JPS6351058B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a solid from which ethylene can be separated from a gas mixture containing ethylene together with nitrogen, oxygen, methane, ethane, carbon dioxide, hydrogen, etc.

Ethylene is the most important basic material in the chemical industry and is commonly used in nitrogen, oxygen, methane, ethane,
It is obtained as a mixed gas containing ethylene along with carbon dioxide, hydrogen, etc. Methods for separating ethylene from this mixed gas include a method using an ethylene absorbent or adsorbent and a cryogenic separation method, and the present invention relates to an adsorbent used for the former.

To date, it is known that a toluene solution of copper()aluminum chloride has the ability to separate ethylene. However, copper()aluminum chloride reacts strongly with water and irreversibly loses its ability to absorb ethylene, so even with 1 ppm of water, the amount of deactivation will gradually increase as the amount of mixed gas processed increases. However, it has the disadvantage that equipment corrosion progresses due to hydrogen chloride generated by the reaction.

Further, since the toluene vapor used as a solvent is contained in the recovered ethylene, a device for removing this toluene is required, and the process is subject to limitations due to the use of a liquid absorbent.

The present invention realizes simple and economically advantageous production of a solid adsorbent for ethylene, which allows ethylene to be directly separated from a mixed gas containing water.

The solid adsorbent produced by the present invention can be obtained by heating and stirring polystyrene or a polystyrene derivative together with copper halide (2) and aluminum halide in a solvent, and then removing the solvent by distilling off under reduced pressure. It is a solid adsorbent.

Copper halides ( ) used in the present invention include, for example, copper chloride ( ), copper bromide ( ), copper iodide ( ), and the like. The aluminum halides used in the present invention include, for example, aluminum chloride, aluminum fluoride, aluminum bromide, and aluminum iodide.

The polystyrene and polystyrene derivatives mentioned herein are, for example, polystyrene-based resins such as polystyrene and copolymers of styrene and 1 to 60 mol% divinylbenzene.

Solvents used in the production of the solid adsorbent in the present invention include, for example, carbon disulfide, dichloromethane, chloroform, tetrachloromethane, dichloroethane, dichloroethane, tetrachloroethane, benzene, toluene, xylene, chlorobenzene, cyclohexane, and decalin. .

The molar ratio of monomer residues of polystyrene and polystyrene derivatives and copper halide (2) in the production of ethylene adsorbent according to the present invention is 0.1 to 30, preferably 1 to 5, and copper halide (2) and aluminum halide are The molar ratio with is 0.5 to 10, preferably 1.0 to 1.5.

The manufacturing atmosphere of the adsorbent in the present invention is, for example, under nitrogen, under helium, under argon, etc.
Water in the atmosphere below 1000ppm, preferably
It is necessary to suppress it to 100ppm or less.

In the present invention, the time for stirring copper halide (2), aluminum halide, and polystyrene or polystyrene derivative in a solvent is 1
The stirring temperature is from 10 to 100°C, preferably from 20 to 60°C, for a period of minutes to 10 hours, preferably 1 to 3 hours.

The degree of reduced pressure during solvent removal in the present invention is 10 ^-6
~10 ² mmHg, preferably 10 ^-2 ~10 mmHg, the temperature is
The temperature is 0 to 250°C, preferably 10 to 180°C.

The adsorption of ethylene using the adsorbent produced according to the present invention is carried out at -40 to 90°C under normal pressure, preferably at 0.
The adsorbent can be carried out at ~40℃, 40~140℃,
Preferably the temperature is raised to 60-100°C, or
By lowering the ethylene partial pressure, the adsorbed ethylene can be released. Ethylene adsorption can be carried out at temperatures of 90° C. or higher by increasing the pressure of the mixed gas to 1 atm or higher.

The solid adsorbents produced according to the invention are stable to water. For example, as seen in Example 1, even when repeatedly brought into contact with ethylene containing water, almost no decrease in ethylene adsorption capacity is observed.

Since the adsorbent according to the invention is a solid, devices such as packed column type and fluidized bed type can be used as devices for adsorption and desorption of ethylene.

Next, the present invention will be further explained by examples.

Example 1 Aluminum chloride was purified by dehydration using a special grade reagent manufactured by Kishida Chemical Industry Co., Ltd. using a vacuum sublimation method.
Copper chloride () was used by reprecipitating a special grade reagent manufactured by Koso Chemical Co., Ltd. with a concentrated hydrochloric acid-water system, washing successively with ethanol and ether, and drying under vacuum at 80° C. for 12 hours. Carbon disulfide was used by dehydrating a first class reagent manufactured by Yoneyama Pharmaceutical Co., Ltd. with phosphorus pentoxide and then distilling it.

