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Biorefinery: petrochemicals processing Biorefinery: petrochemicals processing
of renewable feedstockof renewable feedstock
A.V.Topchiev Institute of Petrochemical SynthesisRussian Academy of Sciences (TIPS RAS)
Moscow, Russian Federation
September 10th, 2011 Hannover, Germany
Alexey Volkov
TIPS RAS: Petrochemistry & Oil Refinery
TIPS RASwww.ips.ac.ru
More than 75 years expertise in Petrochemistry and Oil refinery:
� Fluid Catalytic cracking9 industrial units in the world
� Visbreaking of heavy residue4 industrial units in the world
� Catalytic dewaxing2 industrial units in Russia
� Acid-catalyzed homogeneous alky-
lation processes15 industrial units in the world
� Alkylation process based on zeolite catalysts
1 industrial unit
� More than 35 years of expertise in membrane science and membrane technology.
� New area, membrane catalysis, was created by Prof. M.V.Gryaznov in TIPS RAS.
� Deep expertise in development of novel membrane materials (e.g. high permeable glassy polymer)1970th: first industrial gas separation membranes based on PVTMS.
TIPS RAS: Membrane science and technology
TIPS RASwww.ips.ac.ru
TIPS RAS: Polymers and Nanocomposites
� More than 45 years of expertise in polymer science (novel polymers for different applications).
� Significant contribution in theory of macromolecular reactions and polymer modification.
� Polymer processing: rheology and introduction of nanocomposites.
� Biomedical polymers and drug delivery systems.
� Composite materials.
� Product commercialization (e.g. adhesives for biomedical applications).
TIPS RASwww.ips.ac.ru
TIPS RASwww.ips.ac.ru
Overall strategy
1. Integration with existing processes
� Same process principles used refinery and chemical plants.
� Introduction and further increasing of renewable feedstock part.
2. Flexibility in process scheme
� Utilization of “waste” by-products into new valuable products.
� Variability of products composition by control of catalyst and process conditions.
Organics to gas
TIPS RASwww.ips.ac.ru
TIPS RASwww.ips.ac.ru
Biogas: flexibility in processing
Organic wastes
Methanogenic community
BIOGAS
Heat capability:~21.5 MJ/m3
CH4 (50-70%vol.)CO2 (30-50% vol.)
Gas conditioning
Gas processing
BIOREACTOR
Air+CO2(green house/algae)
Heat capability:~34 MJ/m3
CH4 (>95%vol.)CO2 (<5% vol.)
CH4CO:H2
TIPS RASwww.ips.ac.ru
Biogas conditioning: membrane contactors for CO2 capture
CH4 + CO2(54 + 46 vol.%)
Absorber
Desorber
CH4
Membrane
CO2
CoolerHeater
Solvent Tdes, oC
Gas composition (%)
Absorber Desorber
CO2 CH4 CO2 CH4
H2O 18 16 84 73 27
K2CO3 18 26 74 92 8
K2CO3 60 5 95 99.6 0.4
TIPS RASwww.ips.ac.ru
Biogas conditioning: pilot testing
Unit capacity: 50 m3 biogas/hour
Upscale
Membrane module
Membrane module parameters:
Size, mm: 250х180х250Membrane area: 5 m2
Packing density: 450 m2/m3
TIPS RASwww.ips.ac.ru
Biogas processing to syngas
Major drawbacks in biogas processing to syngas:
� Steam reforming: CO2 content in biogas should be lower than 20% to avoid coke formation.
� Oxidation process: Oxygen production unit significantly increase CAPEX. If oxygen is replaced by air, additional separation unit is required to remove ballast gases (mainly, nitrogen) from syngas.
Solution:
� Partial oxidation in chemical reactor: no limitations for CO2 content in biogas!
� Membrane catalytic systems: compact device.
TIPS RASwww.ips.ac.ru
Biogas processing to syngas
Advantages:� In this approach, there is no nitrogen in syngas.
� Low explosion risk.
� Possibility to varying of syngas composition.
CH4 + MeOx CO + H2
МеМеМеOxМеOx
O2 +MeO2 +Me
CH4 + [О] → СО + 2Н2
CH4 + СО2 → 2СО + 2Н2
H2 + [O] → H2O
CO2 + H2 → CO + H2O
(1)
(2)
(3)
(4)
Pilot unit
TIPS RASwww.ips.ac.ru
Biogas processing to syngas in membrane reactor
Advantages:� Decreasing of unit size and catalyst consumption.
