 h-1

0 50 100 150 200 250 300 350 40030

40

50

60

70

80

90

100

Temperature Yield 6.5 h

225°C 95.5%

200°C 92.5%

175°C 82.7%

G

lyce

rol Y

ield

(%

)

Minutes

Confidential

146.25 g 20% La2O3/ZrO2, 200°C, methanol to rapeseed oil ratio as given above,

LHSV = 4 h-1

0 50 100 150 200 250 300 350 40075

80

85

90

95

100

Methanol Yield 6.5 h

50 vol.-% 98.2%

35 vol.-% 93.2%

20 vol.-% 85.0%

M

eth

yle

ste

r Y

ield

(%

)

Minutes

Confidential

146.25 g 20% La2O3/ZrO2, 200°C, methanol to rapeseed oil ratio as given above,

LHSV = 4 h-1

0 50 100 150 200 250 300 350 40060

65

70

75

80

85

90

95

100

Methanol Yield 6.5 h

50 vol.-% 95.5%

35 vol.-% 85.8%

20 vol.-% 72.7%

G

lyce

rol Y

ield

(%

)

Minutes

Confidential

142.02 g 20% La2O3/ZrO2, 200°C, 250 ml/h methanol, 250 ml/h brown grease from pork,

LHSV = 4 h-1 YIELD OF GLYCEROL 98 %

0

20

40

60

80

100

0 50 100 150 200 250 300 350 4000

1

2

3

4

5

Methylesters

Meth

yle

ste

rs (

%)

Free Fatty Acids

Monoglycerides

Diglycerides

Triglycerides

Inte

rmedia

tes (

%)

Minutes

Confidential

200 400 600 800

0,00

0,05

0,10

0,15

0,20

0,25

0,30

200 400 600 800

0,00

0,05

0,10

0,15

0,20

0,25

0,30

NH3 Desorption Temperature (°C)

TC

D S

ign

al (V

/g)

CO2 Desorption Temperature (°C)

Confidential

• However, 20% La2O3/ZrO2 is an active and stable heterogeneous catalyst

• due to the tight binding of La2O3 in the tetragonal ZrO2 host lattice.

• This new catalyst enables the simultaneous transesterification and

• esterification of even brown grease from pork with 12.0% free fatty acids

• to the methylesters in 96.7% yield. Bifunctional acid – base catalyst

• The glycerol formed is free of salts and typically of 98% purity.

• A new integrated biodiesel process using low quality feedstocks, saving

• food resources and making pure biodiesel and glycerol was presented.

• Therefore, biodiesel can be produced more cost-efficient.

• Pure glycerol becomes a valuable platform chemical for the production

• of acroleine, acrylic acid, allylic alcohol and 1,3-propanediol.

Confidential

•Water soluble, viscous, colorless liquid without known toxicity

•Used in cosmetics, lubricants, explosives, pharmaceuticals,

and more than other 1500 various applications

• Glycerol is a by-product of biodiesel production

OHHO

OH

Glycerol

Vegetable oil

Methanol

Transesterification

Biodiesel

Fatty Acid Methyl Ester

Diesel mix

Glycerol co-production = 10 %

i.e. an expected additional 1 000 kt by 2015

Vegetable oil

Methanol

Transesterification

Biodiesel

Fatty Acid Methyl Ester

Diesel mix

Glycerol co-production = 10 %

i.e. an expected additional 1 000 kt by 2015

Confidential

Confidential

• Substitution of propylene by glycerol for acrolein production

• Acrolein and its derivatives would be based on bio-mass

• Another step to crude oil independency

• Valorization of glycerol would incourage bio-diesel producers

Propylene

OHHO

OH

Glycerol

O

Acrolein

O

Acrylic acid

OH

Confidential

0

500

1000

1500

2000

2500

89 91 93 95 97 99 01 03 05

Year

Pri

ce i

n E

uro

pe

(€/m

T)

STANDARD

GLYCEROL

PROPYLENE

VEGETABLE

GLYCEROL

TALLOW

GLYCEROL

• Glycerol prices drop with increasing biodiesel production

• Propylene prices increase with increasing crude oil prices and the polypropylene demand

