membrane per la separazione di co2 e reattori a membrana per il … · preferred method of...
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Membrane per la separazione di CO2 e
reattori a membrana per il suo uso
A. Iulianelli, P. Morrone, A. Basile
ITM-CNR
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Riace’s Bronze
As a result of the reorganization of the Italian Research National Council scientific network, the Institute for Membrane Technology (ITM-CNR) has been recently created.
The Headquarter and Administration of ITM are located in Rende
(CS) in the Campus of the University of Calabria, with a Section at the Padova University .
The Institute today has 29 units of permanent staff and about 35
temporary units constituted by visiting professors, researchers, Ph.D. students, post-doctoral fellowships, high-educational fellowships from national and international Institutions.
It is a multidisciplinary Institute based on backgrounds in
chemical engineering; process engineering; chemistry (organic and physical); biological science; food science; material science and physics.
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Institute & Activity
ITM-CNR Institute on Membrane Technology
Inorganic membrane reactor
Membrane contactors
Water desalination by
membrane filtration
Gas separation: polymeric and
zeolite membranes
PEM fuel cell
Membrane bioreactor
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A membrane is a permeable phase acting as a selective barrier.
Transport processes depend on a driving force (gradient of P, T, C, pH, etc.).
Polymeric dense membrane
(selectivity CO2/N2 > 50)
Inorganic dense membrane
(infinite selectivity H2/other
gases)
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Transport processes depend on a driving force (as a gradient of P, T, C, pH, etc.).
2
Membranes
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Membrane
Organic
Inorganic
Wide availability of polymeric materials
Low cost
Wide surface area in small volumes (packing density)
Low mechanical resistance
Low maximum operating temperature
Low chemical stability in organic solvents
Wide range of operating temperature and pressure
Excellent chemical stability in organic solvents
Non biodegradable materials
Good mechanical properties
Some materials are brittle
Several materials and different structures
Higher costs
3 ITM-CNR
Why polymeric membrane
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Conceptual scheme of a membrane
module
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1 ITM-CNR
Biogas
• Biogas is generated by the activity of anaerobic bacteria.
• Biogas is comprised of about 60% of methane, 40% of carbon dioxide, and small amount of
hydrogen sulfide, nitrogen, and hydrogen.
• The heating value of biogas is about 60% of natural gas and about 25% of propane.
• Biogas has corrosive nature and storage of biogas is not practical.
Upgrading techniques
Chemical Adsorption
Pressure Swing Adsorption
Cryogenic Distillation
Membrane Separation
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4
Membrane Separation
Figura. Campione di membrana polimerica nanocomposita.
Immagine SEM della superficie ed ingrandimento a 5000X
ITM-CNR
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5
Robeson et al., Journal of Membrane Science 320 (2008) 390–400
1 Barrer = 3.348 x 10-16 mol m / (m2 s Pa)
ITM-CNR
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6
Figura. Schema celletta per prove di permeazione
mediante l’uso di membrane polimeriche nanocomposite
con filler inorganici di tipo TPO
Le condizioni sperimentali da utilizzarsi per l’esecuzione dei test di permeazione a gas puri e miscele sono nel seguito indicate :
T = ~ 25 °C;
DP transmembrana = 450 – 600 kPa;
Gas puri utilizzati = H2, CO2, N2, CH4;
Miscele di gas utilizzate = CO2/CH4 in rapporto molare 30/70, 40/60, 50/50.
Selettività ideale a = (QCO2/Qi)p Fattore di separazione SF = (xCO2/xCH4)p/(xCO2/xCH4)r
Membrane module scheme
ITM-CNR
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7 ITM-CNR
A case study
Flusso permeante attraverso la membrana in funzione della
pressione trans-membrana a 20 °C in due diversi cicli di
prove; campione di membrana TPO20
ΔP [bar] α(CO2 /CH4)
5 11
5,5 12
6 11
ΔP [bar] α (CO2 /CH4)
4,5 13
5 12
5,5 11
6 10
Selettività ideale (CO2/CH4) in funzione della pressione
trans-membrana per membrane TPO20 nel 1° ciclo di testing Selettività ideale (CO2/CH4) in funzione della pressione
trans-membrana per membrane TPO20 nel 2° ciclo di testing
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8 ITM-CNR
A case study
Fattore di separazione vs concentrazione di CO2 per membrane
polimeriche di tipo TPO20
Fattore di separazione CO2/CH4 per un campione di
membrana TPO20 in funzione dei tempi di lavaggio
N° PROVA DETTAGLIO PROVA
1 Membrana esposta a corrente di CO2 pura – lavata con N2
per 5min – esposta a miscela di CO2/CH4 30/70
Acquisizione: dopo 15 min
2 Membrana esposta a miscele CO2/CH4
- 30/70 - 40/60 - 50/50 senza alcun lavaggio intermedio
e successivamente esposta a miscela CO2/CH4 30/70
Acquisizione dati dopo 45 min di permeazione
3 Membrana lavata per 1 h con N2 e successivamente
esposta a miscela CO2/CH4 30/70
Acquisizione dati dopo 30 min di permeazione
4 Membrana lavata per 4h con N2 ed esposta a miscela
CO2/CH4 30/70
Acquisizione dati dopo 30 min di permeazione.
