U.S. patent application number 10/363775 was filed with the patent office on 2003-09-25 for membranes for selective gas separation.
Invention is credited to Gramain, Philippe, Sanchez, Jose-Gregorio.
Application Number | 20030180425 10/363775 |
Document ID | / |
Family ID | 8854359 |
Filed Date | 2003-09-25 |
United States Patent
Application |
20030180425 |
Kind Code |
A1 |
Sanchez, Jose-Gregorio ; et
al. |
September 25, 2003 |
Membranes for selective gas separation
Abstract
The invention concerns a membrane for selective gas separation.
The membrane consists of an ethylene oxide copolymer or a polymeric
material obtained by crosslinking such a copolymer. Said copolymer
is characterised in that it consists of at least 30% in number of
--CH.sub.2CH.sub.2O-- units derived from ethylene oxide, and at
least 2% in number of --CHR--CH.sub.2O-- units derived from an
oxirane bearing a crosslinkable substituent R and/or of
--CHR.sub.1--CH.sub.2O-- units derived from an oxirane bearing a
non-crosslinkable substituent R.sub.1. The membranes are
particularly useful for separating hydrophilic gases contained in a
gas mixture.
Inventors: |
Sanchez, Jose-Gregorio;
(Castries, FR) ; Gramain, Philippe; (Saint Gely du
Fesc, FR) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
8854359 |
Appl. No.: |
10/363775 |
Filed: |
March 7, 2003 |
PCT Filed: |
September 12, 2001 |
PCT NO: |
PCT/FR01/02833 |
Current U.S.
Class: |
426/419 |
Current CPC
Class: |
B01D 71/76 20130101;
B01D 71/52 20130101; B01D 53/228 20130101 |
Class at
Publication: |
426/419 |
International
Class: |
A23K 003/02 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 15, 2000 |
FR |
00/11811 |
Claims
1. A membrane for selective gas separation, composed of an ethylene
oxide copolymer (I) or of a polymer material obtained by
crosslinking such a copolymer (I), said copolymer (I) being
characterized in that it is composed of: at least 30% by number of
--CH.sub.2CH.sub.2O-- units derived from ethylene oxide, and at
least 2% by number of --CHR--CH.sub.2O-- units derived from an
oxirane carrying a crosslinkable substituent R and/or of
--CHR.sub.1--CH.sub.2O-- units derived from an oxirane carrying a
noncrosslinkable substituent R.sub.1.
2. The membrane as claimed in claim 1, characterized in that all
the crosslinkable substituents R are identical and/or all the
noncrosslinkable substituents R.sub.1 are identical.
3. The membrane as claimed in claim 1, characterized in that the
copolymer carries different substituents R and/or different
substituents R.sub.1.
4. The membrane as claimed in claim 1, characterized in that the
substituent R1 is chosen from alkyl radicals having from 1 to 16
carbon atoms, radicals comprising one or more ether or thioether
functional groups, and radicals comprising a carboxyl group or a
hydroxyl group.
5. The membrane as claimed in claim 1, characterized in that the
substituent R is a substituent which makes it possible to crosslink
the copolymer (I).
6. The membrane as claimed in claim 5, characterized in that R is a
radical comprising a functional group which can be crosslinked by
substitution or by addition.
7. The membrane as claimed in claim 6, characterized in that R is a
haloalkyl radical or a radical comprising a double bond
>C.dbd.C<or a triple bond --C.ident.C--.
8. The membrane as claimed in claim 1, characterized in that the
substituent R is a radical which can be crosslinked by UV
irradiation.
9. The membrane as claimed in claim 1, characterized in that it is
composed of a material obtained by crosslinking a copolymer (I) by
irradiation with .gamma.-radiation or with electrons.
10. The membrane as claimed in claim 1, characterized in that it is
prepared from a copolymer of ethylene oxide EO and of
epichlorohydrin EP in which the ratio by number of EO/EP units is
between 50/50 and 98/2.
11. A process for the selective gas separation of a gas mixture,
characterized in that it comprises a stage during which the gas
mixture is passed through the membrane as claimed in one of claims
1 to 10.
12. A process for the selective separation of carbon dioxide
present in a gas mixture, characterized in that it comprises a
stage during which the gas mixture is passed through the membrane
as claimed in one of claims 1 to 10.
13. A process for the storage of fresh fruit and vegetables,
characterized in that it consists in placing said fruit or
vegetables in a wrapping composed of the membrane as claimed in one
of claims 1 to 10.
