design catalytic process for biofuel production

8/4/2019 Design Catalytic Process for Biofuel Production

1/40

www.catalysis.ru1 UIC

DESIGN OF CATALYTIC PROCESSES FOR

BIOFUELS PRODUCTION

III RUSNANOTECH 2010

Vadim A. Yakovlev

Valentin N. Parmon

Boreskov Institute of CatalysisNovosibirsk, Russia

[email protected]


2/40


Contents of the Presentation

I. Situation in World concerning renewable and local fuel

sources

II. The innovative catalytic ways of biomass processing for theenergetics within international projects and perspectivedirections

II.I. Biofuels from wood

II.II. Improved technology of biodiesel production

II.III. Green diesel production

II.IV. Other perspective directions of biofuels production

III. Answer to a question: Can biomass replace fossil oil andnatural gas as feed stock for motor fuels production or not?


3/40


Source: IEA, WEO, Reference scenario, 2002 and 2007.

The present energy model is based on ever-increasing demand andthe perpetuation of fossil fuels

Mtoe = Million tons of oil equivalent


4/40


Shell international BV, Shell energy scenarios to 2050. 2008


5/40


Present problems of biomass processing into fuels andenergy:

At present biofuels have higher first cost than fossil oil-fuels and natural gas

The main reasons:

1. High costs of farming, harvest, transport of biomass2. Lower technological level of biomass processing incomparison with oil refining

On the whole now the situation in bioenergetics issimilar to the one with oil-refining 90-100 years ago.


6/40


Source: New Energy Finance

Bioenergy Technology Pathways


7/40www.catalysis.ru7 UIC

Biofuel pathway costs

Roberto Rodriguez Labastida, BTL investment trends and levelled costs of production, Bloomberg NewEnergy Finance (2010).Note: The final biofuel product from each pathway, and its associated conversion cost, has beencompared with the energy content of a litre of gasoline.

- Feedstock Cost - Conversation Cost - Capital Cost

Gasoline





sources









Biomass

Pyrolysisplant

Biomass

Pyrolysisplant

Biomass

Pyrolysisplant

StandardRefinery

Upgrader

BiomassPyrolysis

plant

Transportation fuels

Chemicals

Heat and power

Schematic representation of the biomass-pyrolysis-upgrading-refinery concept



Fractionationduring and

aftercondensation

Biomassresidues

Co-processing inconventional

petroleum refineryDe-oxygenation

Hydrocarbon-rich fraction

Lignin-richfraction

ConversionDerivatives of hemicellulosesand celluloses

Conventional fuelsand chemicals

Liquefaction

Note: hydrocarbon-rich fractions are formed when the biomass feedstock contains asignificant amount of extractive substances; e.g the case for forestry residues.

Energyproduction

Processresidues

Oxygenated products

(blending)

role of BIC

Netherlands BTG, University of Twente, Shell Global SolutionsInternational, University of Groningen, Albemarle Catalysts Co.Finland VTT, Helsinki University of Technology

France CNRS-IRC, ALMA Consulting Group, Metabolic ExplorerGermany - Ineos-Phenolics, UHDE, Institute of Wood Chemistry HamburgUnited Kingdom - Johnson MattheySweden - STFI-PACKFORSKSlovenia - Slovenian Institute of ChemistryRussia - Boreskov Institute of Catalysis

List of BIOCOUP project participants

Tasks of BIC within the projectDevelopment of bio-oil deoxygenation catalysts


11/40


What is bio-oil?