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Material CO2/N2
selectivit
y
CO2
permeance
(m3·m-2·Pa-1·s-
1)
Polydimethylsiloxane 11.4 3200 (*)
Polydimethylphenilene oxide 19 2750
Poly(4-vinylpyridine)/polyetherimide 20 52
Polyethersulfone 25 665
Polyacrylonitrile with ethylene glycol 28 91
Polysulfone 31 450
Polyimide 43 735
Poly(ethylene oxide) 52 52
Poly(amide-6-b-ethylene oxide) 61 608
Polyvinyl alcohol (cross linked) 170 8278 (*)
Vinyl alcohol / acrylate copolymer - FT 1417 2400 (*)
Polyvinyl alcohol (cross linked
formaldehyde)
1782 338 (*)
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Large scale membrane technology already exists!
www.watertechnology.
net/projects/
israel/israel10.html
Ashkelon, Israel, SWRO
plant
Number of membrane
elements:
40000
Final capacity:
100 million m³ / year
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Photograph of a
hydrochloric acid
electrolysis plant, 215.000
kton Cl2/year, Caojing –
Shanghai.
Pierre Millet - Chapter 28:
“Chlor alkali
membrane/process
technology”, in A. Basile
(Ed.) Handbook of
Membrane Reactors. Vol. 2
– Industrial applications and
economics.
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Treatment 32 RO trains on 4 floors; 40,000
membrane elements
Water price $0.527/m³
Plant footprint 75,000m² (300m x 250m)
Maximum nominal
electrical consumption <4kWh per m³ product water
Feed water salinity 40,750ppm TDS
Product water salinity <40ppm TDS
Salinity reduction 99.9%
Boron reduction >92%
330,000 m3/d
boron < 0.3
mg/L
Ashkelon,
Israel
FILMTEC are the RO membrane elements
utilized at one of the largest seawater desalination
plants: Ashkelon Desalination Plant (SW30HRLE-
400).
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El Paso Desalination Plant, Texas: the site of the world's largest
inland desalination plant (104,000 m3/d)
Deep-well injection was selected as the
preferred method of concentrate disposal.
The concentrate is placed in porous,
underground rock through wells. The sites
would confine the concentrate to prevent
migration to fresh water, provide storage
volume sufficient for 50 years of operation
and meet all the requirements of the Texas
Commission on Environmental Quality.
It uses RO to produce drinking water by
treating previously unusable brackish
groundwater (recovery factor ≈ 83%).
Production costs for the water: less than
0.36$/m3.
View of RO membrane units from inside the desalination
plant
Source: http://www.epwu.org/167080115.html
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The current global installed desalination capacity is 62.8 million m3/d.
Membrane based systems are the most widely used processes: 80% of all desalination
facilities (around 15,000) and ca. 50% of the total capacity of desalination plants.
Reverse
Osmosis
(RO)
90%
Electro
Dialysis
Reversal
(EDR)
10%
Source: V. Frenkel, Desalination & Water Reuse 17
(2008) 47.
Membrane
Desalination
80%
Thermal
Desalination
20%
Multi Effect
Distillation
(MED)
25% Multi Stage
Flash (MSF)
45%Vapor
Compression
(VC)
30%
W.J. Koros, Journal of Membrane Science, 300 (2007) 1:
An optimized thermal distillation plant producing 100 million gallons per day
requires 73 kw hr/m3. A seawater RO system (with an energy consumption of only 2.2 (kw hr)/m3) is over 10 fold more efficient than the thermal approach.
Desalination of brackish and sea waters by Membrane Reverse Osmosis:
the major industrial success of membrane operations in the last years
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Photograph of a Permea Hydrogen recovery
unit installed at an ammonia plat. The hollow
fiber modules are mounted vertically.
[R. W. Baker, “Membrane Gas-Separations”,
in “Membrane Separations”, E. Drioli (Ed.),
Wiley-VCN, 2009]
Photograph of the 550-million scfd CO2 removal plant installed by UOP at
Kandanwari (Pakistan).
The UOP Separex system reduces CO2 content of a natural-gas stream from
6.5 to 2% CO2.
[R. W. Baker, “Membrane Gas-Separations”, in “Membrane Separations”, E.
Drioli (Ed.), Wiley-VCN, 2009]
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Photograph of a system installed by MTR in Qatar in 2007,one of the most successful
petrochemical applications: treatment of resin-degassing vent in a polyolefin plant.
The plant uses hydrocarbon-permeable membranes to recover unreacted monomers from
a polyolefin plant resin degassing unit. [R. W. Baker, “Membrane Gas-Separations”,
in “Membrane Separations”, E. Drioli (Ed.), Wiley-VCN, 2009]
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ITM-CNR