WO1982002342A1

WO1982002342A1 - Removal of hydrocarbon compositions

Info

Publication number: WO1982002342A1
Application number: PCT/US1981/001742
Authority: WO
Inventors: Carlon C Chambers
Original assignee: Carlon C Chambers
Priority date: 1980-12-30
Filing date: 1981-12-23
Publication date: 1982-07-22
Also published as: BR8108941A; JPS57502048A; EP0067870A1; EP0067870A4; NO822880L

Abstract

A process for the removal of hydrocarbon composition(s) from mixtures containing same, whether in liquid, gazeous, or mixed liquid-gazeous phase, comprising contacting the mixture with an elastomer under conditions which cause the elastomer to sorb at least a portion of the hydrocarbon composition(s). The invention has a wide variety of applications in purification, recovery, and detoxifying of hydrocarbons.

Description

REMOVAL OF HYDROCARBON COMPOSITIONS

Cross-Related Patent Application:

This application is a continuation-in-part application in the United States of America of U.S. Serial No. 06/221,295, filed 30 December, 1980.

Technical Field:

This invention relates to a technique for removing hydrocarbons, including substituted hydrocarbons from liquid or gaseous, or mixed liquid-gaseous streams, by bringing the streams into physical contact with an elastomer which will sorb the hydrocarbons sought to be removed. Hydrocarbons may be selectively removed from hydrocarbon mixtures, or from air-hydrocarbon or aqueoushydrocarbon mixtures.

Prior Art Statement:

Many different means can be utilized for the separation of hydrocarbon compositions from mixtures of several hydrocarbons or aqueous or air mixtures containing hydrocarbons. Examples of such techniques include solvent extraction, fractional distillation, steam stripping, biological degradation and the use of various additives, for example, activated carbon. It is known that hydrocarbons have the ability to be absorbed by rubber. For example, the ASTM D471-72 test for change in properties of elastomeric vulcanizates resulting from immersion in liquids measures the change in weight or volume of the test elastomeric specimen caused by the immersion in a liquid . The test is predictive in nature and its purpose is to measure the detrimental effect of a particular liquid on a particular elastomer. It makes no recognition of the fact that an elastomer is useful as a means for removing hydrocarbon compositions from hydrocarbon containing liquid and gaseous mixtures.

An article by L. B. Westover, J. J. Tou, and J. H. Mark, entitled "Novel Mass Spectrometics Sampling Device — Hollow Fiber Probe," 46 Analytical Chemistry

568 (Apr., 1974), discloses the use of a probe comprised of a hollow fiber of silicone rubber which allows certain hydrocarbons to permeate to the interior of the fiber where they can be spectrometrically detected. An article by Patrick R. Jones and Shen K. Yang, entitled

"A Liquid Chromatograph/Mass Spectrometer Interface," 47 Analytical Chemistry, 1000 (June, 1975), describes a similar use of a silicone rubber membrane separator which allows certain hydrocarbons to pass across the membrane. These disclosures are not concerned with the ability of the silicone rubber to sorb hydrocarbons, but rather its ability to allow the hydrocarbons to pass through.

Brief Disclosure of the Invention: The present invention relies on the selective sorption phenomena of elastomers to allow for the removal of hydrocarbons from other hydrocarbons or from aqueous mixtures or mixtures with air. "Hydrocarbons" as used herein include aliphatic, and aromatic hydrocarbons, saturated, and olefinic, and substituted hydrocarbons including halogenated, sulfonated, oxygenated, and nitrated, hydrocarbons. Substitutents may be other organic radicals, OH, carboxyl, nitrile, sulfonate and others. Hydrocarbons may be removed from organic solutions in which they are present as dissolved solids, from aqueous -organic mixtures , and from organic-organic mixtures, in liquid, gaseous or mixed liquid-gaseous states such, as air-vapor streams. Depending on the properties of the elastomer selected, hydrocarbons may be selectively or non-selectively removed. The process is concentration-gradient-driven and does not require the presence of heat (although heat may be beneficial to the process in some cases). The process may be conducted at ambient pressure or at any pressure at which the mixture happens to be. Moreover, it allows for the recovery of most hydrocarbon compositions removed.

The process is performed by bringing the mixture into contact with an elastomer which sorbs the hydrocarbon compositions. The degree of removal of the hydrocarbons from a mixture is dependent primarily on the amount and type of elastomer, the type of hydrocarbon, and the contact time of the mixture with the elastomer. Thereafter, the hydrocarbons can, in most cases, be recovered by desorbing them from the elastomer. Desorption can be accomplished by a variety of means, for example, by applying a vacuum to the elastomer or by displacing the hydrocarbon from the elastomer with a solvent which is more readily absorbed by the elastomer. Since absorption is concentrationgradient-driven, just contacting the elastomer with a gaseous or liquid stream that is devoid of the absorbed molecule will usually desorb it. Heating such a stripping medium enhances desorption.

Many, but not all, elastomers absorb the more aromatic hydrocarbons more readily than the less aromatic hydrocarbons. One embodiment of the invention comprises removing aromatic hydrocarbon compositions from a mixed hydrocarbon stream which contains both aliphatic and aromatic hydrocarbon compositions. Another embodiment involves the reverse, i.e., removing aliphatic hydrocarbons from aliphatic-aromatic mixtures utilizing an elastomer selected for its higher affinity for aliphatics than aromatics. A third embodiment of the invention comprises removing, or selectively removing, hydrocarbon compositions from aqueous streams, for example, waste waters. A fourth embodiment removes, or selectively removes, hydrocarbons from air streams. A fifth embodiment comprises utilizing the absorption ability of an elastomer to alter the relative concentrations amongst hydrocarbons contained within the same stream. Other specific embodiments are described hereinafter, and additional applications of the process of this invention will be readily apparent to those skilled in the art.

The invention is particularly useful in the treatment of a wide variety of industrial process streams. For example, it can be used to remove, recover and concentrate aromatic hydrocarbons having high octane values from mixed hydrocarbon refinery streams. A variety of gas streams containing hydrocarbons, e.g., hydrogen gas streams, can be purified while maintaining their pressure by the process of this, invention. The process permits the removal of hydrocarbons, including aliphatic saturated and unsaturated hydrocarbons, and aromatic and substituted aromatic hydrocarbons, e.g., benzene, toluene, naphthalene, anthracene, phenols, nitrophenols, and toxic halogenated hydrocarbons, including halogenated benzenoid structures including pesticides, insecticides, etc. from waste water without the necessity of heat, activated charcoal or biological degradation. The halogenated forms of many hydrocarbons are more easily sorbed than their non-halogenated forms.

Preferred Modes of the Invention:

The invention is applicable to the removal and recovery, if desired, of a wide variety of hydrocarbon compositions which are defined as hydrocarbons and hydrocarbon mixtures including hydrocarbons which have been nitrated, sulfonated, oxygenated and/or halogenated, and other substituted hydrocarbons. Aromatic hydrocarbon compositions are more readily sorbed by many elastomers than are olefinic compositions. Examples of unsaturated hydrocarbon ring structures include those of the benzenoid series, naphthalene and anthracene. Saturated and paraffinic hydrocarbons are preferentially sorbed by some elastomers, as will appear in the Examples hereinafter set forth.

The removal of a hydrocarbon composition is accomplished by its sorption on or in an elastomer. For the purposes of this invention, unless stated otherwise it does not matter whether the elastomer absorbs or adsorbs the hydrocarbon composition. The terms sorption, absorption and adsorption are used to denote an uptake of a hydrocarbon composition by the elastomer. Any elastomer which is capable of sorbing the hydrocarbon composition sought to be removed from a mixture can be used as long as it meets the requisite that it is not readily dissolved or otherwise deteriorated by the mixture. The elastomer can be a polymer of natural, reclaimed, vulcanized or synthetic rubber. Synthetic elastomers have the advantage of usually being more chemically inert to the mixture being treated and the hydrocarbons being sorbed. However, natural rubber has a high sorption capacity. Reclaimed rubber, such as from tires or other scrap sources, is often preferred when large volumes of elastomer are required because of the economics involved. Most reclaimed rubber from tires is a mixture of both saturated and unsaturated synthetic elastomers and natural rubber.

In one embodiment of the invention, aromatic hydrocarbon compositions, including substituted aromatic hydrocarbon compositions, are removed from hydrocarbon mixtures containing both aromatic and aliphatic hydrocarbons and from aqueous mixtures and air or gas streams containing aromatic compositions and aliphatic hydrocarbon compositions. The mixtures can be in a gaseous phase, a liquid phase or a combination of gaseous and liquid phases, and can contain dissolved hydrocarbon solids. The technique can be applied to any such sorbable mixture which is not corrosive to or a solvent for, the elastomer used to sorb the aromatic hydrocarbon composition. Examples of useful classes of synthetic elastomer include styrene-butadiene rubber, butyl rubber, nitrile rubber, ethylene-propylene copolymers, fluorine elastomers, polyacrylates, etc. Examples of specific suitable synthetic elastomers for the preferential sorption of aromatics include H-1262 (manufactured by the Mercer Rubber Co. of Trenton, N.J.), which is a blend of hycar rubber (polyacrylic rubber) and styrenebutadiene rubber; and JH-21 (manufactured by the Mercer Rubber Co.), an acrylonitrile elastomer. When the aromatic hydrocarbon composition sought to be removed is benzene, then Neoprene (a polychlorobutadiene) and

Hypalon (a chlorosulfonated polyethylene elastomer) are not as effective as some other synthetic elastomers inasmuch, as they are partially dissolved by benzene. The particular synthetic elastomer utilized in a process will be dependent upon the mixture being treated and the hydrocarbon compositions being removed. Different elastomers may exhibit differences in degree of absorption amongst particular hydrocarbons including aromatic hydrocarbons. Additionally, the sorption ability of an elastomer is often more selective toward some hydrocarbons than others in the same mixture. For example, when both olefins and aromatics are present some elastomers will more readily sorb aromatic hydrocarbons as compared to olefinic hydrocarbons. Moreover, such elastomers will more readily sorb the aromatic compositions which are more aromatic in character. This is discussed infra.