Liquid (bio-oil)

Upgraded biocrudeoil

HDOH2

catalysts

up to 70 mass %

to dry biomass

Dry Biomass

Flash pyrolysisT > 450 0C, < 1 s,

heating rates > 1000 0C

The main disadvantages of bio-oil:

Very viscous

Unstable (readily polymerized)

Poorly evaporated

Immiscible with ordinary fuels

Strongly acidic (=3)

Because of high content of oxygen

C 30-60 %

30-60 %

H 6 - 7 %

N


12/40


LMM Lignin:Catechols, ligninederived phenols andguaiacols ( 13%)

OH

R

OH

R

Acids (4%) CR

O

OHCR

O

OHC

O

HO

Aldehydes,Ketones, Alcohols

( 15%)

Sugars (34%)

HMM Lignin ( 2%)

dehydration ( H2O)

hydrogenolysis ( H2O)

decarbonylation ( CO)

decarboxylation ( CO2)

decarboxylation ( CO2)

cat

T

cat

T, H2

cat

T, CO

cat

T

cat

T

Upgrading of Bio--Crude--Oil via Catalytic Deoxygenation


13/40


Hydrodeoxygenation catalysts developmentas key step of HDO process development

Traditional catalysts for

hydrodeoxygenation (HDO):

1. Sulfided Ni-Mo/Al2O3, Co-Mo/Al2O32. Pd, Pd-Pt, Rh-based catalysts

These catalysts dont fit

for bio-oil upgrading:- Noble catalysts are veryexpensive for large-scaleprocesses- Sulfided catalysts aredeactivated in target process

Prices of HDO catalysts active metal

from the year 1996 to 2010.

Conclusion: catalysts have to be cheaper and non-sulfided

Rh $2250Pt $1703Pd $625Ru $178Ni $ 0,62

1996 1998 2000 2002 2004 2006 2008 2010

0

2000

4000

6000

8000

10000

Rh, Pt, Pd, Ni - http://www.kitco.com

Ru - http://www.platinum.matthey.com

US$

/Troyonce

Year

Rh

Pt

Pd

Ru

Ni


14/40


Catalysts screening

Active metal Support

Ni-Mo, Co-Mo sulf.,

Ni-Mo, Co-Mo ox.,

Ni-Mo-Mn, Ni-Mo-Mg,

Rh, Pd, Pt, Rh-Co, Ni,

Co, Cu, Ni-Cu, Co-Cu,

Fe-Cu

Al2O3, SiO2, C-SiO2

, Al2O3- SiO2, Cr2O3,

CeO2, ZrO2, CoSiO3

Step 1: Screening of HDO catalysts

Catalysts Rh/CoSiO3 Rh/ZrO2 Rh/ CeO2

LHSV, h-1 0,5 1,0 0,4

Anisole conversion (%) 82,0 99,6 99,9

HDO degree (%) 79,2 90,8 94,3

HDO tests results:

Catalysts RhCo/Al2O3 Rh/SiO2 RhCo/SiO2

LHSV, h-1 0,3 0,3 0,3

Anisole conversion (%) 98,2 53,4 99,0

HDO degree (%) 74,7 30,3 81,1

Reaction conditions:

Substrate: anisoleTemperature: 300oCPressure H2: 0,5 MPa

LHSV: 6 h-1

Reactor type: flow fixed-bed


15/40


Catalysts screening and comparison with the commercial catalysts

Catalyst S/Ni-Mo/Al2O3

(Albemarle)

IC3-47

(BIC)

Ni/ Cr2O3

(Chirchik)

Rh/CoSiO

(BIC)

H2pressure, MPa 0,5 0,5 0,5 0,5

Temperature, 0C 300 300 300 300

LHSV, h-1 0,6 6 6 0,5

Conversion, % 92,8 78,6 90,2 82,0

HDO degree, % 15,4 95,9 15,7 79,2

%100

i

i

i

i

C

C

HDO iC

iC

HDO degree corresponds to the selectivity of hydrogenated products formation:

- the concentration of oxygen-free iproduct

- the concentration of iproduct

Ni/ Cr2O3

Benzene hydrogenation into

cyclohexane

S/Ni-Mo/Al2O3

Oil hydrotreating

Step 2: Ni-based catalysts


16/40


Catalysts screening and comparison with the commercial catalysts

Catalyst S/Ni-Mo/Al2O3

(Albemarle)IC-3-47(BIC)

Ni/ Cr2O3

(Chirchik)