Description
[0001] The present invention relates to the use of a hydrophilic,
biocompatible and biodegradable elastomer membrane or film for the
selective separation of a gas mixture.
[0002] Gas separation using membranes composed of polymers is a
process which is developing fast and it is used in numerous
industrial fields.
[0003] Various processes for the separation and purification of
gases and in particular hydrogen are employed in plants comprising
very large membrane surface areas (Avrillon et al., "Les Techniques
de Separation de Gaz par Membranes" [Techniques for the Separation
of Gases by Membranes], Revue de l'Institut Francais du Ptrole, 45,
4, July-August 1990).
[0004] In the field of the treatment of natural or synthetic gases,
the separation and the purification of the components are essential
in meeting the increasing requirements of users. Thus, crude
natural gas and the derived components have to be freed, inter
alia, from the carbon dioxide present by a "deacidification"
operation. In this context, organic membrane processes have
numerous advantages (low capital cost, low energy consumption),
provided that the membranes have a high separating power and a high
productive output.
[0005] The preparation of semipermeable organic membranes and their
uses in gas separation were envisaged starting from polymers with
highly varied structures. While the most widely studied polymers
are glassy polymers, such as, for example, polyimides, polysulfones
and polyphenylene oxides, elastomers, such as polysiloxanes, for
example, are also of great interest. Glassy polymers generally have
good selectivity but their permeability is often unsatisfactory,
whereas elastomers have good permeability but are less selective
(A. Stern, J. of Membr. Sci., 94, 1994; S. T. Hwang et al.,
Separation Science, 9(6), 1974). Generally, it has been found that
there exists an inverse relationship between selectivity and
permeability: the better the selectivity, the poorer the
permeability.
[0006] In the field of the packaging of plants (fruit and
vegetables) and in order to slow down internal ripening phenomena,
it proved to be necessary to control the ambient humidity and the
respiratory intensity of the packaged plant, resulting in
absorption of oxygen and release of carbon dioxide. Thus, the
reduction in the content of oxygen and/or the increase in the
content of carbon dioxide in the atmosphere in which the plant is
confined have the effect of slowing down its metabolism. However,
very high concentrations of carbon dioxide and excessively low
concentrations of oxygen can result in fermentation, which is
capable of detrimentally affecting the appearance and the
organoleptic properties of the plant. It is therefore necessary to
adjust the permeability of the films according to the plants to be
stored.
[0007] FR-2 776 534 (SEB) discloses membranes having good
permeability and good selectivity with respect to carbon dioxide
and their use in the storage of fruit and vegetables. These
membranes comprise a support comprising a hydrophobic porous
polymer coated with a layer of nonporous silicone reinforced by
inorganic particles which are capable of regulating transfers of
water vapor. The performance of these membranes in the application
envisaged is, however, limited by the hydrophobic nature of the
polymer used and by its low mechanical strength, which requires the
use of a support.
[0008] U.S. Pat. No. 5,254,354 (Landec Corporation, Menlo Park,
Calif.) discloses membranes with a permeability which varies
radically and reversibly according to the temperature. These
membranes are composed of polymers comprising crystallizable side
chains and particularly small poly(ethylene oxide) chains.
[0009] U.S. Pat. No. 5,506,024 (Atochem, FR) discloses
thermoplastic elastomer films based on polyetheresteramide with in
particular poly(ethylene glycol) blocks. These films are very
permeable to water vapor and to many gases.
[0010] The aim of the present invention is to provide membranes
made of elastomer simultaneously exhibiting good permeability and
good selectivity with respect to a given gaseous compound,
sufficient mechanical strength to be able to be used in the form of
very thin self-supported films, controlled hydrophilicity and good
biodegradability, which are due to their chemical composition.
[0011] A subject-matter of the present invention is therefore a
membrane for selective gas separation, a process for gas separation
employing said membrane, and the application of the process to the
separation and removal of carbon dioxide present in a gas mixture
and to the storage of fresh fruit and vegetables.
[0012] The elastomer membrane according to the present invention is
composed of an ethylene oxide copolymer (I) or of a polymer
material obtained by crosslinking and/or by grafting such a
copolymer (I), said copolymer (I) being characterized in that it is
composed of:
[0013] at least 30% by number of --CH.sub.2CH.sub.2O-- units
derived from ethylene oxide (denoted hereinafter by "EO units"),
and
[0014] at least 2% by number of --CHR--CH.sub.2O-- units derived
from an oxirane carrying a crosslinkable substituent R (denoted
hereinafter by "REO units") and/or of --CHR.sub.1--CH.sub.2O--
units derived from an oxirane carrying a noncrosslinkable
substituent R.sub.1 (denoted hereinafter by "R1EO units").