Polystyrene resin is manufactured by Bio-Rad
“Bio-Beads SM-2” manufactured by Laboratories
(copolymer beads of 80% styrene and 20% divinylbenzene, 20-50 meshes) in 6N hydrochloric acid.
55℃, 2 hours in 4N sodium hydroxide aqueous solution
55°C for 2 hours, 55°C for 2 hours in water, 25°C for 1 hour in methanol, and dichloromethane for 1 hour.
Impurities were removed by stirring and washing successively at 25°C for 1 hour using a magnetic stirrer, followed by vacuum drying at 80°C for 12 hours before use.

The ethylene gas used was cylinder gas manufactured by Takachiho Chemical Co., Ltd., and the water content was 0.6 mol% (6000PPm).
It was prepared as follows. Nitrogen gas was a cylinder gas manufactured by Suzuki Shokan Co., Ltd. (99.999% purity), which was dried and purified by passing it through a packed tower of Molecular Sieve 3A (manufactured by Nikka Seiko Co., Ltd.) immediately before use.

in a 100 ml two-necked eggplant flask under dry nitrogen.
2.88 g (21.6 mmol) aluminum chloride, 2.14
g (21.6 mmol) of copper chloride () and 2.83 g
(26.0 mmol per monomer residue) of cross-linked polystyrene resin "Bio-Beads SM-2" was added, 20 ml of carbon disulfide was added, and the mixture was heated to reflux while stirring using a magnetic stirrer. Thereafter, carbon disulfide was sufficiently distilled off under reduced pressure (4 mmHg) while stirring using a magnetic stirrer for 6 hours at 20 to 50 °C.
Light reddish brown resin particles were obtained. This is a solid adsorbent.

This solid adsorbent was placed in a 100 ml two-necked eggplant flask, and 1 atm of ethylene gas (water content 0.6 mol%) was added.
The mixture was combined with a container containing 20% of the sample, and measurements were taken at 20°C while stirring using a magnetic stirrer. Ethylene adsorption is rapid: 18.0 mmol (83 mol% of the charged copper chloride ()) after 3 minutes, 23.1 mmol (107 mol% of the charged copper chloride ()) after 30 minutes, and 24.4 mmol after 120 minutes.
mmol (113 mol% of the charged copper chloride) of ethylene was adsorbed. Next, use a vacuum pump to reduce the pressure (8mm
Hg) to release the adsorbed ethylene.

Then, the two-necked eggplant flask was combined with a container containing 1 atm of ethylene gas (water content 0.6 mol%), and stirred using a magnetic stirrer.
Ethylene was adsorbed at 20°C. Ethylene adsorption was rapid, with 3.4 mmol (16 mol % of the charged copper chloride ()) of ethylene adsorbed after 3 minutes and 5.2 mmol (24 mol % of the charged copper chloride ()) after 120 minutes. Next, the pressure inside this two-necked eggplant flask was reduced (8 mmHg) at 20°C for 10 minutes using an air extension pump.
Adsorbed ethylene was released.

Thereafter, this two-necked eggplant flask was again connected to a container containing ethylene gas (water content 0.6 mol %) at 1 atm, and while stirring using a magnetic stirrer, ethylene was adsorbed at 20°C. Ethylene adsorption was rapid; 3.3 mmol (15 mol% of the charged copper chloride ()) was adsorbed after 3 minutes, and 5.1 mmol (24 mol% of the charged copper chloride ()) after 120 minutes.

Thereafter, the contact between ethylene gas containing 0.6% water and the solid adsorbent of the present invention was repeated five times, and the amount of ethylene adsorbed was almost the same as the value of the second and third ethylene adsorption.

Example 2 The same reagents as in Example 1 were used, except that toluene was used instead of carbon disulfide as described in Example 1. Toluene was used by dehydrating a special grade reagent manufactured by Takahashi Fujiyoshi Shoten with metallic sodium and then distilling it.

in a 100 ml two-necked eggplant flask under dry nitrogen.
2.46 g (18.4 mmol) aluminum chloride, 2.74
g (27.7 mmol) of copper chloride () and 3.61 g
(33.2 mmol per monomer residue) of cross-linked polystyrene resin "Bio-Beads SM-2" was added, 20 ml of toluene was added, and the mixture was heated to reflux while stirring using a magnetic stirrer. Then 6 at 20-50℃
A solid adsorbent was prepared by thoroughly distilling toluene under reduced pressure (4 mmHg) while stirring using a magnetic stirrer.

When the amount of ethylene adsorption was measured by the same operation as in Example 1, 14.7 mmol of ethylene was adsorbed after 3 minutes and 19.2 mmol after 60 minutes.

The adsorbent was then heated to 106° C. at 1 atm, and ethylene was rapidly released, reaching 9.5 mmol after 10 minutes. The released gas was collected using a gas chromatograph (Polapack Q column, column temperature 60
As a result of analysis at a temperature of 20° C. (column length: 2 m), the released gas was ethylene, and no other components were detected.