Products

selectivity, %

cyclohexane 8,5 24,3 9,5benzene 6,2 59,9 6,2

toluene 1,9 2,9 0

phenoles 70,3 0 0

cyclohexanole 0 2,3 81,7

cyclohexanone 0 1,8 2,6

other products 13,1 2,9 0

OH

desiredproduct

Step 2: Ni-based catalysts


17/40


System NiCu/ Al2O3

Catalyst metal, % wt. supportCu Ni

24.5Cu 24,50 - Al2O35.92Ni18.2Cu 18,20 5,92 Al2O313.3Ni11.8Cu 11,80 13,30 Al2O313.8Ni6.83Cu 6,83 13,80 Al2O3

16Ni2Cu 2,00 16,00 Al2O320.8Ni -- 20,80 Al2O3

Catalyst conversion,% HDO, %

Quartz 2,8 0

Al2O3 11,8 0

24.5Cu 95,3 1,0

5.92Ni18.2Cu 76,9 72,8

13.3Ni11.8Cu 70,3 82,8

13.8Ni6.83Cu 73,8 90,6

16Ni2Cu 78,6 95,9

20.8Ni 66,1 97,8

HDO tests results:

Cu loading into nickel on alumina catalysts increases

the selectivity of hydrogenated aliphatic products

(cyclohexane, methylcyclohexane) formation against

the aromatic products (benzene, toluene)

Spec.cat.activity

molh-1g-1

0,66

0,30

0,34

0,33

0,22

Step 3: Optimization of Ni-Cu catalysts composition


18/40


In-situXRD analysis of NiCu/ Al2O3 system(under the hydrogen atmosphere, heating up to 300 )

Support(-Al2O3) lattice parameter vs. Ni content

(%, wt.) in the catalyst

Ni ions diffuse into the alumina structure with

formation of the solid solution

Lattice parameter of metallic nickel differs

from the PDF card value

Formation of the solid solution Ni1-xCux



19/40


System NiCu/ Al2O3

TPR analysis(thermo-programmed reduction)

1. The presence of copper

promotes the nickel oxide

reduction at a lowertemperatures.

2. The addition of copper

into Ni/Al2O3 promotes

the decrease of the

surface Ni Al solid

solution content in the

samples.



20/40


Conception of bifunctional nature of HDO catalysts

First type (I) of active component hydrogen activation(noble metals, nickel, cupper et al.)

Second type (II) of active component oxy-organic activation(transfer metals in reduced or oxidized forms with variable valence atHDO reaction conditions)


21/40

www.catalysis.ru21 UIC48M General Assembly 38

RUG-Results Highlight

Exploratory Catalyst Screening

Pyrolysis oil, 350 oC, 200 bar H2, 4 h. Catalysts provided by BIC/TKK/ALBE

NiCu catalysts are potential for further development

0.00

10.00

20.00

30.00

40.00

50.00

60.00

Pin

e oil

Ru/C 5

wt%

Ru/C

3.33wt

%

Ru/C

2wt%+a

ctPd

/C

PdPt

/SiO

2-Al

2O3 (

Albe

)

Rh/C

eO2

Rh/Z

rO2

Rh/Co

SiO

3

Rh/Z

rO2

RhPd/

ZrO

2

RhPt/

ZrO

2

Pd/Z

rO2

PdPt/

ZrO

2

Pt/Z

rO2

NiCu/A

l2O3

FeCu/A

l2O3

NiCu/

ZrO

2

NiCu

/CeO

2(co

)

NiCu

/CeO2

(wet)

NiCu

/C

NiCu

/CeO2-

ZrO

2

crac

king

(NiC

u/d-Al

2O3)

crac

k+Ni

Cu/C

eO2-Zr

O2

NiCu

/sib

unite

NiCu/C

eO2

Catalyst

Oxygenconte

nt(wt-%)

noble metals

cheaper transition metals

: flowable products at RT


22/40




sources







1 I d T h l f Bi di l P d ti


23/40


Problems:- Low quality of biodiesel- a lot of waste at the production

1. Improved Technology of Biodiesel Production

Application:as additives (5-20%) to traditional diesel

Plant oils + Methanol Glycerine + Biodiesel

Homogeneous

catalyst

H2SO4 orNaOH

Traditional technology:

Manufacture of biodiesel:more than 12 million tons in 2009

Prediction:biodiesel production growth ~10-15% per year

O

OH2C

O

O

HC O

OH2C

R1

R2

R3

CH3OH OHH2C

OHHC

OHH2C

O

OH3CR

Wh h l ?