[0015] In a specific embodiment of the invention, all the
crosslinkable substituents R are identical and/or all the
noncrosslinkable substituents R.sub.1 are identical. In another
embodiment, the copolymer carries different substituents R and/or
different substituents R.sub.1, which makes it possible to adjust
certain properties of the membranes.
[0016] The respective proportions of the various EO, REO and R1EO
units are chosen so that the polymer exhibits, optionally after
crosslinking, a crystallinity which is sufficiently low not to harm
the permeability of the membrane, a mechanical strength which is
satisfactory for the membrane and a hydrophilic/hydrophobic nature
suited to the use envisaged for the membrane, in particular for
promoting the diffusion of water-soluble gases, such as CO.sub.2,
for example. Specific choices made in the abovementioned
composition range make it possible to adjust the properties and the
characteristics of the membrane to the treatment of a specific gas
or gas mixture.
[0017] When the membranes are intended to be used at low
temperatures, it is preferable to use a copolymer which is richer
in --REO-- units and/or in --R1EO-- units. When the membranes are
intended to be used at higher temperatures, of greater than
approximately 60.degree. C., the crystallinity of a
poly(oxyethylene) tends to disappear and copolymers having a very
high content of --EO-- units can therefore be used. In this case,
however, it may be useful to improve the mechanical strength of the
membrane by crosslinking the copolymer to a greater or lesser
extent according to the result desired.
[0018] The substituent R1 is chosen from alkyl radicals having from
1 to 16 carbon atoms (more particularly alkyl radicals having from
1 to 8 carbon atoms), radicals comprising one or more thioether
functional groups and/or one or more ether functional groups (for
example, --(CH.sub.2).sub.n--O--((CH.sub.2).sub.m--O).sub.p--R'
radicals, R' being H, an alkyl or a phenyl, 0.ltoreq.n.ltoreq.4,
1.ltoreq.m.ltoreq.4 and 0.ltoreq.p.ltoreq.20), or radicals
comprising a carboxyl group or a hydroxyl group (for example,
--CH.sub.2OH or --(CH.sub.2).sub.n--COOCH.su- b.3). It is
particularly advantageous to use, for the membrane of the
invention, a copolymer comprising --R1EO-- units in which R.sub.1
is CH.sub.3, said units being derived from propylene oxide.
[0019] R is a substituent which makes it possible to crosslink the
copolymer (I). R can be a radical comprising a functional group
which can be crosslinked by substitution, such as, for example, a
haloalkyl radical, halomethyl or haloethyl radicals being
particularly preferred, in particular the chloromethyl radical.
[0020] The substituent R can also be a radical comprising a
functional group which can be crosslinked by addition, for example
a double bond >C.dbd.C< or a triple bond --C.ident.C--.
Mention may in particular be made of the alkenyl radicals
CH.sub.2.dbd.CH--(CH.sub.2).sub.q-- in which 1.ltoreq.q.ltoreq.6
and the radicals CH.sub.3--(CH.sub.2).sub.y--CH-
.dbd.CH--(CH.sub.2).sub.x-- in which 0.ltoreq.x+y.ltoreq.5 and
0.ltoreq.x, in particular those which have from 3 to 10 carbon
atoms, such as --CH.sub.2OCH.sub.2--CH.dbd.CH.sub.2 or
--CH.sub.2--CH.dbd.CH--CH.sub.3. Mention may also be made of the
allyloxyalkylene radicals having from 4 to 8 carbon atoms, for
example --CH.sub.2--O--CH.sub.2--CH.dbd.CH.sub.2).
[0021] The substituent R can additionally be a radical which can be
crosslinked by UV irradiation; mention may be made, among these
radicals, of those which comprise a double bond >C.dbd.C<or a
triple bond --C.ident.C--. R can also comprise an activated double
bond capable of crosslinking by cycloaddition; mention may be made,
by way of example, of the cinnamate or chalcone groups. Such groups
can in particular be incorporated in the copolymer by grafting onto
the haloalkyl substituents.
