basata sui bio-alcoli: alcuni esempi
TRANSCRIPT
Workshop conclusivoMartedì, 22 maggio 2018
Sala ConvegniTecnopolo di Reggio Emilia
Fabrizio Cavani
Gruppo di lavoro:Rita Mazzoni, Cristiana Cesari, Valerio ZanottiCarlo Lucarelli, Tommaso Tabanelli, Juliana Velasquez Ochoa, Francesco Puzzo, Giada Innocenti
Dipartimento di Chimica Industriale «Toso Montanari»
L’industria chimica
basata sui bio-alcoli:
alcuni esempi
Ethanol
EthyleneAcetaldehydeAcetonitrileAcetic acidButadieneEthylacetate
1-ButanolButenesMaleic anhydride
Ethanol
EthyleneAcetaldehydeAcetonitrileAcetic acidButadieneEthylacetate
1-ButanolButenesMaleic anhydride
Reazione di Guerbet
103 tons
1-Butanol is used in the manufacture of butyl acrylate, butyl acetate, glycols, plasticizers and solvents.
Traditionally, it has been produced either by fermentation of sugars with Clostridium Acetobutylicum (ABE process) or via the oxo petrochemical process from propylene. The scarcity of propylene (because of less use of naphtha steam cracker) has pushed new technologies for butanol production.
4 M tons
An alternative raw material: bio-1-butanol ?
Acetone-butanol-ethanol from biomass with the ABE process
Cordite was the most important explosive during the 1st WW, made from nitrocellulose, nitroglycerin and petroleum jelly.
Cordite was formulated with acetone as solvent, butacetone in Britain was imported from the US (done by distillation from wood) via shipping lanes that were under attack by German submarines. So, England was searchingfor a new process to make acetone.
Chaim Weizmann (Manchester Univ.), had published a paper describing the fermentation of carbohydrates with Clostridium acetobutylicum («The Weizmann organism») resulting in a mixture of ethanol, acetone and 1-butanol (1/3/6): the ABE process.
The first patent: William Perkin Jr, Chaim Weizmann, Auguste Fernbach filed on June 1911 covered the formation of acetone from a carbohydrate feedstock that included potato starch and acid-hydrolysed wood by fermentation using a butylic bacillus of the type Fitz: a second-generation biochemical !!!!
But also corn from maize was imported from USA. A campaign was launched in England to collect horse chestnuts(conkers).Industrial scale production of acetone started in six British distilleries in early 1916, with 30,000 tonnes produced during the war. After the war, the Weizmann process was operated by Commercial Solvents Corporation from 1920 to 1964 with plants in the US and UK.After World War II, ABE fermentation became generally non-profitable, compared to the production acetone, butanol and ethanol from petroleum.
Royal Navy Cordite factory: acetone fermentation tank
Chaim Weizmann, 1874-1952He was also a leader of British ZionismFirst President of Israel, 1949-1952
As a recognition for his discovery, the Balfour declaration in 1917 stated that Britain looked with favour on the founding of Jewish state in Palestine, whch had been under British control for many years. This declaration played a key role in the creation of Israel in 1948, after the 2nd WW. Weizmann became the first President of Israel.
butadiene from bio-1-butanol
ABE process
1-butanol
1-butene
butadiene
½ O2
- H2O
- H2O
Ind. Eng. Chem. 1957
Chaim Weizmann1874-1952
The process for gas-phase synthesis of 1-butanol by Guerbetcondensation of bio-ethanol developed by Abengoa Bioenergy
Abengoa Bioenergy technology is claimed to convert ethanol into 1-butanol and other linear higher alcohols (hexanol, octanol and decanol).
From patents: best yield to 1-butanol, with a Pd-Ga/Mg/Al (ex HT) catalyst, in a N2/(H2) atmosphere, in liquid phase, T 200°C, P 32 bar, ca 15% (selectivity > 80%, with H2 > 90%).However, it is likely that the reaction will be conducted in the gas-phase.