Confidential

• Acetone

• Acetaldehyde

• Propanaldehyde

• CO/CO2

OHHO

OH

OH

H

HPO

H3COH

O

HO O

HPA

H

H O

OHO

O

OH

HOH

+

Oligomers

O

HOOHHO

HO

OH

O

O

OH

- H2O

- H2O

2H2O

+ H2O

Acetals

Confidential

Temperature: 280° C, Glycerol conc: 20 wt. %, Feed: 12 g/h, Oxygen: 0 or 0,34 nl/h,

Catalyst: 4,23 g

Catalyst: H Beta Zeolite

Without oxygen assistance

0

20

40

60

80

100

0 10 20 30 40

Reacted glycerol [g]

Catalyst: H-Beta Zeolite

With oxygen assistance

0

20

40

60

80

100

0 10 20 30 40

Reacted glycerol [g]

X Glycerol

S Acrolein

Y Acrolein

Y Hydroxypropanone

Y Acetaldehyde

Y Propanaldehyde

Y Acetone

Confidential

Catalyst Oxygen Y Acrolein

[%]

X Glycerol

[%]

S Acrolein

[%]

S By-products*

[%]

HZSM5 - 36 77 47 9

HZSM5 + 39 89 44 5

H-Beta Zeolite - 49 95 52 20

H-Beta Zeolite + 54 100 54 12

Phosphated Zirconia - 38 99 39 29

Phosphated Zirconia + 37 100 37 17

ZrO2/WO3 - 70 100 70 21

* Quantified by-products

Temperature: 280° C ; Glycerol concentration: 20 wt. % ;

Feed: 12 g/h ; Oxygen flow: 0,34 nl/h ; Catalyst: 10 ml

Confidential

Catalyst: ZrO2/WO3

Changed Parameter: Reaction temperature

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

220 240 260 280 300 320 340

Temperature [° C]

Conversion Rate

Acrolein Yield

Acrolein Selectivity

Oxygen flow: 2,5 ml/min

Feed: 35 g/h

Confidential

Reactor

Glycerol solution

Oxygen

Oven 1

Cat.

Cooling

(0° C)

Glycerol: 20. % water solution

Oxygen: 11,33 ml/min

Oven 1: 280° C

Oven 2: 300° C

Cat 1: 10 ml H3PO4/ZrO2

Cat 2: 10 ml Mixed oxides

Cold trap: 0° C

Method of analysis: Qualitative and quantitative GC

Dehydration

Oxygen

Reactor Cat.

Oven 2

Oxidation

Nitrogen

Confidential

Confidential

▪ Direct dehydration of glycerol to acrolein is technically possible

in particular over WO3 / ZrO2 and WO3 / TiO2 catalysts

▪ The acid / basic properties of the WO3 / ZrO2 catalysts have to be well

adjusted by tungston content and calcination to achieve good a

catalytic performance. In the case of WO3 / TiO2 there are no basic sites.

▪ Avoiding basic sites helps to suppress the HPO formation.

▪ Service time of WO3 / TiO2 longer than WO3 / ZrO2 catalysts

▪ Presence of oxygen:

• suppresses by-products, in particular hydroxypropanone

• inhibits catalyst desactivation

▪ The best results so far are:

85 % selectivity to acrolein at 100 % conversion of glycerol

Confidential

Synthesis of new environmentally benign

lubricants based on renewable feedstock

Confidential

• Release of lubricants to the environment

40 – 70% of the total consumption

• Loss of lubricants due to spillage, evaporation, accidents etc.

• in Germany : consumption approx. 1.2 Mio t / a

loss approx. 0.5 Mio t / a

• globally : consumption approx. 37.8 Mio t / a

loss approx. 17 Mio t / a

Environmental pollution

Confidential

• hardly biodegradable

• hazardous and toxic

• difficult to recycle

Confidential

Glyceroltrioleate

O

O

O

O

O

7

O

4

Confidential

R1

R2 R

3CO2H

R1

H

R2

OR3

O

+catalyst

e.g. Addition of pivalic acid to oleic acid methyl ester forming

2,2-dimethyl propionyloxy octadecanoic acid methyl ester

reaction conditions:

temperature 120 °C, reaction time = 8 h, catalyst: SAC 13

44% conversion, 93% selectivity

Patent: WO 01/53438 A1, Hölderich, Keller, Fischer, Weckes, Mang, Luther, Wagner

R3= H, CH3, (CH3)3

Confidential

• Heterogeneous acid catalysts such as Amberlyst 15, SAC 13,

H-Y zeolites and different kind of metal oxides have been

examined for the addition of methanol and neopentanol.