Although the elastomer has the ability to sorb hydrocarbons at atmospheric pressure, the process can also take place under negative pressure or at positive pressure. The pressure at which a particular process is conducted is dependent upon the mixture being treated. for example, whether it is in a gas or a liquid phase. Additionally, the pressure will be a function of the economics of the process. The higher the pressure, the more expensive a process becomes. The pressure of a particular sorption process can be the same pressure at which that process stream normally operates, for reasons of economics. A gaseous mixture might readily be processed at a pressure somewhat greater than atmospheric, up to the maximum achievable. For example, a hydrogen stream pressurized at 2,000 psi could simply be processed in a way to maintain the pressurization of the gas. A liquid mixture is generally processed under a pressure of less than 600 psi.

The temperature at which the process is conducted is not critical, as long as it is below that which causes degradation of the elastomer in use, and may vary over a fairly wide range. For convenience and economics, the normal temperature of the process stream may be used. As previously mentioned, absorption is concentration-gradientdriven, and so long as the concentration gradient favors absorption by the elastomer, heat tends to enhance the sorption process. Low grade waste heat may often be utilized to achieve desired temperature elevations.

The degree, and rate at which an elastomer has been previously impregnated with a hydrocarbon will, also influence its ability to sorb and desorb that or another hydrocarbon. An elastomer which is being reused to sorb a hydrocarbon, after having the hydrocarbon desorbed from it, will frequently be more efficient in sorbing the hydrocarbon than when it was fresh. Further, an elastomer which has been allowed to sorb more of a hydrocarbon than another, for example, because the sorption has been carried out at a higher temperature, will desorb at a faster rate than the other, even though desorption of both elastomers is carried out at the same temperature. Temperatures for both sorption and desorption up to between about 300 and 500°F (150-260°C), and preferably between about 300 and 400°F (150-205°C), for both sorption and desorption effectively increase the elastomer's efficiency.

The elastomer may be utilized in the form of sheets, coupons, shreds, or any other convenient manner. Usually, a granular form is preferable, the size grains determined on the basis of process parameters such as allowable pressure drop in the system, and concentration. After the elastomeric material has come into contact with the mixture and it has sorbed the hydrocarbon compounds, the elastomeric material may usually be regenerated for further use by desorbing the hydrocarbons from it. Thereafter, the desorbed hydrocarbons may usually be readily recovered. Any technique which allows for the desorption of the elastomeric material can be utilized. For example, the hydrocarbons can usually be desorbed by subjecting the elastomeric material to a vacuum or to a heated inert gas, air and/or vapor, or a heated carrier gas or steam. The hydrocarbon composition which is desorbed from the elastomeric material may be processed through a condenser to obtain a liquid product or to obtain a more concentrated gas product. The desorption can also occur through the use of a solvent which will remove the hydrocarbon compositions from the elastomeric material or through the use of a displacement agent which will be sorbed by the elastomeric material, thereby displacing the hydrocarbon composition which had been removed from the mixture. Other conventional techniques known by those skilled in the art for the desorption of the hydrocarbon compositions from the elastomeric material can also be used.

In cases where the hydrocarbon is not readily desorbed, or where there is no economic incentive to do so, the pregnant elastomer may be burned to recover its heating value, or simply encapsulated by suitable means and buried. Where highly toxic hydrocarbons have been sorbed, desorption may not be desirable. Not only is the process of the present invention useful for removing hydrocarbons from hydrocarbon streams or mixtures, it is also useful for removing such compositions from air, gas, vapor, or aqueous streams. Waste waters of industrial processes containing hydrocarbons, including substituted hydrocarbons and ones exhibiting some water solubility, can be purified by contacting the waste water with an elastomer. The process is useful in the removal of aromatics such as benzene, toluene, and anthracenes from waste water, and in removing phenols, chlorinated benzenes, nitrophenols, pesticides, insecticides, other toxic substances such as PCB, and a wide variety of other hydrocarbon types. The process may also be used to purify air-streams and off-grases of industrial processes.

An elastomer can also be utilized to alter the relative concentrations of hydrocarbons within a hydrocarbon stream or mixture. Many elastomers more readily sorb aromatic hydrocarbons which have a greater aromatic character as compared to ones with less aromatic character, other parameters such as substituents being held constant. Thus, by allowing an aromatic hydrocarbon mixture to come into physical contact with such an elastomer for a very short time period, the more aromatic hydrocarbons can be preferentially sorbed. For the purposes of this discussion, benzene is considered to have the most aromatic character. The aromaticity of an aromatic hydrocarbon decreases as the number of rings increase; thus, napthene is less aromatic in character than benzene, but more aromatic than anthracene. The closer a hydrocarbon composition is in its structure and properties to benzene, the more aromatic its character. Usually the aromaticity also decreases with alkylation. Thus, toluene is less aromatic than benzene, and xylene is less aromatic than toluene. Of course, it is understood that these are merely general principles and that preliminary testing to determine the sorptive capacity of the particular elastomer to be used for the particular hydrocarbon composition to be removed under varying conditions of time, pressure, temperature, and other parameters should be undertaken prior to making specific applications of the process of this invention, and such testing may reveal exceptions to the aforesaid general principles. Exemplary of such preliminary testing methods are those described in applicant's copending application U.S. Serial Number 06/054,690 directed to "Measuring The Aromatic Reactivity Of A Hydrocarbon Composition." Many hydrocarbon compositions are more readily sorbed than benzene, including, among others, a number of halogenated hydrocarbons, several mono-ketones, ethers, amines, aldehydes, amides, Nitro's, and nitrogen and sulfur hetrocyclics. As certain of the Examples hereof illustrate, certain generalizations may be made correlating various properties of hydrocarbons with sorbability. For example, in general, within each hydrocarbon class, molecular weight correlates with weight gain in inverse fashion for liquids and in direct fashion for gases. Where such generalizations apply, process parameters for specific applications may be calculated. Otherwise preliminary testing to determine the sorption capacity of the particular elastomer for the particular hydrocarbon should be undertaken prior to making specific applications of the process of this invention.

Where the elastomer used has a greater ability to sorb saturated or clefinic aliphatic compounds, of course, it may be used to selectively remove these compounds from mixtures also containing aromatics, thus increasing the relative aromatic content of the mixture. For example, silicone rubber exhibits a higher affinity for aliphatic saturated compounds than for aromatics. The process of the present invention can be conducted as a batch or continuous operation. The time of contact between the mixture being treated and the elastomer is dependent upon a number of parameters including the surface area of the elastomer, the allowable system pressure drop, the volume, concentration and. processing rate of the mixture being treated, the particular aromatic hydrocarbons and/or aliphatic hydrocarbons being removed, the elastomer's sorptive capability for the aromatic or aliphatic hydrocarbon being removed, the particular mixture being treated, including the presence of solvents which may enhance the capacity of a particular hydrocarbon to be sorbed by a particular elastomer, and the economics of the process. All of these parameters are related to a specific process' design.

Where certain elastomers have less affinity for one particular type of hydrocarbon compound than another, such as those with most affinity for aromatic compounds, a lesser affinity for olefinic compounds, and least affinity for saturated compounds, all hydrocarbons may be removed from the same mixture by means of more elastomer, and a longer time period for the process than used for the removal of only aromatic hydrocarbons. In such cases, a process which contacts the mixture with fresh elastomer more than once is preferred. Such a process has the ability to remove the aromatic hydrocarbons first, using more than one cycle as necessary. Thereafter the olefinic hydrocarbons may be likewise removed, and saturated compounds may be left in the mixture or removed last, depending on the elastomer selected. Since certain elastomers selectively remove certain types of hydrocarbons, many processing combinations will be apparent to those skilled in the art for using different elastomers to sequentially remove different hydrocarbon types, and thus selectively recover such hydrocarbons or alter the relative proportions of hydrocarbons in the remaining mixture. Certain solvents enhance the ability of hydrocarbons to be sorbed by particular elastomers. The ability of solid hydrocarbons to be sorbed is particularly dependent on the solvent in which the solid hydrocarbon is dissolved. Further, certain combinations of hydrocarbons are more readily sorbable than either hydrocarbon alone. For example, benzene-acetone mixtures sorb more readily than either hydrocarbon by itself, and ethanol sorbs more readily as a 25 volume percent solution in benzene than by itself or in greater concentrations in the benzene. Such synergistic effects, when discovered through testing, may readily be incorporated into the process of this invention to increase the efficiency of the process. The process of this invention may be used to improve the economics of water-alcohol separation, as an alternative to distillation. In addition to the synergistic effect of benzene on ethanol removal, it has been discovered that certain elastomers such as copolymers of vinylidene fluoride and hexafluoropropylene are effective for the selective removal of methanol. Other examples of alcohol removal are shown in the Examples hereof.