Maleic anhydride by n-butane selective oxidation
ALMA process, Polynt(VO)2P2O7
Steam Drum
Reactor
Air
Off Gas Filters
CatalystHandlingSystem
Spent Catalyst
TransportGas
SaturatedHP Steam
ReactionEffluent
Butane
Cyclones
Off GasCooler
ButaneEvaporator
Air Compressor
BFW
World capacity, MT/yYear China Rest2008 0.7 1.02012 1.2 1.02013 1.5 1.02014 1.7 1.0
O
O
O
O
O
O O
O
O
O
O
O
O
O
O O
O
O
1-butanol
air
1-butanol
(air)
MA, by-productsMA, by-products
1-butanol → butenes + H2O
butenes + O2 → MA
T 300-400°C
Single-step
configuration
1-butanol → butenes + H2O
butenes + O2 → MA
(air)
Two-step
configuration
T 300-350°C
T 250-300°C
C4H9OH- H2O
Oxidative stepsAcid-catal. step
O
O
O
O
O
O O
O
O
O
O
O
O
O
O O
O
O
1-butanol
air
1-butanol
(air)
MA, by-productsMA, by-products
1-butanol → butenes + H2O
butenes + O2 → MA
T 300-400°C
Single-step
configuration
1-butanol → butenes + H2O
butenes + O2 → MA
(air)
Two-step
configuration
T 300-350°C
T 250-300°C
O
O
O
O
O
O O
O
O
O
O
O
O
O
O O
O
O
1-butanol
air
1-butanol
(air)
MA, by-productsMA, by-products
1-butanol → butenes + H2O
butenes + O2 → MA
T 300-400°C
Single-step
configuration
1-butanol → butenes + H2O
butenes + O2 → MA
(air)
Two-step
configuration
T 300-350°C
T 250-300°C
C4H9OH- H2O
Oxidative stepsAcid-catal. step
O
O
O
O
O
O O
O
O
O
O
O
O
O
O O
O
O
1-butanol
air
1-butanol
(air)
MA, by-productsMA, by-products
1-butanol → butenes + H2O
butenes + O2 → MA
T 300-400°C
Single-step
configuration
1-butanol → butenes + H2O
butenes + O2 → MA
(air)
Two-step
configuration
T 300-350°C
T 250-300°C
«bifunctional» catalyst: DuPont vanadylpyrophosphate
Reaction conditions: 1% 1-butanol in air, W/F 1,3 g· s/mL
0
20
40
60
80
100
0
10
20
30
40
50
280 300 320 340 360 380 400 420
Co
nve
rsio
n (
%)
Yiel
d (
%)
Temperature (°C)
MA
conversion
CO2
CO
2-butenes
1-butene
acids
PA
Reaction mechanism as inferred from Operando-DRIFTS and reactivity of intermediates
Reaction conditions:
1% 1-butanol in airContact time = 1,3 g· s/mLTemperature: 340°C
CB BB1 BB2 BB30
5
10
15
20
25
30
35
40
S
ele
cti
vit
y (
%)
MA
PA
Bio-butanols from 3 suppliers1-Butanol from petroil
MA MA
MAMA
PA
PAPA
PA
CB BB1 BB2 BB30
5
10
15
20
25
30
35
40
Sele
cti
vit
y (
%)
MA
PA
Name Impurities
Chemical n-butane (CB)
1-propanol, ethanol, 2-butanol, n-butylether, acrolein, butanoic acid ethyl ester/propanoic acid propyl ester
Bio-1-butanol BB1
1-propanol, 1,1-dibutoxybutane, 2-methyl-1-butanol, butyraldehyde, acrolein, benzaldehyde, 2-butanol, 2-methyl-1-propanol (isobutanol), propionaldehyde, 3-methyl-1-butanol, butylacetate, butylformate, styrene, C21H15N (tentative identification: 5H-Naphtho[2,3-C]carbazole-5-methyl)
Bio-1-butanol BB3
n-butylether, 1,3 diazine, 1-propanol, butyrraldehyde, 2-butanol, 1-butanol 3-methyl, 1,1-dibutoxybutane, methanol, acetone, 2-propanol 2-methyl, 2-pentanol, 1,3 butanediol After Claisen: 1-propanol, butanal, 2-butanol, 2-pentanol, 1-propanol 2-methyl, 1-butanol-2-methyl, 1-butene-2-butoxy, 2-butene-1-butoxy, n-butyleter, butylacetate, 1,1 dibutoxy butane, 1,3-diazine (CAS 000289-95-2). No carbazole.
N
What about the cost of 1-butanol ?
acetone
1-butanol
ethanol
Projected product prices based on expected future market conditions and historical trends(for the products of the ABE fermentation process)
From P.H. Pfromm et al. BIOMASS & BIOENERGY 34, 515, 2010
Integration in a n-butane-to-MA plant (same catalyst, differentconditions, no PA from n-butane) Integration in a o-xylene-to-phthalic anhydride plant (same productsand by-products)
Fermentation
RefiningNaphtha
reforming oxidationoil o-xylene
air
saccharidesBio-butanol
Separationpurification
Maleic anhydride
Phthalic anhydride
By-products
Integration in a co-location scenario
How to decrease OPEX and CAPEX for 1-butanol oxidehydration to MA ?