• In this case the reactions resulted in transesterification.

• The direct addition to the double bond was not observed

R1

R2

R1

H

R2

R3OH+

catalystO

R3

Confidential

I

II

R1

R2

R3OH

+oxidizing

agentcatalyst

R1

R2

O

+

R1

OH

R2

O

R3

R1

R2

Ocatalyst

Confidential

0

10

20

30

40

50

60

0 5 10 15 20 25Time (h)

Ep

ox

ide

yie

ld (

%)

Ti-MCM-41(0,8)

Ti-MCM-41(2,2)

Ti-MCM-41(2,9)

Ti-MCM-41(2,7)

TS-1

Activity increases by increasing

Ti dispersion

Under equal Ti dispersion, the

activity is proportional to external

surface area

Conditions: TBHP/oleate = 1,1 mol/mol, oleate /catalyst=20 g/g, toluene/oleate = 1 g/g, temp. = 70°C.

Ti-MCM-41(x): x is Ti/Si x 100

Selectivity > 95%

Confidential

Si source + Ti source + hydrolysing agent

heating over a few hours

synthesis gel

Confidential

0

10

20

30

40

0 5 10 15 20 25

Time (h)

Ep

oxid

e y

ield

(%

)

Ti-SiO2(0,8)C

Ti-MCM-41(2,7)

Ti-SiO2(1,6)D

Ti-SiO2(2,0)A

Ti-SiO2(5,6)B

Activity increases by

increasing Ti dispersion.

Under equal Ti dispersion,

the activity is proportional to

external surface area.


Ti-SiO2(x): x is Ti/Si x 100

Selectivity > 95%

Confidential

0

0,01

0,02

0,03

0,04

0,05

0 5 10 15 20 25

Time (h)

Ep

oxid

e y

ield

/BE

T a

rea (

%/m

2)

Ti-MCM-41(0.8)

Ti-SiO2(0.8)C


Selectivity > 95%

Confidential

0

10

20

30

40

50

0 5 10 15 20 25

Time (h)

Ep

oxid

e y

ield

(%

)

Ti-SiO2(0,8)C, with

catalyst removal

Ti-SiO2(0,8)C,

without catalyst

removalTime when catalyst

is removed

Conditions: hydroperoxide/oleate = 1,1 mol/mol, oleate/catalyst = 20 g/g, solvent/oleate = 1 g/g, temp. = 70°C.

Selectivity > 95%

10

12

14

16

18

20

22

Run 1 Run 2 Run 3 Run 4

Ep

oxid

e y

ield

(%

)

75

80

85

90

95

Ep

oxid

e s

ele

ctivity (

%)

Yield

Selectivity

Confidential

[CH2]7

[CH2]7

O

O

O

H3C

CH3

[CH2]7

[CH2]7

OR1

O

O

H3C

CH3

OH

[CH2]7

[CH2]7

O

O

O

R1

CH3

[CH2]7

[CH2]7

O

O

O

H3C

CH3 [CH2]7

[CH2]7

OR1

O

O

R1

CH3

OH

H+

R1OH

H++ R

1OH

- CH3OH

+ R1OH

- CH3OH

H+

H+

1

2 3

4

1 Hydroxy-ether (desired product)

2 Ketone

3 Transesterified hydroxy-ether

4 Transesterified ketone

Confidential

0

10

20

30

40

50

60

70

0 2 4 6 8

Time (h)

Hyd

roxy-e

ther

yie

ld (

%)

OH

OH

OH

OH

OH

OH

OH

OH

OOH

OOH

0

10

20

30

40

50

60

70

0 2 4 6 8

Time (h)

Hyd

roxy-e

ther

yie

ld (

%)

OH

OH

OH

OH

OH

OH

OH

OH

OOH

OOH

Alcohol/epoxide=5 mol/mol, toluene/epoxide=2 g/g, epoxide/Amberlyst15=2.5 g/g, temp.=24°C.

Hydroxy-ether selectivity > 98%.