[0022] A copolymer (I) can be crosslinked by irradiation with
.gamma.-radiation, with electrons or with other energetic
particles. In this case, the presence of REO repeat units is not
essential. The highly energetic radiation used can create, by
tearing off atoms, highly reactive radicals which react with one
another, the performance being improved by addition of
proton-donating molecules, for example water. Depending on the
composition of the copolymers and the nature of the repeat units
constituting them, the membranes may exhibit a thermoplastic nature
due to a residual crystallinity which [lacuna] be taken advantage
of to facilitate the forming. Thus, an EO/EP copolymer of ethylene
oxide and of epichlorohydrin in which the substituent R is a
noncrosslinked chloroethyl radical and the EO/EP ratio by number is
90/10 has, at ambient temperature, a crystallinity which represents
approximately 20% of that of a pure PEO.
[0023] A membrane according to the invention will preferably have a
thickness of between 10 and 100 .mu.m if it is intended to be used
in the self-supported form. A very thin membrane, for example
having a thickness of a few microns, is preferably deposited on a
porous support.
[0024] Membranes comprising EO units and REO units and membranes
comprising EO units, PO units (derived from propylene oxide) and
REO units in which R is a haloalkyl are particularly useful as
membranes in a process for the treatment of a gas mixture targeted
at selectively separating carbon dioxide. Copolymers of ethylene
oxide (EO) and of haloalkyl, in particular when the haloalkyl is an
epihalohydrin (EH), can be used to prepare hydrophilic films which
have a low glass transition temperature (between -60.degree. C. and
40.degree. C.) and which exhibit both high permeability and good
selectivity for carbon dioxide. For the separation of the carbon
dioxide present in a gas mixture, use is advantageously made of a
membrane obtained from a copolymer of ethylene oxide (EO) and of
epichlorohydrin (EP) in which the ratio by number of the two
comonomers is preferably such that 50/50<EO/EP<98/2, more
particularly 70/30<EO/EP<95/5. In these copolymers, a portion
of the ethylene oxide units can advantageously be replaced by
propylene oxide units.
[0025] The copolymers (I) can be obtained by processes of the prior
art, such as by anionic or cationic copolymerization of ethylene
oxide and of oxirane carrying a group R and/or of oxirane carrying
a group R.sup.1. The cationic polymerization employs in particular
a catalyst of the Vandenberg type and generally involves a
coordination mechanism. In addition, use may advantageously be made
of copolymers sold in the noncrosslinked form. Mention may be made,
as example of EO/EP copolymers, of the copolymers sold by Daiso
under the name Epichlomer or by Zeon under the name Hydrin. These
copolymers are composed of different substituted or unsubstituted
oxirane units derived in particular from ethylene oxide, propylene
oxide, epichlorohydrin and allyl glycidyl ether.
[0026] The membranes are prepared by forming a composition
comprising the copolymer (I) and optionally an inorganic filler or
an organic filler. The forming can be carried out, for example, by
extrusion or by coating, which makes it possible to obtain
crosslinked or noncrosslinked films with very low thicknesses, of
the order of a few micrometers. The weight-average molecular masses
of the copolymers used will be adjusted to the forming process
chosen and to the targeted application. Thus, use will preferably
be made of high weight-average molecular masses, typically obtained
by cationic polymerization, to favor the mechanical strength of the
films.
[0027] If a copolymer which has to be subjected to crosslinking is
used for the preparation of a membrane according to the invention,
the copolymer (I) composition additionally comprises appropriate
reactants, for example a crosslinking agent, an acid scavenger
(when the crosslinking reaction releases an acid compound) and
optionally a crosslinking accelerator. The crosslinking can be
carried out during or after the forming of the membranes. The
degree of crosslinking of the copolymer used for the preparation of
a membrane must be sufficient to ensure the mechanical strength and
cohesion of the membrane. The crosslinking and in particular the
amount of crosslinking agent are preferably adjusted so that 2 to
20% of the --REO-- units participate in the crosslinking. When the
comonomer is epichlorohydrin, the crosslinking agent, which is
generally di- or trifunctional, is advantageously chosen from those
which react with the chloromethyl radical to form HCl or a chloride
salt. Mention may be made, by way of example, of trithiocyanuric
acid or its salts, sold under the Zysnet.RTM. trade mark by Zeon,
or 6-methylquinoxaline-2,3-dithiocarbonate, sold under the Daisonet
trade mark by Daiso. Use may generally be made of di- or
multifunctional compounds comprising reactive groups of the thiol
type or their salts, alcohols, alkoxides or amines. Thus, for
example, use will advantageously be made of
2,5-dimercapto-1,3,4-thiadiazole (Bismuththiol) or its salts,
bis(aminopropyl) ether compounds, such as, for example, the
products sold under the Jeffamine.RTM. trade mark by Huntsman, and
cyclic amines, such as 1,4-diazabicyclo[2.2.2]octane, sold under
the Dabco trade mark by Air Products and Chemicals. The degree of
crosslinking is controlled by the amount of crosslinking agent, the
temperature and the duration of the treatment.