24/40


Why heterogeneous catalysts?1. Cleaner process

2. Zero soap production

3. Recovery of the catalysts is reusable

4. Cleaner Biodiesel

5. Cleaner Glycerol (99% against 75-80%)

Affordability:

reduction of process cost2 - 2,1 times

heterogeneous systems dont form soap during the reaction,

reduce the generation of effluents, no corrosion, simplify the purification of by products, facilitate the separation of biodiesel from the reaction media

and also allow the recovery of the catalyst by filtration, allow regenerate the catalysts by washing with solvents,

oxidation or thermo treatment,

purity of the glycerinic phase obtained after thealcoholysis reaction.

disadvantages deactivation and/or lixiviation of the catalysts usage, the increase in of the time reaction, higher molar ratio

of alcohol/fatty material.

Technological scheme of biofuels production


25/40


Technological scheme of biofuels production(within RG project).

R1

MeOH

Rectifyingcolumn

R2

H2O

CH4

Combustion,Q

Rapeseedoil

HydrogenGlycerin

GreenDiesel

2400

2,0 P

34004,0 P

20% RO30% BD20% RO

80% BD

Peculiarities of processes:

- Conjugation of interesterification and hydrocracking processes- Incomplete conversion of rapeseed oil (up to 80%)- 50% biodiesel + 50% green diesel

Biodiesel50% to consumer

Methanol



26/40


Technological scheme of biofuels production(within RG project) Interesterification.

R1

MeOH

Rectifyingcolumn

R2

H2O

CH4

Combustion,Q

Rapeseedoil

HydrogenGlycerin

GreenDiesel

2400

2,0 P

34004,0 P

20% RO30% BD20% RO

80% BD

HC

H2C

H2C O

O

O

R1

O

R2

O

R3

O

+ CH3OH

H+

OH-

HC

H2C

H2C

OH

OH

OH

+ H3C

O

R

OT=60

0C

Peculiarities of process:

- Heterogeneous catalyst- One step of interesterification- Conditions: 2400, 2.0 P,- trickle-bed reactor employment


Methanol


27/40


Development of heterogeneous catalysts for plant

oils interesterification

Heterogeneous basic catalysts : MAl12O19 (M = Ca, Sr, Ba),

so-called hexaaluminates

Cristal structure - magnetoplumbit and -Al2O3

Advantages of hexaaluminates

Chemical stability

Thermal stability

Possibility of catalysts regeneration

Development of heterogeneous catalysts for plant oils


28/40


Development of heterogeneous catalysts for plant oilsinteresterification

rapeseed oil, % Sr-La-O > Ba-La-O > Y-Mg-O La-Mg-O > Ba-Al-O700 > Sr-Al-O700

2240-2251cm-1, mol/m2 2.23 1.77 1.55 1.35 1.21 1.16

0 2 4 6 8 100

20

40

60

80

100

Rap

eseedoilconversion,

%

Reaction time, hours

Sr-Al-O (700)

Sr-Al-O (1200)

Ba-Al-O (700)

Ba-Al-O (1200)

Y-Mg-O (750)La-Mg-O (750)

Sr-La-O (750)

Ba-La-O (750)

Concentration of middle base centers (determined via vibrational C-Dfrequencies ((CD)) of CDCl3 adsorbed on samples) is correlated with activity ofcatalysts


29/40



I. Situation in World concerning renewable and local fuelsources









30/40


Technological scheme of biofuels production(within RG project). Hydrodeoxygenation

R1

MeOH

Rectifyingcolumn

R2

H2O

CH4

Combustion,Q

Rapeseedoil

HydrogenGlycerin

GreenDiesel

2400

2,0 P

34004,0 P

20% RO30% BD20% RO

80% BD


Methanol

H3CO

R

O

H2

CatAlkanesPeculiarities of process:

- Heterogeneous catalyst- One step of hydrocracking- Conditions: 3400, 5.0 P,- trickle-bed reactor employment


31/40


Hydrodeoxygenation of biodiesel :Structure of biodiesel:

Methyl ether of linolenic acid

(19332) 8 %

Methyl ether of linoleic acid(19352) 20%

Methyl ether of oleic acid(19372) 59%

Methyl ether of erucic acid(23452) 3%

Methyl ether of stearic acid(19392) 10%

1 2 3

2

3

1

2

3

- Plant oil

- Biodiesel

- Green diesel


32/40


Hydrodeoxygenation of biodiesel in thepresence of nickel catalysts

250 275 300 325 350 375 400

20

30

40

50

60

70

80

90

100

,%

,0C

Ni-Cu/CeO2-ZrO

Ni-Cu/ ZrO2

Ni-Cu/ CeO2

Ni / ZrO2

Ni/ CeO2

CeO2-ZrO

2

250 300 350 400

0

4

8

12

16

20

Y

(CH4/biodiesel)

Temperature,

0

C

P =1,0

LHSV=2 h-1

1. Ni-Cu/ZrO2-CeO2 is the most active catalyst of hydrodeoxygenation of biodiesel

2. Process of the methanization begins at temperature 280 0 with nickel catalysts,

addition copper moves the beginning of the methanization in high temperature zone

Temperature

Conversionofbiodiesel,%


33/40


Hydrocarbons

1. High-cetane diesel components production from biodiesel

Biodiesel

Mild

Hydrocracking

Bio-hydrogen

C12-C17

diesel

Peculiarities:Using of non-sulfidedand Ni-based catalysts

Process conditions:290-340oC, 3,0-8,0 MPa H2

Cetane value - 100

ApplicationEmployment asimproved additive totraditional diesel

O

OH2C

O

O

HC O

OH2C

R1

R2

R3

O

OH3CR

Plant oils

Products of fatty acids triglycerides hydrocracking at


34/40


Products of fatty acids triglycerides hydrocracking atthe mild conditions (0,5 MPa H2)

Alkanes C7-C19

Carbonic acids

Aldehydes

Methyl esters of fatty acids

Alcohols

Ketones

Wax

products +4+2+ 2

O C

O

R

O C

O

R

O C

O

R

R OH

R CO

H

R CO

CH3

R CO

R

R CO

OR

R CO

OCH3

R CO

OH


35/40


Activity of Ni-Cu/CeO2-ZrO2 at the severer conditions(2=7,0 P =360

0, LHSV= 1,1 h-1 )

Y = mole 4/ mole TGs C15- C18 alkanes yields

0 2 4 6 8 10 12 140

5

10

15

20

Y,[mole/mole]

Time (h)

0 2 4 6 8 10 12 140

10

20

30

40

50

6070

80

90

100

Yield

sofC15-C18,m

ol.%

Time (h)

0 4 8 12 16 20 24 28 0 4 8 12 16 20 24 28

Possible scheme of non-food renewable feedstock


36/40


Possible scheme of non food renewable feedstockprocessing for biofuels production

Jatrophaoil

Algae

Biodiesel

Green diesel

Transetherification

Mild hydrocracking

+ CH3OH

+ CH3OH

+ H2

+ H2

The most perspective directions for transportation biofuels production


37/40


The most perspective directions for transportation biofuels production(for diesel engine )

Biomass

Wood

Solidbio-waste

Bio-oil

Plant oil

Fats

Algae

LiquidBio-waste

Gasification

+ 2

Shift

Bio-H2

Mildhydrocracking

Green Diesel

Oil (problem: high content of sulfur)

Merits:

Renewable Low content of sulfur Possibility of fuels

production with differentcomposition

Transetherification

Biodiesel


38/40


39/40


40/40

Thank you very much for

your attention !

design catalytic process for biofuel production

Documents