� Decreasing of side reaction due to lower contact time in reaction zone.
СН4 + [O]s → СО + 2Н2 (1)
СН4 + 4[О]s → СО2 + 2Н2О (2)
СН4 → С + 2Н2 (3)
С+ СО2 → 2СО (4)
СО + Н2О⇄ СО2 + Н2 (5)
[O]s – “structured” oxygen
Support
Active
components
(oxides)
Productivity,
L/h·dm3membr
Syngas
composition,
H2/CO
Conversion, %vol.
CH4 CO2
Ni-Al (granules) La-Ce 250 0.66 10.3 6.8
Ni-Al (membrane) La-Ce 3780 0.63 51.2 26.1
T=600оC, Wfeed=40 L/h, СН4/СО2=1
CH4 + CO2 → 2CO + 2H2Catalytic
membrane
Catalytic
membrane
CH4
CO2
CO
H2
TIPS RASwww.ips.ac.ru
Biogas processing to syngas in membrane reactor
La-Ce/Ni-Al
Pd-Mn/Ni-Al
Optimized membrane/catalytic system: conversion of CH4 and CO2as a function of T
Organics to liquid
TIPS RASwww.ips.ac.ru
TIPS RASwww.ips.ac.ru
Biomass and polymer waste: flexibility in processing
Biomass
Fermentation processing
Alcohols(EtOH, BuOH)
Synthetic oilBy-products(Acetone…)
Polymer waste
Thermo-catalytic processing
Heavy oilresidue
TIPS RASwww.ips.ac.ru
Pervaporation membrane bioreactor:biomass conversion into alcohols
General idea Fermentation product inhibition
<1% BuOH
1- 2 % BuOH
> 20 % BuOH
TIPS RASwww.ips.ac.ru
Recovering of organics from fermentation broth: thermopervaporation as a next step in energy efficient PV
Vacuum pervaporation(conventional approach)
Feed
CondenserТ < 0оС Permeate
Vacuumpump
Cooling plate
40оС
Permeate> 20 % BuOH
10 oC
Fermenter(Alcohols+СО2)
40 oC
< 0.5% BuOH
1-2% BuOH coolant
coolant
Air
gap
Membrane
Thermopervaporation
Advantages:
� No vacuum.
� Low condensation temperature 10-20оС.
0
0,2
0,4
0,6
0,8
1
1,2
0 50 100 150
membrane thickness mkm
Flu
x kg
/m2 h
0
20
40
60
80
1-b
uta
no
l in
per
mea
t, w
t.%
α = 11
α = 120
TIPS RASwww.ips.ac.ru
Thermopervaporation: model fermentation mixture
Liquid mixture
wt. %
Ethanol Butanol AcetoneButyric
acidAceticacid
Feed 0.15 1.00 0.45 0.10 0.40
Permeate 0.74 20.41 1.70 0.07 0.15
Model fermentation mixtureFeed temperature: 60oCCondensation temperature: 15oC
Feed: CBuOH=2 wt.%∆T = 45 oC
TIPS RASwww.ips.ac.ru
Alcohol conversion
~90 wt.% ~70 wt.% ~40 wt.%
Catalyst Hydrocarbons Fraction of non-linear molecules, %
Pt/Al2O3 Alkanes 6-8
Cu/support Olefines 25
W-Re Olefines 50
Pd - Zn Alaknes+Olefines 50
Pt/Al2O3 + MgO + [TiFeZrMo] Alkanes 91
Control of product composition:
� Reaction mechanism depends on catalytic system.
� Presence of some compounds could improve total yield and change product composition (20% glycerin in EtOH → double yield of hydrocarbons).