Another embodiment of this invention involves its use for the removal of hydrocarbons from process water from oil shale retorting processes, particularly the modified in situ process. Some of the hydrocarbons present in such process water are extremely difficult to remove by other means, but are readily sorbed with certain elastomers.

The process of this invention is useful in recovering and reclaiming valuable hydrocarbons which might otherwise escape to the environment. For example, when filling tanks with liquid hydrocarbons, vapors present in the empty tank are pushed out. These vapors may be sorbed with elastomers, such as scrap rubber; and as the liquid level in the tank goes down through withdrawal of the liquid, the vapors will be desorbed. In this way loss of valuable hydrocarbons may be prevented. The following Examples illustrate the process of this invention, and will suggest other specific applications to those skilled in the art.

Example 1

Rubber coupons were prepared from samples of H1262 synthetic elastomer which were of a thickness of between 0.025 and 0.125 inches and cut into strips 0.5 inches wide and of a length such that each coupon had a weight of from between 0.7 and 1.0 grams. Exactly 25 milliliters of each liquid to be tested were placed in separate, numbered 250 milliliter Erlenmeyer flasks. The numbers on the flasks correspond to the numbers given to the coupons. To each flask was added the corresponding elastomer coupon, a cork stopper wastightly installed and the flask was lightly swirled, and set aside for a period of two hours at a temperature of 65 to 75°F and at ambient pressure. At exactly two hours for each sample and within 30 seconds time, the stopper was removed, the liquid was dumped, the coupon was shaken out onto a paper towel, blotted dry and the weight of the coupon was obtained to the nearest 0.1 milligram. The weight increase of each coupon was calculated as a percentage increase from the original weight. The liquids tested were 100 percent n-decane, 100 percent benzene and varying mixtures of these two liquids. The sorptive ability of the H-1262 elastomer was measured by the amount of weight gain of each elastomer coupon. The results are given in Table 1.

Table 1

Composiition

% Benzene: % n-decane Weight Gain, % 0.2 99.8 3.58

0.5 99.5 3.67

3.0 97.0 4.80

6.0 94.0 5.33

11.0 89.0 7.06

20.0 80,0 11.67

36.0 64.0 24.18

45.0 55.0 34.78

50.0 50.0 40.14

55.0 45.0 44.69

60.0 40.0 52.67

70.0 30.0 65.21

80.0 20.0 79.23

85.0 15.0 88.26

90.0 10.0 97.57

Example 2

The same techniques of Example 1 were utilized with the exception that the liquids tested were isooctane, benzene and mixtures of these two liquids. The elastomer coupons used were of JH-21 synthetic rubber. The data is given in Table 2.

Table 2

Composition

% Benzene: % iso-octane Weight Gain, % 0.2 99.8 0.13

0.4 99.6 0.15

0.6 99.4 0.21

0.8 99.2 0.17

1.0 99.0 0.15

2.0 98.0 0.35

4.0 96.0 0.76

6.0 94.0 0.98

8.0 92.0 1.52

10.0 90.0 2.08

20.0 80.0 6.15

30.0 70.0 11.81

40.0 60.0 20.67

50.0 50.0 32.13

60.0 40.0 43.13 70.0 30.0 57.58

80.0 20.0 76.22

90.0 10.0 95.05

Example 3

Using the technique of Example 1, the ability of H-1262 elastomer to sorb different hydrocarbons was measured. The results are given below in Table 3. Table 3

Composition Weight Gain, %

Toluene 94.35

T-350 * 0.21 n-Hexane 1.28

Shale Oil ** 0.97

Tosco Tire Oil *** 4.92 n-decane 3.82

Methyl alcohol 0.81

Ethyl alcohol 0.61

Methyl ethyl ketone 82.78 n-Methyl isobutyl ketone 53.72

Xylene 81.8

Isoamyl alcohol 0.20

Iso-octane 2.70

T-350 is a non-aromatic, low vapor pressure, mixture of hydrocarbons.

** Occidental retort #4 shale oil was used.

*** Tosco Tire Oil is a product of the destructive distillation of automobile tires.

Example 4

Using the technique of Example 1, silicone rubber coupons of a thickness of .063 inches , supplied by Dupont of Chicago, Illinois (No. SS-5550, 50 duro), were tested for their ability to sorb benzene and iso-octane, and various mixtures thereof. Results are set forth in Table 4. Table 4

% Benzene in iso-octane Weight gain, %

100 101.15

95 110.47

90 118.27

85 124.79

80 133.52

75 137.00

70 140.79

65 146.04

60 146.47

55 149.87

50 151.01

45 151.07

40 146.38

35 146.38

30 145.04

25 143.93

20 140.18

15 136.26

10 132.63

5 126.17

0 120.19.

Example 5

Using the technique of Example 1, various synthetic and natural elastomers were tested for their ability to sorb six liquids. For comparison, each elastomer was also tested for percent weight gain using water. Results are set forth in Table 5. Table 5 1 of 7

100% 5% 1% 100% 100% 100% benzene benzene in benzene in iso- ethyl methyl iso-octane iso-octane octane alcohol alcohol water

Neoprene, (trans 1,4- 62.9 2.12 1.05 0.80 0.01 0.04 0.164 polychloroprene) , NOS,* t**=.105", Mercer Rubber Co., Trenton, N.J,

Neoprene, (trans 1,4- 88.29 2.33 -0.15 0.75 -0.29 -0.31 0.199 polychloroprene), 250B280, t=.081", 50 duro, Kirkhill Rubber Co., Brea, CA

Neoprene, (trans 1,4- 74.79 1,43 0,11 -0.02 -0.28 -0.21 0.058 polychloroprene), 260- Y182, t=.079", 60 duro, Kirkhill Rubber Co., Brea, CA

Hypalon, (chlorosulfonated 71.62 1.23 0.34 0.29 -0.02 0.02 0.067 polyethylene), NOS, t=.076", Mercer Rubber Co., Trenton, N.J.

Hypalon, (chlorosulfonated 71.18 1.94 0.50 0.45 0.02 -0.02 0.025 polyethylene), Hy-2660, t=.076", Mercer Rubber Co., Trenton, N.J.

* NOS = "not otherwise specified by vendor." ** t = thickness

Table 5 (Cont'd.) 2 of 7

Butyl , from inner tube, 68.32 69.51 60.26 61.09 -0.22 -0.17 -0.108 t= . 060"

Butyl, 660C1269, t=.077", 43.68 27.44 23.37 22.12 0.18 0.02 0.028 60 duro, Kirkhill Rubber Co., Brea, CA

Vitop, (Vinylidene fluoride 1.01 0.01 -0.01 0.01 0.16 9.20 0.033 and Hexafluoropropylene Copolymer), NOS, t=.076", Mercer Rubber Co., Trenton, N.J.

Nordel (EPDM, Ethylene/ 102.04 108.98 100.67 99.70 0.03 -0.21 0 propylene diene copolymer), DS-0001, t=.059", Dupont, Beaumont, TX

Nordel, (EPDM, Ethylene/ 74.87 80.01 74.44 73.75 -0.13 -0.52 0 propylene diene copolymer), t=.025", Dupont, Beaumont, TX

Nitrile, (acrylonitrile, 69.79 1.15 -0 .63 -0 .09 1.45 3. 52 0 .099 butadiene), Pairprene BS5565, t=.062", Dupont, Beaumont, TX

Table 5 (Cont'd.) 3 of 7

Nitrile, (acrylonitrile, 81.89 0.84 -0.16 -0.33 5.05 4.67 0.230 butadiene), t=.016", BS5565, Dupont, Beaumont, TX

Nitrile, 81EZ2 (20% acrylo120.81 3.68 2.01 1.83 1.66 2.08 0.117 nitrile, 80% butadiene), black, peroxide cured, t=.071", Polysar, Inc., Akron, Ohio

Nitrile, 81EZ3, ((2277%% acrylo- 107.64 1.29 0.45 0.34 1.75 2.81 0.072 nitrile, 73% butaaddiieennee) , black, peroxide cured, t=.072", Polysar, Inc., Akron, Ohio

Nitrile, 81EZ4, (34% acrylo- 93.66 0.50 0.11 0.04 1.89 3.45 0.081 nitrile, 66% butadiene), black, peroxide cured, t=.072", Polysar, Inc., Akron, Ohio

Nitrile, 81EZ5, (40% acrylo- 68.96 0.14 0.01 -0.06 1.76 3.97 0.153 nitrile, 60% butadiene), black, peroxide cured, t=.070", Polysar, Inc., Akron, Ohio

Table 5 (Cont ' d . ) 4 of 7

100% 5% 1% 100% 100% 100%^" benzene benzene in benzene in iso- ethyl methyl iso-octane iso-octane octane alcohol alcohol water

Nitrile, 81EZ6, (50% acrylo- 40.47 -0.02 -0.06 -0.08 1.07 3.42 0.188 nitrile, 50% butadiene), black, peroxide cured, t=.070", Polysar, Inc., Akron, Ohio

Nitrile and PVC, 81HZ33, 74.68 0.25 -0.04 -0.05 1.09 1.87 0,238 (acrylonitrile/butadiene polyvinyl chloride copolymer), black, ts=.075", Polysar, Inc., Arkon, Ohio

Carboxylated Nitrile, 78.80 0.62 0.13 0.03 2.79 4.74 1.426 80JK296XNBR, non-black, t=.083", Polysar, Inc., Arkon, Ohio

Carboxylated Nitrile, 79.37 0.38 0.02 -0.03 2.48 4.43 0,244 80JK238XNBR, black, t=.083", Polysar, Inc., Akron, Ohio

Nitrile/SBR, H 1262, 103.15 3.67 2.21 2.13 1.02 1.15 0.093 t=.076", Mercer Rubber Co., Trenton, N.J.