[0028] Depending on the nature of the REO and R1EO units
participating in the composition of the copolymer, the crosslinking
reaction can be initiated by the thermal route, by the
photochemical and radiative route or by microwaves. Thus, when the
membrane is prepared by extrusion or coating, the crosslinking
reaction can be carried out during or after the forming.
[0029] In a specific embodiment, a membrane formed from a
crosslinked material carrying R.sup.1 groups is prepared by
partially crosslinking a copolymer of ethylene oxide and of an
oxirane carrying crosslinkable haloalkyl groups R, preferably
chloromethyl groups, and by reacting the partly crosslinked
material obtained with an appropriate compound capable of reacting
the haloalkyl groups, attaching R.sup.1 groups. In this specific
case, the R.sup.1 groups are introduced into the membrane not
during the preparation of the copolymer but during the preparation
of the membrane from a copolymer. In this case, use is made, for
the preparation of the membrane, of a composition comprising the
copolymer of ethylene oxide and of an oxirane carrying
crosslinkable groups R, a crosslinking agent (in an amount less
than that which would be necessary to crosslink all the R groups)
and a compound capable of reacting with the R groups which do not
participate in the crosslinking. The reaction can be carried out
during the extrusion at the same time as the crosslinking or else
by a subsequent treatment. This specific embodiment is advantageous
as it makes it possible to avoid the use of oxiranes carrying
R.sup.1 substituents, which it is often expensive or difficult,
indeed even impossible, to produce.
[0030] The membranes of the invention are particularly effective
for the selective separation of gas mixtures. The presence of the
EO units confers on them a hydrophilic nature which can be adjusted
by the presence of REO or R1EO units with hydrophobic natures. The
EO/EP membranes in particular are highly effective for the
selective separation of a hydrophilic gas present in the gas
mixture, in particular carbon dioxide. This is why the membranes of
the invention, in particular those which are prepared from
copolymers of ethylene oxide and of epichlorohydrin, are of great
interest in various industrial fields involving carbon dioxide.
Mention will be made, for example, of the use for the separation
and removal of the carbon dioxide present in natural or industrial
gases (deacidification of gases) or for the storage of plants
(fruit and vegetables).
[0031] The present invention is described in more detail with
reference to the examples given below, to which, however, the
invention is not limited.
EXAMPLE 1
[0032] Preparation of the Crosslinked Membranes from Copolymers of
Ethylene Oxide (EO) and of Epichlorohydrin (EP)
[0033] The membranes 100, 200-1, 200-2, 300-1, 400-1, 400-2, 1200a,
1300a and 1100c were prepared according to the following procedure
using copolymers with the compositions (in number of moles) shown
in table I. The copolymer used for the membrane 300-1 is sold under
the name Hydrin C2000 by Zeon.
[0034] 10 g of copolymer are dissolved in 250 cm.sup.3 of
acetonitrile. For the copolymers rich in epichlorohydrin, a portion
of the acetonitrile is replaced by dichloromethane. After complete
dissolution, the solution is concentrated by evaporation under cold
conditions in order to obtain approximately 60 ml of viscous
solution. 0.5 g of K-Bismuthiol, dissolved beforehand in 5 cm.sup.3
of acetonitrile, is added. The solution is subsequently cast on a
flat antiadhesive support, dried at ambient temperature and then
treated in an oven at 150.degree. C. for 10 minutes.
[0035] The crosslinking is monitored by measuring the degrees of
swelling of the membranes in water and in dichloromethane.
EXAMPLE 2
[0036] Preparation of the Noncrosslinked Membranes
[0037] The membranes 500 and 600 were prepared from copolymers with
the compositions (in number of moles) shown in table I, and the
membrane 700 was prepared from an epichlorohydrin homopolymer, by
way of comparison.
[0038] The procedure of example 1 was employed, the crosslinking
agent being omitted.