Data for ethanol
0
5
10
15
20
25
30
35
С1 С2 С3-С9 Oxygenates
yiel
d, w
t.%
Alkanes
Olefines
Oxygenates
0
5
10
15
20
25
30
35
С1 С2 С3-С9 Oxygenates
yiel
d, w
t.%
Alkanes
Olefins
Oxygenates
Effect of precursor (mono- and hetero-metallic complexes)
TIPS RASwww.ips.ac.ru
Ethanol conversion: control of process selectivity
0
1 0
2 0
3 0
4 0
5 0
Pd Z n Pd -Z n
Yield (fractionС3-С10),wt.% O le f in s
A lk a n e s
~90 wt.% ~70 wt.% ~40 wt.%
Effect of catalyst type
T=350oC, Ar
TIPS RASwww.ips.ac.ru
Conversion of alcohols mixture (C2-C5)
T=350oC, Ar
0
2
4
6
8
10
12
14
С3 С4 С5 С6 С7 С8
Yie
ld, w
t.%
Composition
алканы
Олефины
Alkanes
Olefines Feed composition
Ethanol 80%
Propanol 5%
Butanol 5%
Isoamyl alcohol 10%
� ∼40% of alkanes (C4-C8).
� ∼60% molecules with non-linear structure.
Fe2O3-MgO/Al2O3+Pt/Al2O3
TIPS RASwww.ips.ac.ru
Octane number buster: solketal
►
►
By-product in biodiesel production (∼100 kg per 1 ton of biodiesel)
Poor mixing with gasoline (hydrophilic nature: logKow=-1.76)
►
►
By-product of large-scale petrochemical processes (excess on the market)
Poor mixing with gasoline (hydrophilic nature: logKow=-0.24)
►
►
►
Increasing of octane number
Reduction of gum formation (good for gasoline from CC with high olefin content)
Good mixing with gasoline (hydrophobic nature: logKow=1.07)
+ =H+
Ketalization of glycerin
1/v, ч
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5
Выход
золькеталя, %
65
70
75
80
85
90
95
100
Цеолит бета Zeolyst CP811Tl
Цеолит бета Zeolyst CP811Tl ("Реактор с структурированным режимом")Цеолит бета Zeolyst CP814ЕЦеолит бета Zeolyst CP814Е (Реактор со структурированным режимом)
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
1/v, h
100
95
90
85
80
75
70
65
Solk
eta
lyie
ld,
%
Zeolyst CP811TI
Zeolyst CP811TI (Reactor with “structured regime”)
Zeolyst CP814E
Zeolyst CP814E(Reactor with “structured regime”)
New ketalization process developed by TIPS RAS:
� continuous reactor with “structured regime”
� zeolite-based catalyst
� acetone:glycerin = 6:1
� Treaction=25-40oC
continuous reactor with “structured regime”
TIPS RASwww.ips.ac.ru
Solketal synthesis: continuous reactor + zeolite
Ketalization is reversible reaction!
Increasing of conversion by:
� Continuous removal of water (distillation cannot be used).Solution: membrane(but still not so effective).
� Selection of catalysts.Solution: zeolites.
� Excess of substrate (acetone) in the feed.Solution: local increasing of acetone:glycerin ratio (like in alkylation process).
Size distribution of catalytic particles
TIPS RASwww.ips.ac.ru
Thermo-catalytic processing: concept of novel heavy residual hydroconversion
Catalystnanoparticles
Traditional catalyst
TIPS RASwww.ips.ac.ru
Scaling up of heavy residual hydroconversion technology
10
30
50
70
90
380 420 460 500
Con
vers
ion,
%w
t.
Temperature, оС
Capacity unit: 0.5 kg/h
Capacity unit: 2.0 kg/h
Capacity unit: 1000 kg/h
TIPS RASwww.ips.ac.ru
Tar conversion with wood and polymer wastes
Gas
Liquid
Unreacted residue
Water
Tar+Wood 20%
+PE 10%+Wood 20%+PE 10%
Yie
ld, %
T=450oC, p=7MPa, Mo-based catalyst (0.05%)
Advantages:
� Wood waste fraction can be increased up to 50% (or even higher after modification of mixing unit).
� Lignin is not a problem in this process.
� Nano-sized catalyst is recycled with unreacted residue.
TIPS RASwww.ips.ac.ru
Summary
� Biorefinery is the future of downstream industry.
� Renewable feedstock can be used at existing refineries and chemical plants (after some process improvements).
� Wide range of valuable products can be produced from biomass and polymer wastes.
THANK YOU FOR YOUR ATTENTION!!!
Biorefinery: petrochemicals processing of renewable feedstockBiorefinery: petrochemicals processing of renewable feedstock
Alexey Volkov
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