Table 5 (Cont'd.) 5 of 7

Nitrile (acrylonitrile), 117.85 0.77 0.14 0.08 1.22 2.13 0.154 JH-21, t=.072", Mercer Rubber Co., Trenton, N.J.

Silicone, SS-5550, 50 duro, 101.33 126.37 121.55 119.53 2.74 1.65 0.028 t=.063", Dupont, Chicago,

Illinois

Silicone, 950C1777, 50 100-25 126.51 121.56 122,20 2.34 1.39 0.745 duro, t=.080", Kirkhill Rubber Co., Brea, CA

Silicone, 960C1778, 60 65.44 77 .69 75.14 75.37 1.85 1.12 0.024 duro, t=.075", Kirkhill Rubber Co., Brea, CA

Silicone, 70DSA70, 1/16", 64.47 73.75 71. 33 71. 28 1.79 1.00 0.154 70 duro, t=.067", Baxter Rubber Co., Fairfield, N.J.

Silicone, 50DSA50, 1/8", 53.28 63.72 61.39 62.02 1.13 0.50 0.020 50 duro, t=.132", Baxter Rubber Co., Fairfield, N.J.

Table 5 (Cont ' d . ) 6 of 7

SBR, 550C1958, 50 duro, 150.71 23.58 17.82 16.45 -1.01 -1.17 0.074 t=.077", Kirkhill Rubber Co., Brea, CA

SBR, 560C2935, 60 duro, 140.28 14.41 9.79 10.01 0.12 0.04 0.020 t=.088", Kirkhill Rubber Co., Brea, CA

Tire tread buffings. Fleet 200.00 Service Recapping, Grand Junction, CO, +4 mesh chunks, (Hi SBR)

Tire tread buffings. Fleet 180.00 Service Recapping , Grand Junction, CO, -4 mesh, +10 mesh chunks (Hi SBR)

Tire tread buffings. Fleet 304.00 Service Recapping, Grand Junction, CO, -40 mesh, +100 mesh, (Hi SBR)

Ground whole tire scrap 324.00 #9303, 20 mesh, U.S. Rubber Reclaiming Co., Vicksburg, Miss.

Table 5 (Cont'd.) 7 of 7

Ground natural rubber scrap 275.00 (vulcanized), #G-248, U.S. Rubber Reclaiming Co., Vicksburg, Miss.

Ground whole, tire scrap, 254.00 16 mesh. Genstar Conservation Systems, Inc., Phoenix, AZ

Ground whole tire scrap, 227.00 10 mesh, Genstar Conservation Systems, Inc., Phoenix, AZ

Natural Rubber (Poly- 159.40 57.31 48.73 46.46 0.48 0.14 0.095 isoprene), 81KQ33 - 10 @ 166, NOS, t=.075", Polysar, Inc., Akron, Ohio

Butadiene rubber, NOS, 176.99 39 . 17 31.38 30 .48 1.07 0 . 38 0 .094 81KQ34 - 12 @ 166, t=.082", Polysar, Inc. Akron, Ohio

Example 6

Using the technique of Example 1, various halogensubstituted aromatic, olefinic and aliphatic hydrocarbons were tested for their ability to be sorbed by JH-21. Results are set forth in Table 6.

Table 6

Compound Weight gain, %

1-Bromopropane 232.16

1-Bromobutane 171.15

2-Bromobutane 149.03

1-Bromopentane 99.25

1-Bromohexane 41.84

Bromoform 370.98

Chloroform 495.0

1-Chlorobutane 95.73

1--Chloropentane 65. 84

1-Chlorohexane 45.91

1-iodopropane 217. 83

Allyl bromide 295.94

Allyl chloride 192.16

3-chloro 2-methylpropene 166.42

2,3-Dichloropropene 318.21

Trichloroethylene 256. 20

Bromobenzene 225.95

Chlcrobenzene 228.84

Fluoroben zenm 180 .72

Iodobenzene 158.42

Dichloroacetic acid 133.90

Benzoyl chloride 139.39

2-Chloroethanol 84.72

2,3-Dichloro-2-propanol 47.52 o-Cliloroaniline 144.72 n-Butyl chloro formate 82.25

Ethyl Bromσacetate 134.15 Table 6 (cont ' d. )

Compound Weight gain, %

Bis (2-Chloroethyl) ether 117 .73 1-Chloro-1-nitropropane 176. .69 o-Chlorophenol 130. .00 Dichlorophenyl Phosphine 82. .72 Dichlorophenyl Phosphine Oxide 54. .06 Dichlorophenyl Phosphine Sulfide 42. 62 Benzenesulfonyl chloride 66. 06 Ethanesulfonyl chloride 96. 59

Example 7

Using the technique of Example 1, with the exception that the time of exposure of the elastomer was varied as indicated, the sorptive capacity of JH-21 for benzene was tested. The results are set forth in Table 7.

Table 7

Time (hours) Weight Gain, %

0.5 47.85

1.0 79.0

1.5 102.90

2.0 120.00

2.5 132.3

3.0 139.28

3.5 144.18 Example 8

Two flasks were prepared, each containing 100 ml. of 5.0 volume percent benzene in iso-octane. Approximately five grams of JH-21 coupons were loaded into flask #1, and approximately 10 grams of JH-21 coupons were loaded into flask #2. The amount of benzene absorbed was checked after various intervals of elapsed time. Results are set forth on Table 8.

Table 8

V% benzene

Elapsed Weight g, absorbed, remaining Flask time,hrs. gain, % benzene in solution

1 0 5.0 2 0 5.0

1 2 0.6962 0.0356 4.96 2 2 0.6586 0.0660 4.93

1 4 0.9469 0.0484 4.95 2 4 0.9709 0.0973 4.89

1 6 1.1799 0.0603 4.93 2 6 1.1864 0.1189 4.86

1 22 2.1278 0.1087 4.88 2 22 2.0784 0.2083 4.76

1 35 2.66 0.1359 4.85 2 35 2.60 0.2604 4.70

1 48 3.09 0.1577 4.82 2 48 3.01 0.3017 4.66

1 60 3.3851 0.1729 4.80 2 60 3.2908 0.3298 4.63

1 146 4.0078 0.2047 4.77 2 146 3.9014 0.3910 4.56

1 194 3.9745 0.2030 2 194 3.8994 0.3908 Example 9

Using the technique of Example 1, with the exception that the time of exposure of the elastomer was varied as indicated, various proprietary "cutters" were tested for their ability to be sorbed by H-1262. "Cutters" are process distillation fractions within a certain boiling range,, which are sold as solvents.

Table 9

Composition Time (hrs.) Weight Gain, %

Western Cutter 2 9 .76

Dalton 2 6. 67

Gary Western/ Hydrobon Feed 1 5.55

Gary Western/ Hydrobon Feed 2 7.32

Gary Western/ Hydrobon Feed 3 10.18

Texaco Cutter 2 8.98

Example 10

Using the technique of Example 1, the sorptive capacity of JH-21 for decane and iso-octane was tested. Results are set forth in Table 10. Table 10

Weight gain , %

Decane 0.47

Iso-octane 0.10

Example 11

Two coupons of JH-21 were exposed to 100 percent benzene for two hours, coupon #1 at 70°F (21°C) and coupon #2 at 120°F (48.9°C). At the end of two hours coupon #1 showed a weight gain of 120.60 percent and coupon #2 showed a weight gain of 136.80 percent over their- original weights. Coupon #1 was then desorbed at 120°F (48.9°C) and coupon #2 was desorbed at 70°F (21ºC), and the percent weight gain or loss over the original coupon weights were checked at varying intervals. Results are set forth on Table 11.

Table 11 % Weight Gain or Loss

Time Elapsed (Hours) 18 20 22 24 32 44

Coupon #1 6.28 - 2.05 -3.85 -4.47 -7.31 -7.55 -7.77 -7.99 -8.53 -8.92 (120°F)

Coupon #2 22.61 7.18 4.06 3.03 -1.49 -1.94 -2.40 -2.82 -3.90 -4.70

(70°F)

Example 12

Deionized water was saturated with benzene by letting equal parts of the water and benzene stand in contact with each other for 30 days, with daily mixing, until the calculated solution concentration of ben≥ene was 0.0858 g per 50 ml (1948 ppmv). Coupon #1, a JH-21 coupon, weighing 0.9830 g, was exposed to the saturated benzene solution for varying periods of time, and coupon #2, a JH-21 coupon weighing 0.9797 g was exposed to plain deionized water for corresponding periods of time at the same temperature (70ºF, 21°C). At the end of approximately 312 days, coupons #1 and #2 were replaced with coupons #3, weighing 1.1398 g, and coupon #4, weighing 1.1283 g, in the benzene and plain water solutions respectively to test for complete removal of benzene from the water. Results are set forth in Table 12.