EXAMPLE 3
[0039] Measurement of the the Permeability of the Membranes to Pure
Gases
[0040] The measurements of permeability to pure gases were carried
out by the "manometric" method based on the ASTM D 1434 standard
(Standard test method for determining gas permeability
characteristics of plastic film and sheeting, reapproved 1988). In
addition, a controlled temperature chamber (.+-.0.1.degree. C.) and
pressure sensors of very high accuracy (MKS Baratron 0-100 mbar)
were used. Use of the data is based on solving the Fick's equations
for gas diffusion in a dense film according to S. W. Rutherford and
D. D. Do [Review of time lag permeation technique as a method for
characterization of porous media and membranes, Adsorption, 3,
(1997) 283-312].
[0041] The equipment is composed essentially of a membrane module
suited to the flat geometry of the films, said module being
connected upstream to a compartment which allows gas to be fed (up
to 7 bar). A compartment forming a calibrated volume is found
downstream. A vacuum system (low vacuum and ultrahigh vacuum, up to
10.sup.-9 mbar) makes it possible to carry out exhaustive degassing
of the membranes and of the two compartments (upstream and
downstream compartments). After degassing, a constant pressure of 3
bar is introduced on the upstream side, while the increase in
pressure in the calibrated volume downstream is recorded (through a
data acquisition system coupled to a computer) as a function of the
time. The curve obtained exhibits a transitory part (time lag) and
a constant part, the permeability being deduced from the
latter.
[0042] The permeability properties of the membranes prepared
according to examples 1 and 2, measured in pure gases, are collated
in table (I) below. The permeability is the Barrer permeability,
expressed in
10.sup.-10cm.sup.3STP.cm.cm.sup.-2s.sup.-1.cmHg.sup.-1. The
selectivity is the ratio of the permeabilities.
[0043] The results confirm that the membranes obtained from a
copolymer of ethylene oxide and of epichlorohydrin have an
excellent performance in the separation of carbon dioxide present
in a gas mixture, both in terms of permeability and of selectivity.
The comparative example, produced from an epichlorohydrin
homopolymer membrane, shows the very low permeability to CO.sub.2
of this membrane.
1TABLE (I) Membrane 100 200-1 200-2 300-1 400-2 400-1 700 500 600
1200a 1300a 1100c references % EO/EP/PO 93/7/0 83/17/0 83/17/0
50/50/0 96/4/0 96/4/0 0/100/0 85/2/13 50/0/50 55.9/ 61/39 87/13
44.1 Thickness 429 522 200 590 250 486 850 212 550 100 110 330 in
microns Perme- ability CH.sub.4 6.2 4.5 4.6 3.3 3.9 3.3 4.9 10.0
0.35 CO.sub.2 104 75.0 84.8 17.6 66.5 58.7 0.33 180 97.8 15.1 21.8
69.4 H.sub.2 9.5 8.5 7.5 5.2 8.0 5.5 12.4 2.95 4.5 7.7 He 7.5 5.0
2.7 3.9 4.3 3.3 8.2 2.5 2.7 4.3 N.sub.2 1.7 2.0 1.5 0.55 4.1 0.95
0.25 3.6 5.8 1.4 3.6 1.4 O.sub.2 4.6 4.0 5.7 1.1 3.1 2.8 8.5 9.5 1
1.3 7.2 C.sub.2H.sub.6 15.2 -- 11.5 3.0 8.15 -- 42.4 C.sub.3H.sub.8
39.8 -- -- 23.0 10.8 -- 13.4 C.sub.4H.sub.10 59.7 -- 82.5 89.0 46.7
-- 101.0 Selec- tivity CO.sub.2/N.sub.2 61 37.5 56.5 32 16.2 18 1.3
50 16.9 10.8 6.1 49.6 CO.sub.2/He 14 15 31.4 4.5 15.5 18 22 6.0 8.1
16.1 CO.sub.2/H.sub.2 11 8.8 11.3 3.5 8.3 10.4 14.5 5.1 4.8 9.0
CO.sub.2/O.sub.2 23 18.8 14.9 16 21.5 21 21.2 10.3 15.1 16.8 9.6
CO.sub.2/CH.sub.4 17 16.7 18.4 16 17.1 18 36.7 9.8 43.1 --
O.sub.2/N.sub.2 2.7 2.0 3.8 2.0 0.8 3.0 2.4 1.6 0.7 0.4 5.1
* * * * *