Confidential

0

10

20

30

40

50

60

OM

E

eOM

E

HM

SM

HPrS

M

HBSM

HPSM

HIS

M

HIp

SM

HNSM

100°C

40°C

kin

. V

iskosität

[cS

t]

OH

OH

OH

OH

O OH

OH

OH

modified OME:

monohydroxy

ethers

Confidential

Lab scale(ca. 2-4g product/batch)

Benchscale

(ca. 1400g product/batch)

Methanol

Butanol

Propanol

Isopropanol

Isobutanol

Pentanol

Neopentanol

tert.-Butanol

3-Phenoxy-2,2-

diemthylpropanol

3-(2'-ethyl)-butyloxy-2,2-

dimethylpropanol

substrats: Alkohol + OME

Methanol (HMSM)

Butanol (HBSM)

Propanol (HPrSM)

Isopropanol (HIpSM)

Isobutanol (HISM)

Pentanol (HPSM)

Neopentanol (HNSM)

substrats: Alcohol + OME

GTO

PTO

TMPO

substrats: Isobutanol + Triester

Decision:

reaction reasonable according to:

conversion

selectivity

catalysts costs

substrate availability

Evaluation:

viscosity, VI

acid number

oxidation satbility ROBOT

biodegradability

surface tension

Pilot plant

(ca. 7 Kg product/batch)

HISM

HIGTO

Confidential

Confidential

• Amorphous Ti-SiO2 are suitable catalysts for the epoxidation of oleochemicals with organic

hydroperoxides . They are robust i.e. no leaching of Ti and re-usability without regeneration

is proven .The cheap amorphous Ti-SiO2 shows a catalytic performance in the epoxidation

of oils as good as the very expensive Ti-MCM 41.

• Catalysts to perform the addition of alcohols to epoxidized vegetable oils must provide

enough accessibility to the active sites.Highly acidic catalysts like Amberlysts , Nafion/SiO2

, aluminosilicates and zeolites with a high external surface area can be used as catalysts.

But cheapest clay smectite showed best catalytic performance in the epoxide alcoholysis .

• The alcohol molecular structure imposes a strong steric hindrance effect:

linear > b-branched > a-branched > b-branched alcohol

alcohol alcohol alcohol with bulky substituents

• The oxidation stability of the new compounds is improved maintaining the good

biodegradability of the starting material and are not toxic . The structure of the added

alcohol has a strong advantageous influence on the viscositiy and other properties .

Confidential

Starch , cellulose and sugars for the synthesis

of value added chemicals

Confidential

-MDG = -methyl-D-glucose pyranoside

CH2OH

HO

O

H

H

H

OH

OH

H

H

OMe

The catalytic oxidation processes only of primary hydroxyl groups, but not

of the secondary hydroxyl groups of sugars and starch offer specific opportunities

for commercial exploitation including :

- surface coatings for the paint and paper industry

- biodegradable super absorbent materials

- biodegradable detergent co-builders

The methods used in the present technology for the oxidation of sugar and

starch in the primary position suffer from several disadvantages.

Confidential

Confidential

O

OH

H

OH

CH2OH

H

OH

OH

O

OH

H

OHH

OH

OH

OHO

O

OH

H

OHH

OH

OH

ONaO

NaOH

N

O

N

O

O2

+

Heteroge-neous

catalyst

Confidential

0

20

40

60

80

100

Conversion (%)

Selectivity (mol%)

Ag-celite Ag-Y Ag-Al2O3 Ag-AlPO4

Confidential

OH

OH

O

CH2OH

HH

OH

H

OH

OH

HOMe

H

O

HH

OH

H

OH

OH

H O

H

CH2OH

O

CH2OHH

CH2OHHO

H

H

OH

H

O

HH

OH

H

OH

OH

HOMe

H

CH2OH

n

Substrate Conversion (%) Selectivities (mol%) acid others 90 75 25 78 99 1 39 100 0 20 100 0

Confidential

• At present, in most cases products obtained from renewable raw materials are not

competitive with products of petrochemistry. That will change rapidly when the oil

price rises and oil resources will diminish. There are only a few commercialised

examples right now.

• There is no doubt : The trend is to use the synthesis performance of the nature due

to the fact of the future lack of fossil energy sources. Production processes based on

renewables need less energy and raw materials as well as create less waste and by-

products .

• Extensive use of the carbon framework of renewable resources for the synthesis of

chemicals, i.e. starting from a higher level.

• In the long run, renewable resources are considered to become a viable solution.

Their catalytic processing will make it possible to replace the fossil feedstock oil and

coal.

• Chemists, biotechnologists and growers are requested to work together

interdisciplinary to develop e.g. mutated oils and fats as renewable feedstock for the

chemical industry / oleo chemistry.

catalytic conversions of biosourced raw materials : … · 2011-12-01 · catalytic conversions of...

Documents