Table 12 coupon elapsed net increase number time,hrs. weight gain, % over blank, g

1 2 0.478 0.0029

2 2 0.184

1 4.5 0.824 0.0055

2 4.5 0.265

1 12 1.0475 0.0103

2 12 0.429

1 21 2.035 0.0146

2 21 0.551

1 98 4.334 0.0317

2 98 1.1126

1 122 4.751 0.0350

2 122 1.194

1 146 4.9542* 0.0360

2 146 1.2963

1 ~312 days 21.5666 0.1434

2 ~312 days 7.0021

3 2 hours 0.1491 0.0001

4 2 hours 0.1418

Benzene concentration of solution 1130 ppmv. Example 13

To test an elastomer' s capacity for incremental ben-zene sorption coupons #1 through #5, composed of JH-21, were first allowed to sorb benzene from solutions of varying benzene concentrations. Each coupon was then placed, without desorption, in contact with a 100 percent benzene solution for two hours, following which benzene was desorbed from each coupon by exposure to the air for 36 hours. Results are set forth in Table 13.

Table 13 desorption

Initial two hours in %weight gain from %weight gain from original %weight gain from orig. in the indicated ben- original for 1st after 2nd 2hr. absorption after indicated hours zene concentration, % 2 hour absoprtion (in 100% benzene) 18 hrs 36 hrs 145

100 125.08 151.70 -0.86 -6.74 -8.22

80 82.67 142.48 -0.65 -6.48 -8.00

60 44.90 136.33 0.47 -5.52 -7.07

40 20.57 128.80 1.33 -4.75 -6.30

20 5.43 122.22 2.06 -4.04 -5.64

E xample 1 4

The sorptive and desorptive capacities of JH-21 and H-1262 with respect to benzene were tested by coupons of each elastomer to solutions of varying benzene concentrations! at ambient temperature, and testing the percent weight gain of each after varying periods of time. Two coupons of each elastomer were used for each benzene concentration. The pairs of coupons were then separately desorbed by exposure to the air at 70°F (21°C) and 140°F (60°C) respectively for two hours. Results are set forth in Table 14.

Table 14

JH-21

Identification Absorption Desorption benzene % absorb desorb % weight gain from original % weight gain from original concentration temp, °F 2 hr 4 hr 6 hr 26 hr 2 hr 4 hr 24 hr

100 70 121.76 149 .37 157.00 ~ same 19.44 4.86 -7.03

100 140 122.26 151.68 158.23 ~ same -2.14 -8.10 -13.50

80 70 81.25 99.63 103.52 ~ same 16.71 5.34 -6.28

80 140 79.93 99.72 103.25 ~ same -0.44 -6.50 -12.60

60 70 47.28 57.69 58.68 ~ same 13.2 5.91 -3.79

60 140 45.79 56.97 58.79 ~ same -0.23 -4.67 -10.86

40 70 21.11 29.67 32.88 ~ same 10.39 6.07 -1.91

40 140 20.27 29.10 32.26 ~ same 0.99 -3.03 -8.94

20 70 5.13 7.49 9.38 15.11 9.82 7.88 2.59

20 140 5.17 7.62 9.44 15.28 3.51 0.52 -6.29

Table 14 (Cont'd.) H-1262

100 70 104.35 121.12 122.30 ~ same 14.07 1.87 -8.86

100 140 101.46 119.82 121.65 ~ same -3.26 -8.99 -13.89

80 70 82.0 95.86 95.96 ~ same 12.29 1.81 -8.76

80 140 79.42 94.97 95.67 ~ same -2.21 -7.81 -13.30

60 70 54.75 67.07 67.22 ~ same 10.80 2.23 -8.84

60 140 54.64 67.02 67.09 ~ same -1.09 -6.60 -12.81

40 70 28.76 40.58 42.9 ~ same 10.06 3.68 -7.04

40 140 29.49 40.73 43.09 ~ same -0,50 -5.60 -12.27

20 70 11.13 16.48 20.0 ~ same 5.81 1.85 -7.13

20 140 10.52 15.37 19.39 ~ same -0.46 -4.52 -11.29

Example 15

The capacity of scrap rubber for re-use in successive sorptionr-desorption cycles was tested using scrap grindings from a tire-retreading operation. This rubber has a high styrene-butadiene content. Particles of +4 mesh size (U.S. standard sieve) and particles of 4 to +10 mesh size were separately tested. One gram of each size was soaked in benzene in a stoppered flask for two hours and the absorption determined by reweighing. Desorption was carried out by exposure to the air, and was monitored at varying intervals. The material was then air-dried for 24 hours before starting the next cycle. Results are set forth in Table 15.

Table 15

2 hr. weight gain, % of Desorption weights, % of original

Cycle Size original 1 hr. 2 hr. 4 hr. as noted

8 hour

1 +4 169.90 -2.48 -6.98 -9.38 1 -4 153.83 _mm -10.95^* -11.55 _. -11.62

2 +4 198.48 - - - - 2 -4 179.30 - - - -

3 +4 202.21 - - - - 3 -4 181.55 - - - -

24 hour

4 +4 201.92 26.72 9.94 3.80 -0.08

4 -4 175.23 2.29 0.68 0.06 -0.22

5 +4 201.03 41.12 13.49 5.05 0.16 5 -4 180.70 4.35 1.27 0.28 -0.11

6 +4 198.29 33.18 10.22 3.80 0.04 6 -4 178.52 3.22 0.78 -0.16 -0.44

7 +4 204.75 21.13 8.26 3.71 0.06 7 -4 177.23 2.62 0.71 0.13 -0.08

8 +4 206.47 27.38 9.70 3.69 0.12 8 -4 186.39 2.37 0.34 -0.31 -0.50

9 +4 205.65 24.83 9.09 3.39 0.05 9 -4 190.83 3.15 0.64 -0.02 -0.23 Table 15 (Cont' d. )

2 hr. weight gain, % of Desorption weights, % of original

Cycle Size original 1 hr. 2 hr. 4 hr. as noted

10 +4 204.18 23.66 8.83 3.39 0.13 10 -4 194.96 2.71 0.82 0.18 -0.01

11 +4 209.88 32.65 9.78 3.47 0.13 11 -4 203.57 2.91 0.77 0.13 -0.09

12 +4 208.43 28.36 9.45 3.47 0.10 12 -4 207.30 2.76 0.37 -0.24 -0.45

13 +4 194.07 25.62 9.02 3.34 0.07 13 -4 184.98 3.41 0.83 0.06 -0.04

14 +4 199.59 23.47 8.21 3.11 0.05 14 -4 180.49 2.11 0.57 0.04 -0.44

15 +4 195.09 23.19 9.01 3.68 0.24 15 -4 169.81 2.88 0.88 0.17 -0.04

16 +4 198.76 26.96 9.64 3.47 -0.14 16 -4 187.06 3.08 0.48 -0.22 -0.45 17 +4 200.77 25.34 9.07 3.56 0.1817 -4 184.75 3.12 0.04 -0.07 -0.3118 +4 198.44 23.15 7.46 2.64 0.05 18 -4 181.84 2.03 0.42 0 -0.3619 +4 N.A. 20.66 7.44 2.80 0.1019 -4 185.35 2.16 0.51 0.02 -0.0720 +4 199.57 22.17 8.06 2.87 0.0320 -4 183.60 0.98 -0.38 -0.99 -1.1921 +4 199.77 23.00 8.11 2.87 -0.0521 -4 184.43 1.53 -0.93 -1.35 -1.5922 +4 199.55 24.08 8.22 2.80 0.0422 -4 186.75 2.17 0.62 0.08 -0.0623 +4 196.44 19.19 6.92 2.57 0.0123 -4 179.53 1.89 0.36 -1.14 -0.1524 +4 196.85 19.75 7.00 2.57 0.0624 -4 182.26 2.02 0.51 -0.21 -0.3525 +4 197.86 19.70 7.11 2.54 N.A.25 -4 171.61 1.70 0.46 0.37 N.A.26 +4 195.97 21.05 7.76 2.91 0.1426 -4 187.48 2.40 0.64 0.15 0.04 Table 15 (Cont'd.)

2 hr. weight gain, % of Desorption weights, % of original

Cycle Size original 1 hr. 2 hr.- 4 hr. as noted

27 +4 197.73 18.64 7.04 2.74 0.12

27 -4 182.73 1.88 0.19 -0.28 -0.39

28 +4 195.88 17.66 6.27 2.05 -0.32

28 -4 185.60 2.34 0.91 0 0.65

29 +4 193.65 17.77 6.84 2.56 0.06 29 -4 174.93 1.96 0.5Q -0.04 -1.34

Example 16

A coupon of H-1262 synthetic elastomer was tested for its capacity for re-use in successive sorption-desorption cycles. The procedure of Example 15 was followed, except that a coupon, rather than ground and screened particles of the elastomer, was used. Results are set forth in Table 16. Table 16

2 hr. weight gain, % of Desorption weights, % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 103.15 38.51 20.82 8.82 -3.09

2. 108.93 44.53 27.27 14.76 2.54

3 106.53 40.50 23.88 12.13 0.42

4 114.81 43.39 26.21 14.40 3.74

5 104.17 40.67 25.37 14.92 3.40

6 110.54 41.71 24.72 12.96 1.75

7 113.38 42.95 25.51 14.31 2.96

8 114.27 43.38 27.07 16.17 4.24

9 111.32 42.01 25.44 14.29 2.85

10 109.54 41.14 25.86 15.06 3.78

11 115.85 44.72 25.85 14.18 2.97

12 111.86 44.14 27.92 16.78 5.50

13 108.87 43.93 28.63 17.97 7.03

14 106.48 39.23 22.84 12.36 1.24

15 107.06 40.50 24.75 14.13 2.99 16 105.51 39.98 23.77 13.13 1.83

17 105.72 40.12 24.79 14.58 3.32

18 111.79 40.19 23.41 13.57 3.51

19 110.73 38.57 22.25 12.22 2.08

20 110.77 40.20 24.19 14.04 3.35

21 111.10 40.31 23.18 12.41 2.02

22 111.12 38.51 22.23 11.85 1.76

23 114.17 38.56 22.55 12.59 2.64 24 112.67 37.77 21.81 11.94 1.6325 112.12 37.86 21.44 11.75 N.A. 26 110.59 41.61 25.13 14.74 3.61 27 114.38 39.15 22.86 12.84 2.7728 115.73 39.09 23.08 13.48 3.5829 114.56 39.58 23.82 14.25 4.19 Example 17

A coupon of JH-21 synthetic elastomer was tested following the procedure of Example 16. Results are set forth in Table 17.