Conventional phthalic anhydride plant
In collaboration with Process Design Center PDC, Breda, NL
Retrofitted process for the co-production of MA/PA from bio-butanol
In collaboration with Process Design Center PDC, Breda, NL
Summary of the retrofit scenarios evaluated on their industrial economics
( = MA yield at total 1-butanol conversion)
Summary of the retrofit scenarios evaluated on their industrial economics
( = MA yield at total 1-butanol conversion)
Target for economicsustainability in a co-location scenario
Cradle-to-gate analysis of maleic anhydride synthesis
LCA of Maleic Anhydride
Natural gas
Petroil
n-butanerecovery
n-Butane oxidation
separationNaphtha
Reforming
separationBenzene
Fluid-bed separation
Corn
cultivation
Bio-ethanol
ABE
Bio-butanol
oxidation
Fixed-bed
Oxidehydration(in a dedicated plant)
harvesting
Bio-butanol & by-products
Guerbet
Raw matAcetone-Butanol-Ethanol
separation
Maleic
anh
ydrid
e
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
MA frombenzene, fixed
bed
MA frombutane, fixedbed - thermalincineration
MA frombutane, fluidbed - ALMAtechnology
MA frombiobutanol
(40%) - Guerbet
kPt
Cumulative impact
MidPoint Impact categoriesClimate change Human HealthOzone depletionHuman toxicityPhotochemical oxidantformationParticulate matter formationIonising radiationClimate change EcosystemsTerrestrial acidificationFreshwater eutrophicationTerrestrial ecotoxicityFreshwater ecotoxicityMarine ecotoxicityAgricultural land occupationUrban land occupationNatural land transformationMetal depletionFossil depletion
MA from fossil hydrocarbonsMA from bio-butanol
ReCiPe Score
SimaPro, PhD version 8.0.4.30.Ecoinvent Centre (2014) Ecoinvent 3.1 Database.
0
1000
2000
3000
4000
5000
6000
MA frombenzene,fixed bed
MA frombutane, fixedbed - thermalincineration
MA frombutane, fluidbed - ALMAtechnology
MA frombiobutanol
(40%) -Guerbet
kg C
O2
eq
.Carbon footprint
0
500
1000
1500
2000
2500
MA frombenzene,fixed bed
MA frombutane, fixedbed - thermalincineration
MA frombutane, fluidbed - ALMAtechnology
MA frombiobutanol
(40%) -Guerbet
kg o
il e
q.
Fossil fuels depletion
020406080
100120140160180200
MA frombenzene,fixed bed
MA frombutane, fixedbed - thermalincineration
MA frombutane, fluidbed - ALMAtechnology
MA frombiobutanol
(40%) -Guerbet
GJ
eq
.
Total resources consumption
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
MA frombenzene,fixed bed
MA frombutane,
fixed bed -thermal
incineration
MA frombutane,
fluid bed -ALMA
technology
MA frombiobutanol
(40%) -Guerbet
MA frombiobutanol
(80%) -Guerbet
kPt
Cumulative impact
MidPoint Impact categoriesClimate change Human HealthOzone depletionHuman toxicityPhotochemical oxidantformationParticulate matter formationIonising radiationClimate change EcosystemsTerrestrial acidificationFreshwater eutrophicationTerrestrial ecotoxicityFreshwater ecotoxicityMarine ecotoxicityAgricultural land occupationUrban land occupationNatural land transformationMetal depletionFossil depletion
40% yield to MA
80% yield to MA
MA from bio-butanol
ReCiPe Score
Is it possible to increase the yield to MA ?
Because of surface saturation by 1-butanol (as from DRIFT), we have two options to obtain better yield to MA (and PA):1. To lower 1-butanol inlet pp, to increase the availability of oxidised V sites (but not toomuch)2. To accelerate products desorption and reoxidation of V sites.
Is it possible to increase the yield to MA ?
Because of surface saturation by 1-butanol (as from DRIFT), we have two options to obtain better yield to MA (and PA):1. To lower 1-butanol inlet pp, to increase the availability of oxidised V sites (but not toomuch)2. To accelerate products desorption and reoxidation of V sites.
0
20
40
60
80
100
180 220 260 300 340 380 420
Co
nve
rsio
n, s
ele
ctiv
ity
(%)
Temperature (°C)0.4 mol% 1-butanol in feed, 20% O2
1% butanol
MA
PA
Acknowledgements
LCA Fabrizio PassariniDaniele Cespi
1-butanol to MAGiulia PavarelliFrancesco PuzzoEuroBioRef FP7
The VALSOVIT TeamRita MazzoniCristiana CesariValerio ZanottiTommaso TabanelliCarlo LucarelliFrancesco PuzzoGiada InnocentiJuliana Velasquez OchoaCAVIROGiovanni MaraniRosa Prati
20162014