simultaneous hydrotreatment and isomerization of waste ... · th aocs latin american congress and...

Martin MittelbachCancun, September 13, 2017

M.Mittelbach, S.Schober, A.Studentschnig, [email protected]

Institute of Chemistry (IFC)Department of Renewable Resources

University of GrazA-8010 Graz, Austria

17th AOCS Latin American Congress and Exhibition on Fats, Oils, and LipidsSeptember 11-14, 2017, Cancun, Mexico

1

Simultaneous Hydrotreatment and Isomerization of Waste Fats and Oils

Using Heterogeneous Catalysis


Biomass Biooils

Biohydrogen

Synthesis gasCO/H2

BtLBiomass to liquid Biodiesel

(FAME)

BioethanolBiogas

Fatty oils

Extraction

Pyrolysis

Fermentation: from sugar,starch: 1st Gen.From lignocellulose: 2nd Gen.Fermentation

Gasification

FTSynthesis

(Trans)esterification

Hydrogenation

HydrotreatedVegetable Oils (HVO)Hydro-processed esters and fatty acids (HEFA)

2


World Biodiesel Production: 16 mill. tWorld HVO Production: 2 mill. tWorld Bioethanol Fuel Production: 78 mill. t

Global Biofuel Production: 96 mill. t

Global Demand for Transport Fuel 2,400 mill. t

Current share of biofuels in transport fuel: 4.0 %

(world energy council, 2016IEA: world energy statistics, 2016)

Global Production and Utilization(2017, estimated)

3


4


Biodiesel

vs.

Hydrotreated Vegetable Oils (HVO),Hydroprocessed Esters and Fatty Acids (HEFA)


hydro isomerization

branched hydrocarbons (HVO)

6

3 R - CH3 + 6 H2O + H3C - CH2 - CH3

R

O

O

O

R

O

O

RO

triglyceride

3 MeOH3 FAME + glycerol

Biodiesel (FAME)

n H2

Vegetable oil/fat based Biofuels


7

FAME vs. / HVO (HEFA)

FAME HVO

Feedstock fatty acid material: triglycerides, fatty acidsConversion reaction with methanol reaction with hydrogenReaction conditions moderate; low T and p high T and pPlant scale any kind industrialYield up to 100 % < 100 %Side products glycerol propane, decomposition pr.Purification washing, distillation distillationProduction costs relatively low higher than FAMEOxid. Stability antioxidants highCold T behaviour low with saturated feedstocks hydrothermal upgrading

Fuel properties depending on feedstock flexibleOEM acceptance varying, up to 100 % high


8

Comparison of Selected Fuel Properties

M.Mittelbach, EJLST 2015


Hydotreated Vegetable Oils (HVO) Production in Europe: 1.29 Mt

Finland: 380.000 t/aSingapur: 800.000 t/aRotterdam: 800.000 t/a

9

USA: 400.000 t/aItaly: 500.000 t/a

Vegan TM


10

CO2

Ru unsaturated fatty acidRs saturated fatty acid

n-C15n-C17Propane

Isomerization iso-C15iso-C17

Isomerization

lighter alkanes

Cracking

Crackingiso-C16iso-C18

CO

H2

H2

H2H2O

n-C16n-C18Propane Hydrogenation

Dehydration

DiglyceridesMonoglyceridesFatty Acids

Decarboxylation Decarbonylation

Rs

Rs

RsO

OO

O

O

OO

RuO

Ru

O

O

ORu

O

ReactionRoutes for HVO: Hydration, Decarbonylisation, Decarboxylation

• Catalysts: Commercial desufurization catalysts, • NiMo or CoMo on support (Al2O3, SiO2)• High p (~5 MPa) and T (>300 °C) • Cracking and isomerization preferred at high

temperatures (450°C)

M.Mittelbach, EJLST 2015


11

Energy&Fuels 2013, 27, 7480−7484

Biofuels 2016, 7, 279-287


12

Hydrotreatment of Non-Edible Feedstocks with Raney NickelHC-chain length distribution

3 % Raney Ni, 360°C, 5htotal yield: 63-73 %

PFAD: palm oil fatty acid distillateWT: waste tallowCO: castor oil

Cold Temperature Behaviour:PFAD WT CO

CFPP 16 13 12CP 19 19 18PP 3 4 6


13

Hydrotreatment of Non-Edible Feedstocks with Raney NickelPFAD: palm oil fatty acid distillate

WT: waste tallowCO: castor oil

H.Studentschnig et al., 2016


14

Biofuels from TalloilSideproduct from paper production

kg talloil/t cellulosetree spruce pinewood type round logs saw mill round logs saw milloriginnorth Finland 70 45 23 15

east Finland 58 38 19 13

south Finland 45 30 15 10

Global production: 5 mill tons/a


15

Biofuels from Talloilchemical composition

abietic acid C20H30O2

pimaric acid C20H30O2

dehydroabietic acid C20H28O2 neoabietic acid C20H30O2

laevopimaric acid C20H30O2

C H3

C H3

CH3

C H3

COOH

CH3

C H3

C H3

C H3

COOHCH3

C H3

C H3

C H3

COOH

CH3

C H3 C H 2

C H3

COOH

CH3

C H3

C H3

C H3

COOH

Fatty acids: 42 – 55 %Rosin acids: 33 – 47 %Unsaponifieable (sterols, terpenes): < 25 %Sulfur: 600 - 2100 mg/kg