Table 17

2 hr. weight gain, % of Desorption weights, % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 117.85 47.21 27.16 13.47 -0.05

2 120.74 50.73 31.75 17.67 3.81

3 117.22 45.66 27.37 14.10 0.72

4 127.34 49.58 30.43 16.66 4.38

5 115.78 46.56 28.83 16.80 3.75

6 119.89 46.53 27.55 14.24 1.78

7 123.50 46.15 27.18 14.37 1.81

8 126.95 49.57 30.67 18.16 4.77

9 122.16 49.07 28.25 15.63 3.00 10 121.57 47.66 29.49 16.93 4.27 11 128.43 51.70 29.44 15.83 3.31 12 122.90 49.69 31.29 18.92 6.40 13 120.11 50.40 33.23 21.14 8.93 14 116.52 43.51 25.33 13.59 1.37 15 115.95 45.24 27.52 15.64 3.30 16 114.09 44.22 26.40 14.30 1.88 17 115.89 44.81 27.72 16.20 3.81 18 122.48 45.13 26.46 15.33 4.09 19 119.00 43.01 24.79 13.51 2.3320 121.04 45.42 27.38 15.83 3.9021 119.78 44.86 25.83 13.81 2.33 22 120.68 43.06 24.79 13.31 2.0023 123.12 43.17 25.23 14.11 3.1124 120.83 41.88 24.11 13.16 1.7525 120.55 41.98 24.22 13.27 N.A.26 119.25 46.47 28.12 16.36 4.0127 122.47 42.83 25.42 14.28 3.1228 125.23 43.95 26.08 15.28 4.2129 123.08 43.92 26.43 15.77 4.75 Example 18

A coupon of Dupont SS-5550, Silicone synthetic elastomer was tested following the procedure of Example 16. Results are set forth in Table 18.

Table 18

2 hr. weight gain, % of Desorption weights, % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 101.33 10.07 0.48 -1.26 -1.40

2 106.74 8.28 0.44 -0.47 -0.51

3 108.89 8.29 0.73 -0.20 -0.24

4 112.03 6.51 0.60 -0.18 -0.22

5 108.59 6.41 0.67 -0.08 -0.10

6 111.92 5.42 0.50 -0.09 -0.10

7 113.77 5.79 0.41 -0.09 -0.09

8 114.11 4.69 0.43 -0.03 -0.05

9 112.46 5.82 0.38 -0.13 -0.12

10 112.59 6.20 0.26 -0.07 -0.07

11 116.87 8.54 0.6.4 -0.05 -0.09

12 113.00 6.49 0.05 -0.04 -0.03

13 109.90 6.28 0.04 -0.14 -0.14

14 112.41 5.79 0.45 -0.06 -0.08

15 111.15 5.25 0.52 0 -0.03

16 112.36 5.82 0.35 -0.07 -0.09

17 111.26 4.69 0.42 0.01 0.01

18 115.51 4.15 0.18 -0.07 -0.03

19 112.64 4.64 0.24 -0.05 -0.01

20 111.91 4.41 0.23 -0.07 -0.05

21 114.40 5.47 0.40 0 -0.02

22 113.85 4.11 0.16 -0.15 -0.14

23 115.6 3.81 0.12 -0.04 -0.03

24 115.24 3.57 0.14 -0.07 -0.07

25 115.40 4.11 0.06 -0.14 N.A.

26 113.69 4.86 0.27 -0.02 -0.03

27 116.38 4.19 0.18 -0.01 0.12

28 116.98 . 3.49 0.10 -0.04 0.01

29 116.52 3.20 0.06 -0.07 -0.02 E xample 19

A coupon of Kirkhill 250B280 Neoprene synthetic elastomer was tested following the procedure of Example

16. Results are set forth in Table 19.

Table 19

2 hr. weight gain, % of Desorption weights, % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 88.29 33.99 18.79 8.93 -0.76

2 89.67 34.30 20.51 10.79 1.34

3 82.82 32.60 18.83 9.42 0.22

4 95.48 33.98 20.18 10.67 2.41

5 87.63 32.95 19.84 11.29 2.33

6 92.42 33.11 19.02 8.63 1.17

7 93.15 32.46 18.52 9.67 1.17

8 94.91 33.14 20.46 11.76 2.89

9 92.14 33.13 19.41 10.56 1.92 10 92.68 33.34 20.00 11.39 2.58 11 96.79 35.57 19.96 10.57 2.0912 92.17 33.17 20.58 11.91 3.45 13 89.49 33.71 20.90 12.29 3.99 14 90.61 31.23 17.69 9.38 0.9415 88.13 31.98 18.96 10.63 2.1216 89.33 32.32 18.63 9.83 1.1817 89.35 31.71 18.89 10.75 2.2618 94.41 32.54 18.05 9.95 2.3219 93.08 30.61 17.31 9.18 1.3920 93.76 31.87 18.50 10.23 2.2021 94.21 31.83 17.86 9.35 1.4222 93.89 30.28 17.02 8.54 1.2223 94.24 30.19 17.12 9.22 1.7624 94.32 29.55 16.58 8.78 1.1025 94.48 30.06 16.83 8.85 N.A.26 92.46 32.52 18.97 10.66 2.3127 94.37 30.63 17.46 9.65 1.8828 96.40 30.56 17.44 9.76 2.3229 94.46 30.49 17.19 10.21 2.67 Example 20

A coupon of Kirkhill 550C1958, styrene-butadiene rubber synthetic elastomer was tested following the procedure of Example 16. Results are set forth in Table 20.

Table 20

2 hr. weight gain, % of Desorption weights \ , % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 28.36 1.60 - 10.22 -15.96

2 186.55 46.16 16.02 3.28 -3.72

3 196.38 48.73 18.40 5.56 -0.95

4 201.56 44.71 16.44 4.74. -0.43

5 192.80 46.05 17.50 6..07 -0.03

6 201.24 44.70 17.40 5.12 -0.03

7 201.59 44.00 16.21 5.30 -0.01

8 202.78 43.09 16.76 6.10 0.17

9 197.35 44.07 16.67 5.56 0.09

10 198.70 44.04 17.13 5.95 0.03

11 204.36 49.23 17.23 5.53 0.04

12 198.42 44.81 16.64 5.58 0.06

13 195.85 43.87 15.86 5.37 0.05

14 197.35 42.60 15.12 5.09 -0.01

15 194.08 43.45 16.39 5.90 0.17

16 195.96 46.12 16.98 5.71 0.10

17 194.82 40.27 15.54 5.51 0.12

18 198.73 36.78 12.59 4.02 0.01

19 200.91 39.28 13.86 4.49 0.01

20 198.28 40.31 14.36 4.62 -0.04

21 199.96 42.03 14.95 4.86 0.03

22 200.79 38.77 13.67 4.10 -0.04

23 201.28 35.67 12.33 3.84 -0.04

24 199.38 35.35 12.44 3.99 0.03

25 200.48 35.74 12.50 3.94 N.A.

26 198.95 41.57 14.58 4.79 0.09

27 199.97 37.95 13.21 4.56 0.08

28 201.81 36.11 12.72 4.24 0.03

29 198.87 36.45 13.49 4.69 0.03 E xamp le 21

A coupon of Kirkhill 560C2935 styrene-butadiene rubber synthetic elastomer was tested following the procedure of Examply 16. Results are set forth in Table 21.

Table 21

2 hr. weightt gain, % of Desorption weights , % of original

Cycle original 1 hr. 2 hr. 4 hr. 24 hr.

1 140.28 60.19 34.78 14.44 -2.85

2 34.09 22.61 13.26 2.18

3 152.40 56..91 31.12 14.17 -0.30

4 38.78 23.74 12.78 2.23

5 150.93 55.73 31.01 15.18 2.14

6 160.14 55.69 30.16 13.74 1.06

7 162.12 55.68 29.77 13.95 1.10

8 153.33 57.45 31.83 16.14 2.80

9 161.47 56.50 30.83 15.16 2.17 10 161.35 57.21 31.31 15.62 2.80 11 168.70 60.72 31.64 15.01 2.2112 159.98 57.49 31.58 15.92 3.17 13 162.20 57.38 31.37 15.75 3.5214 162.12 54.85 28.74 13.47 0.91 15 158.73 55.12 30.13 15.12 2.39 16 158.60 54.14 29.53 14.01 1.47 17 159.40 52.98 29.21 14.87 2.4318 167.97 53.58 27.26 13.20 2.2019 167.27 53.22 27.17 12.70 1.4620 165.89 54.45 28.49 13.80 2.1521 166.74 54.86 28.21 13.12 1.6122 168.95 53.09 27.21 12.21 1.3423 169.48 51.39 26.36 12.66 1.8424 169.37 51.04 25.91 12.03 1.1425 171.30 52.97 26.82 12.44 N.A.26 165.68 55.61 29.32 14.35 2.2427 170.44 53.69 27.34 13.63 2.0828 172.37 52.12 26.58 12.93 2.1529 168.40 51.32 26.92 13.35 2.50 Example 22

Conditions under which polychlorinated biphenyls (PCB's) are sorbed were tested using coupons of JH-21. Pyranol, a PCB of the askarel type, manufactured by the General Electric Company, was contacted as a 100% solution, and as a 50/50 pyranol-benzene mixture at varying temperatures for two hours, then desorbed by exposure to air. After 26 hours desorption in Test 3, the temperature was lowered from 110°C to 24ºC. Results are set forth in Table 22.

