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