16

Biofuels from Talloil: Hydrotreatment and Isomerization

Parameter step 1 step 2 isomerisation

Amount of catalyst 2,5 w% NiMo* 2,5 w% NiMo* 2,5 w% Pt/ZY**

H2-pressure at 20°C 100 bar 100 bar 100 bar

stirring 300 rpm 300 rpm 300 rpm

temperature 400°C 400°C 300°C

Reaction time 4.0 h 4.0 h 0.5 h

*10 % Ni, 12%Mo ** 2% Pt on Zeolith ZY

after 2nd step

after isomerization

n-C18

n-C17

branchedproducts

crackingproducts


17

Parameter[Unit]

Tall oil Aim after 1st step after 2nd stepafter

isomerisationAcid number[mg KOH/g]

84< 0,5

(EN 14214)5.1 1.7 < 0.5

Water[mg/kg]

0.31< 500

(EN 14214)444 90 172

Sulfur[ppm]

948< 10

(EN 590)80 3 < 1

95 % (V/V) residue [°C]

< 360(EN 590)

446 429 320

Distill. range250-350°C [%]

65-85(EN 590)

45 50 35

Biofuels from Talloil: Hydrotreatment and Isomerization


18

Catalyst preparation for one-step reaction

• Pellets from kaolin (3mm x 6 mm)• Sintering 4 h at 1150°C• Incipient wetness impregantion with Ni/Mo salts; Ni:Mo = 1:2• Final metal content: 6 % Ni; 4 % Mo• Calcination at 400°C


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Time [min]-->

Abundance

5.00 10.00 15.00 20.00 25.00 30.00

Pellet_C_Talloel_5h

Fettsäuren

Harzsäuren Sterole

Pellet_C_Talloel_0h

Pellet_C_Talloel_1h

Pellet_C_Talloel_2h

Pellet_C_Talloel_3h

Pellet_C_Talloel_4h

UMSATZ: >99,9%

Biofuels from Talloil: One-step reaction5% Ni/Mo on Kaolin Pellets, 420°C, 100 bar H2


20

Biofuels from Waste Tallow: One-step reaction5% Ni/Mo on Kaolin Pellets, 420°C, 100 bar H2

Abundance

Time [min]--> 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00 28.00

Pellet_C_Tallow_0h

Pellet_C_Tallow_1h

Pellet_C_Tallow_2h

Pellet_C_Tallow_3h

Pellet_C_Tallow_4h

Pellet_C_Tallow_5h

StearinsäurePalmitinsäure

Ölsäure

n-C18

n-C19

n-C21

1-Octadecene

UMSATZ: >99,9% Cloudpoint: -16°C


21

Biofuels from Waste Tallow: Reaction Time5% Ni/Mo on Kaolin Pellets, 420°C, 100 bar H2

0

20

40

60

80

100

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

[%]

[h]

Reaction Time

ISO

CRACK

UMSATZConversion


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Biofuels from Waste Tallow: Catalyst Recycling5% Ni/Mo on Kaolin Pellets, 420°C, 100 bar H2

0

10

20

30

40

50

60

70

80

0 1 2 3

Recycling of Catalyst Without Calcination

Isomerization Cracking Yield


23

Biofuels from Waste Tallow: Catalyst Recycling5% Ni/Mo on Kaolin Pellets, 420°C, 100 bar H2


24

Comparison of Catalysts 420°C, 430°C

Catalyst Raney-Nickel ZSM5 Pellet_C_NiMo Pellet_C_NiMo

Reaction Temperature[°C]

420 420 420 430

∑Iso [%] 17.76 97.97 54.92 51.47

∑Crack [%] 96.16 92.22 76.97 93.94

Yield [%] 10.06 12.15 55.84 33.48

Cloud Point [°C] -15.0 -33.0 -13.5 -33.0

Biofuels from Waste Tallow: Results from One-Step Reaction


Conclusions and Outlook

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• Hydrotreatment and hydrothermal upgrading of non-food feedstockslead to tailor made biofuels

• Heterogeneous catalysts based on impregnation of kaolin with Ni/Mo couldbe developed

• The best reaction conditions for waste fats and oils could be found:100 bar hydrogen pressure, batch, 3h, 420 °C

• Hydrotreatment and isomerizazion in 1 step was succesful yielding productswith good cold temperature behaviour

• The catalyst could be recycled without further treatment at least for 3 times

• Considerable losses of yield due to decomposition have to be considered


Sigurd Schober, Senior ScientistStephanie Flitsch, PhDAlexander Studentschnig, PhD studentPhilipp Neu, PhD studentPamela Hidalgo, PhD student, ChileKatharina Strohmaier, PhDAndrea Schroeck, Dipl.Ing.Aline Munez, PhD student, BrazilSebastian Jäger, PhD student, ArgentinaM.Meissner, F.Raffler; Master students

Acknowledgements

http://www.google.at/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0CAQQjRw&url=http://www.bioliquids-chp.eu/index.php?id%3D3%26PHPSESSID%3Dgbspfi0k8b5hjmd4tk8a9lucv3&ei=Q5qIU_mOHcvE4gSvj4CICw&psig=AFQjCNFTwP_rEFwA6vg6B5IPhws8ziwedA&ust=1401547715506532

http://www.google.at/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0CAQQjRw&url=http://www.bioliquids-chp.eu/index.php?id%3D3%26PHPSESSID%3Dgbspfi0k8b5hjmd4tk8a9lucv3&ei=Q5qIU_mOHcvE4gSvj4CICw&psig=AFQjCNFTwP_rEFwA6vg6B5IPhws8ziwedA&ust=1401547715506532

http://www.vtu.com/?lang=de

http://www.vtu.com/?lang=de

http://www.steiermark.at/

http://www.steiermark.at/

http://www.conicyt.cl/

http://www.conicyt.cl/

http://www.bmvit.gv.at/

http://www.bmvit.gv.at/

simultaneous hydrotreatment and isomerization of waste ... · th aocs latin american congress and...

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