Table 22

Sorption

% Pyranol Percent Desorption % of original weight after :

Test T(°C) (in Benzene) weight gain 1 hr. 2 hr. 4 hr. 26 hr. 32 hr. 37 hr. 73 day

1 24 100 2.31 - - - - 1.97 - 1.84

2 24 50 49.92 - - - - 29.58 24 .74

3 110 100 65.5 63 .16 62. 30 60 .66 44.45

24 44.6 44.67

Example 23

Retort water from a modified in situ oil shale retort was filtered and then run through a 1 inch diameter absorption column containing 10 mesh (U.S. standard sieve) ground tire scrap rubber to a depth of 27 inches, the rubber having a total weight 103.5 g. The superficial velocity through the column was approximately 2.8 inches, per minute. The benzene aromatic equivalent (BAE) test (according to the process of U. S . Serial No. 06/273 , 850) and a method 502A gravimetric freon extraction were done on the feed water after filtration and the product water. Results are set forth in Table 23.

Table 23

Freon Extractables, BAE. mg/1

Feed water 0.8038 104.25

Product water 0.3816 35.0

Example 24

The effect of various solvents on the sorbability of several solid chemicals dissolved therein, as measured by the benzene aromatic equivalent (BAE) of each mixture, was "tested by mixing the solid chemicals and solvents in the proportions shown in Table 24. Results are set forth in Table 24.

Table 24

Measured Calculated

V% of Chemical BAE of BAE of

Chemical solvent in solvent Blend chemical

3-Chloropropionic acid water 23.08 23.82 94.67 3-Chloropropionic acid benzene 24.73 126.34 206.51

Hydrocinnamic acid water 4.11 27.59 611.56 Hydrocinnamic acid benzene 3.95 95.94 -2.78

Phenol water 10.57 65 .58 598 .78 Phenol benzene 12.94 130 . 78 337. 87

2-Aminopyridine water 11. 94 6 . 53 35. 81 2 -Aminopyridine benzene 11. 43 113 .36 216 . 89

3 , 4-Dichloroanaline ethanol 25.71 39 . 42 127.32 3 , 4-Dichloroanaline benzene 19 . 72 127. 89 241.44 3 , 4-Dichloroanaline benzene 16.28 284.7

Example 25

The effect of various solvents on the sorbability of a liquid (Dalton cutter), mixed therewith, as measured by the benzene aromatic equivalent (BAE) of each mixture, was tested by mixing the Dalton cutter with the solvents in the proportions shown in Table 25. Results are set forth in Table 25.

OMPI Table 25

V% of chemical Measured BAE Calculated BAE solvent in solvent of blend of chemical

None 100 - 6.51

Benzene 50 50.56 1.12

Xylene 50 34.75 -9.40

Western cutter 50 10.47 7.61

Example 26

Certain combinations of chemicals give rise to synergistic effects on sorbability. Several combinations were tested following the procedure of Example 25. Results, expressed in terms of percent weight gain and BAE, are set forth in Table 26.

Table 26

V% of Chemical % weight gain BAE of

Chemical solvent in solvent blend Chemical

Benzene none 100 ~120 100

Ethanol none 100 1.74 9.0

Ethanol benzene 75 22.72 19.12

Ethanol benzene 50 82.59 57.01

Ethanol benzene 25 145.80 122.53

Acetone none 100 97 90.5

Acetone benzene 55 172 120

Acetone benzene 50 169 123

Acetone benzene 37.5 180 122

Acetone benzene 28. .57 195 194.15 Example 27

To test the ability of various elastomers to sorb hydrocarbons in the gaseous phase, coupons of various elastomers were suspended in a stoppered Erlenmeyer flask. Hydrocarbon gas was pumped into the flask through a tube passing through an inlet in the stopper and extending to the bottom of the flask. An outlet in the stopper allowed gas to vent to the outside. The coupons were removed and weighed at intervals as set forth in Table 27. The test procedure was varied in the case of pentane. In this case, the coupon was suspended in the vapor space above the surface of 25 ml. liquid pentane. The pentane vapor was in equilibrium with air at 70°F (21°C) and barometric pressure 628.52 mm. Hg. For comparison, coupons were also immersed in liquid pentane. Results are set forth in Table 27.

Table 27

(LIQUID) RESPONSE

RESPONSE TO (GAS) RESPONSE TO (GAS) RESPONSE TO TO PENTANE IN A 2 hr iso-octane, METHANE wt. gain, % PROPANE wt. gain, % weight gain, %

ELASTOMER Wt. gain, % 0.5 hr 1 hr 2 hr 0.5 hr 1 hr 2 hr 0.5 hr 1 hr 2 hr

BUTYL 61.09 0.0096 0.07 64.53

NORDEL 99.70 0.04 0.31 83.25 to 0.11

NITRILE 0.08 0 0.02 1.83 (JH-21)

SILICONE 119.53 0.06 0, .20 0 .22 0.55 0.96 0.99 110.31 to 0.15

SBR 16.45 0.13 0.36 29.01

SBR N.A. 0.29 0.21 N.A. (TIRE SCRAP)

NATURAL 46.46 0.058 0.13 64 .41

BUTADIENE 30.48 0.083 0.30 43727

Table 27 (Cont' d . )

(GAS) 70°F, RESPONSE (GAS) RESPONSE TO (GAS) RESPONSE TO TO PENTANE IN AIR H₂S C₂H₂ weight gain, % weight gain, % weight gain, %

ELASTOMER 0.5 hr 1 hr 2 hr 0.5 hr 1 hr 2 hr 0.5 hr 1 hr 2 hr

BUTYL 19.90 0.11 0.04

NORDEL 24.89 0.19 0.03

NITRILE 1.20 0.14 0.06 (JH-21)

SILICONE 29.84 0.43 0.47 0.47 0.18

SBR 17.94 0.44 0.05

SBR 21.47 1.34 -0.23

(TIRE SCRAP)

NATURAL 14.04 0.30 0.09

BUTADIENE 13.88 0.79 0.06

Example 28

The effects of preleaching on an elastomer's ability to sorb various hydrocarbon species was tested by preleaching certain elastomers with various solvents, and the percent capacity increase was calculated. Results are set forth on Table 28.

Table 28

SOLVENT ABSORBED SPECIES

% wt gain from original % wt gain from %

Chemical 2 hour 24 hour cycle absorbed original absorpcapacity

Name elastomer absorption desorption no. species tion time as noted increase benzene silicone 99.13 -1.35 1 methane 30 min 0.059 0 pentane silicone 110.31 -1.94 1 methane 30 min 0.0951 60.37 acetone silicone 17.66 -1.02 1 methane 30 min 0.1073 80.94 pentane Nordel 83.25 -16.57 1 methane 30 min 0.0756 84.39 pentane butyl 64.53 -6.50 pentane butadiene 43.72 -1.14 benzene +4 mesh tire 169.9 8 hr -9.38 1 benzene 2 hr 198.48 16.82 tread scrap

2 benzene 2 hr 202.21 19.02

10 benzene 2 hr 209.88 23.53 benzene -4 mesh +10 153. 83 8 hr -11 .62 1 benzene 2 hr 179 . 3 16 .56 mesh tire tread scrap

2 benzene 2 hr 181.55 18.02

11 benzene 2 hr 207.30 34.76

Table 28 (Cont'd.) SOLVENT ABSORBED SPECIES

% wt gain from original % wt gain from %

Chemical 2 hour 24 hour cycle absorbed original absorpcapacity

Name elastomer absorption desorption no. species tion time as noted increase benzene H-1262 103.15 -3.09 1 benzene 2 hr 108.93 5.60 3 benzene 2 hr 114.81 11.30 benzene JH-21 117.85 -0.05 1 benzene 2 hr 120.74 2.45 3 benzene 2 hr 127.34 8.05 benzene silicone 101.33 -1.40 1 benzene 2 hr 106.71 5.31 3 benzene 2 hr 112.03 10.56 benzene neoprene 88.29 -0.08 1 benzene 2 hr 89.66 1.55 3 benzene 2 hr 95.48 8.14 benzene 1958 SBR 150.71 -15.96 1 benzene 2 hr 186.55 23.78 3 benzene 2 hr 201.55 33.73 benzene 2935 SBR 140.28 -2.85 2 benzene 2 hr 152.40 8.64 6 benzene 2 hr 162.12 15.5

Example 29

The potential for preleaching with certain solvents to increase the sorptive and desorptive capacity of JH-21 for various hydrocarbon species was tested as shown in Table 29. Solvents showing air desorption weight loss from original were considered as having high potentials. Results are set forth in Table 29.

Table 29

SOLVENT

% wt gain from original mole, 2 hour 24 hour

Chemical Name wt. Elastomer absorption desorption

1,1-Dimeth- 90.12 JH-21 72.18 -2.58 oxyethane

Allylaminβ 57.09 JH-21 135.81 -1.72

Butylamine 73.14 JH-21 75.05 -2.85 sec. -Butyl- 73.14 JH-21 61.81 -2.89 amine

Diallylamine 97.16 JH-21 50.67 -2.55

Dimethyl 90.08 JH-21 68.01 -1.94 carbonate

Allyl acetate 100.1 JH-21 88.50 -3.14

Ethyl acetate 88.1 JH-21 96.07 -5.67 96.16 -4.89

Ethyl butyrate 116.16 JH-21 70.03 -1.38

Ethyl formate 74.08 JH-21 103323 -5.38

Methyl acetate 74.08 JH-21 96.60 -6.75

Methyl formate 60.05 JH-21 74.85 -3.45

Toluene 92.13 JH-21 110.21 -1.82

Benzene 78.11 JH-21 124.23 -1.71 Table 29 (Cont ' d. )

SOLVENT

% wt gain from original mole, 2 hour 24 hour

Chemical Name wt. Elastomer absorption desorption

Methylene 84.94 JH-21 370.10 -3.24 Chloride

Chlorobutane 92.57 JH-21 95.73 -2.87

Cis-1,2-Di- 97 JH-21 326.22 -2.00 chloroethylene trans-1,2-Di- 97 JH-21 180.77 -3.14 chloroethylene

Methylal 76.1 JH-21 64.91 -5.32

Methyl 88.10 JH-21 117.09 -2.81 propionate

Propyl 102.13 JH-21 84.21 -2.41 acetate

Propyl 88.10 JH-21 104.66 -3.47 formate

Propyl 116.16 JH-21 74.35 -1.71 Propionate

Ethylidene 146.15 JH-21 12.46 -2.26 diacetate

Allyl Ether 98.1 JH-21 64.05 -3.87

1,2-Dimeth- 90.1 JH-21 150.46 -4.32 oxyethane

Ethyl ether 74.12 JH-21 24.86 -5.27

Methylfuran 82.1 JH-21 100.04 -1.30

Propylene 58.08 JH-21 172.87 -8.55 oxide

Tetrahydro- 72.10 JH-21 213.75 -3.11 furan

3-Heptanone 114.19 JH-21 101.39 -1.53

Methyl iso- 100.16 JH-21 96.13 -1.13 butyl ketone Table 29 (Cont'd.)

SOLVENT

% wt gain from original mole. 2 hour 24 hour

Chemical Name wt. Elastomer absorption desorption

Methyl ethyl 72.11 JH-21 145.02 -6.98 ketone

3-Pentanone 86.14 JH-21 153.78 -5.90

Acetonitrile 41.05 JH-21 29.02 -4.00

Iso-Butyronitrile 69.11 JH-21 78.90 -1.85

Propionitrile 55.08 JH-21 80.47 -4.81

Nitroethane 75.07 JH-21 155.06 -1.72

Nitromethane 61.04 JH-21 56.75 -1.41

Acrylonitrile 53.07 JH-21 104.81 -7.31

Iso-Butyl 100.16 JH-21 29.28 -2.71 vinyl ether

Ethyl acrylate 100.11 JH-21 111.69 -5.28

Ethyl 142.17 JH-21 94.70 -2.94 Methacrylate

Ethyl vinyl 72.11 JH-21 43.69 -7.41 ether

Isoprene 86.09 JH-21 25.24 -2.08

Methyl acrylate 86.09 JH-21 130.15 -6.48

Methyl 100.12 JH-21 130.30 -4.68 methacrylate

Vinyl acetate 86.09 JH-21 86.53 -6.26

Acetone 58.08 JH-21 101.64 -7.61

Methyl alcohol JH-21 3.20 -1.05 Example 30

To test the ability of various elastomers to sorb and.desorb gasoline vapors displaced from storage or fuel tanks upon filling, 1.0 g coupons of various elastomers which had been preleached with pentane were exposed to vapors from a summer grade leaded regular gasoline that had been stored in an atmospheric vented Jerry can for six months. For comparison, coupons of each elastomer were also exposed to the liquid gasoline. Results are set forth on Table 30.

Table 30 weight gain, % from original

0.5 hr 2.0 hr 0.5 hr 1.0 hr

Description absorption absorption desorption desorption

Silicone, SS-5550, 50 7.74 2.88 duro, t=.063", Dupont, Chicago, 111., in vapor same, in liquid 91.15 146.37 90.99 69.18

JH-21, aery lonitrile, 1.76 1.04 t=.072", Mercer Rubber Co., Trenton, N.J. in vapor same, in liquid 5.80 12.45 9.31 8.40

Nordel (EPDM, Ethylene/ 6.62 3.92 propylene diene copolymer) DS-0001, t=.059", Dupont, Beaumont, TX, in vapor same, in liquid 101.61 207.33 131.63 98.75

Butyl, from innertube, 4.02 2.39 t=.060"., in vapor same, in liquid 50.28 138.66 88.22 67.28 Table 30 (Cont ' d. ) weight gain, % from original

0.5 hr 2.0 hr 0.5 hr 1.0 hr

Description absorption absorption desportion desportion

SBR, 550C1958, 50 duro, 6.43 3.62 t=.077", Kirkhill Rubber Co., Brea, CA., in vapor same, in liquid 25.18 66.16 46.75 39.02

Natural Rubber, (Poly- 4.93 2.73 isoprene), 81KQ 33-10 @ 166, NOS, t=.075", Polysar, Inc., Akron, Ohio, in vapor same, in liquid 45.25 122.64 84.87 66.42

Butadiene Rubber, 5.31 2.77 81KQ34-12 @ 166, t=.082", Polysar, Inc., Akron, Ohio, in vapor same, in liquid 52.28 120.85 85.38 66 .13

Tire tread buffings. 11.97 1.87 Fleet Service, Recapping, Grand Junction, CO, -40, + 100 mesh, hi SBR, in vapor

From the foregoing, it is evident that the process of this invention for removing hydrocarbons may be used in a large number of specific applications, including purification of process streams, separation of hydrocarbons, alteration of relative hydrocarbon concentrations; recapture of hydrocarbons otherwise lost to the environment; safe disposal of toxic hydrocarbons, and others which will be apparent to those skilled in the art.

Claims

1. A process for the removal of at least one hydrocarbon composition from a mixture containing saidhydrocarbon composition comprising contacting the mixture with at least one elastomer at least once under conditions which cause the elastomer to sorb at least a portion of the hydrocarbon composition.

2. The process of Claim 1 wherein the elastomer used is selected from the group consisting of natural rubber, scrap rubber, and synthetic elastomers.

3. The process of Claim 1 in which the hydrocarbon composition is desorbed from the elastomer.

4. The process of Claim 1 in which the hydrocarbon composition is not desorbed.

5. The process of Claim 3 in which the elastomer is reused for at least two successive sorption-desorption cycles.

6. The process of Claim 3 in which the desorbed hydrocarbon composition is recovered.

7. The process of Claim 1 in which substantially all of at least one hydrocarbon composition is removed from the mixture, resulting in a mixture which has been purified of the hydrocarbon composition(s).

8. The process of Claim 1 in which the relative concentration of differing hydrocarbons in a mixture containing said hydrocarbons is altered by contacting the mixture with an elastomer under conditions which cause the elastomer to selectively sorb at least a portion of at least one of the hydrocarbons present in the mixture, and the resulting, altered mixture is recovered.

9. The process of Claim 1 in which the hydrocarbon mixture comprises at least two different hydrocarbon compositions selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, olefinic hydrocarbons, and saturated hydrocarbons, and at least a portion of one of said hydrocarbon compositions is removed.

10. The process of Claim 1 in which the hydrocarbon composition removed is a substituted hydrocarbon composition.

11. The process of Claim 1 or Claim 6 in which the hydrocarbon composition removed is an alcohol.

12. The process of Claim 1 or Claim 7 in which the hydrocarbon composition removed is a toxic substance.

13. The process of Claim 1 in which the mixture containing the hydrocarbon composition (s) is in the liquid phase.

14. The process of Claim 1 in which the mixture containing the hydrocarbon composition(s) is in the gaseous phase.

15. The process of Claim 1 in which at least one hydrocarbon composition is a solid, and the mixture contains a solvent for said solid.

16. The process of Claim 1 in which a selected solvent in a selected amount is added to the hydrocarbon mixture to maximize the ability of the hydrocarbon composition to be sorbed by the elastomer.

17. The process of Claim 13 in which the mixture containing the hydrocarbon compositions is effluent water from an oil shale retorting process.

18. The process of Claim 1 in which the composition of a second hydrocarbon mixture is altered by means of selectively recovering desired hydrocarbons from the first hydrocarbon mixture and adding said recovered hydrocarbons to said second hydrocarbon mixture to alter the composition thereof.

19. The process of Claim 18 in which, the octane value of the second hydrocarbon mixture is increased by means of selectively recovering aromatic hydrocarbons from the first hydrocarbon mixture and adding said aromatic hydrocarbons to said second hydrocarbon mixture to increase the octane value thereof.

20. The process of Claim 1 in which the hydrocarbon composition comprises vapors displaced from a tank during filling of the tank with a liquid hydrocarbon.

21. The process of Claim 1 in which the elastomer is pre-leached with at least one solvent selected to increase its capacity to sorb at least one hydrocarbon composition prior to being used therefor.

22. The process of Claim 1 or Claim 21 in which the sorption and/or desorption are carried out at a temperature of between about 150°C and about 260°C to increase the rate of sorption and/or desorption.