Example 3 The same reagents as in Example 1 were used, except that dichloromethane was used instead of carbon disulfide as described in Example 1. Dichloromethane is a special grade reagent manufactured by Hanui Chemical Co., Ltd., which is dehydrated with phosphorus pentoxide.
It was distilled and used.

in a 100 ml two-necked eggplant flask under dry nitrogen.
2.46 g (18.4 mmol) aluminum chloride, 2.74
g (27.7 mmol) of copper chloride () and 3.61 g
(33.2 mmol per monomer residue) of cross-linked polystyrene resin "Bio-Beads SM-2" was added, and 20 ml of dichloromethane was added, followed by heating to reflux while stirring using a magnetic stirrer. Then 20-50
A solid adsorbent was prepared by thoroughly distilling dichloromethane under reduced pressure (4 mmHg) while stirring using a magnetic stirrer at °C for 6 hours.

When the amount of ethylene adsorption was measured by the same operation as in Example 1, 13.6 mmol of ethylene was adsorbed after 3 minutes and 19.0 mmol after 60 minutes.

Next, when this adsorbent is heated to 110℃ at latm,
Ethylene is released quickly and the amount released is after 10 minutes.
It reached 9.9 mmol. As a result of analyzing the released gas using a gas chromatograph in the same manner as in Example 2, it was found that the released gas was ethylene and no other components were detected.

Example 4 The same reagents as in Example 1 were used except that aluminum iodide (manufactured by Yanagishima Pharmaceutical Co., Ltd., special grade reagent) was used instead of aluminum chloride.

in a 100 ml two-necked eggplant flask under dry nitrogen.
8.2 g (20 mmol) aluminum iodide, 2.0 g
Copper chloride (20 mmol) and 2.5 g (24 mmol per monomer residue) of cross-linked polystyrene resin “Bio-Beads SM-2” were added, and carbon disulfide 20
ml and heated to reflux while stirring using a magnetic stirrer. After that, the pressure was reduced (4mm) while stirring using a magnetic stirrer for 6 hours at 20-50℃
A solid adsorbent was prepared by thoroughly distilling off carbon disulfide.

When the amount of ethylene adsorption was measured by the same operation as in Example 1, 2.1 mmol of ethylene was adsorbed after 3 minutes and 3.2 mmol after 60 minutes.

The adsorbent was then heated to 106° C. at latm, and ethylene was rapidly released, reaching 1.2 mmol after 10 minutes. As a result of analyzing the released gas using a gas chromatograph in the same manner as in Example 2, it was found that the released gas was ethylene and no other components were detected.

Example 5 The same reagents as in Example 1 were used, except that aluminum iodide was used instead of aluminum chloride and copper iodide ( ) was used instead of copper chloride ( ) described in Example 1. Both aluminum iodide and copper iodide () were special grade reagents manufactured by Yanagishima Pharmaceutical Co., Ltd.

in a 100 ml two-necked eggplant flask under dry nitrogen.
8.2 g (20 mmol) aluminum iodide, 3.8 g
(20 mmol) of copper iodide () and 2.5 g (24 mmol per monomer residue) of cross-linked polystyrene resin “Bio-Beads SM-2” were added, and carbon disulfide 20
ml and heated to reflux while stirring using a magnetic stirrer. After that, the pressure was reduced (4mm) while stirring using a magnetic stirrer for 6 hours at 20-50℃
A solid adsorbent was prepared by thoroughly distilling off carbon disulfide.

When the amount of ethylene adsorption was measured by the same operation as in Example 1, 3.4 mmol of ethylene was adsorbed after 3 minutes and 4.4 mmol after 60 minutes.

The adsorbent was then heated to 106° C. at latm, and ethylene was rapidly released, reaching 1.8 mmol after 10 minutes. As a result of analyzing the released gas using a gas chromatograph in the same manner as in Example 2, it was found that the released gas was ethylene and no other components were detected.

Example 6 Bio-Rad Laboratories as described in Example 1
Bio-Beads SM, a cross-linked polystyrene resin manufactured by
-2", cross-linked polystyrene resin S-2001 manufactured by Shoko Tsusho Co., Ltd. (beads of copolymer of 71% styrene and 29% divinylbenzene, approximately 3" in diameter)
The same reagents as in Example 1 were used except that mm) was used.

in a 100 ml two-necked eggplant flask under dry nitrogen.
2.88 g (21.6 mmol) aluminum chloride, 2.14
g (21.6 mmol) of copper chloride () and 2.83 g
(26.0 mmol per monomer residue) cross-linked polystyrene resin "S-2001" was added, 30 ml of carbon disulfide was added, and while stirring using a magnetic stirrer,
The mixture was heated to reflux. After that, the pressure was reduced (4 mmHg) while stirring using a magnetic stirrer for 6 hours at 20-50℃.
A solid adsorbent was prepared by thoroughly distilling off carbon disulfide.

When the amount of ethylene adsorption was measured by the same operation as in Example 1, 19.2 mmol of ethylene was adsorbed after 3 minutes and 22.0 mmol after 60 minutes.

The adsorbent was then heated to 100° C. at latm, and ethylene was rapidly released, reaching 21.8 mmol after 10 minutes. As a result of analyzing the released gas using a gas chromatograph in the same manner as in Example 2, it was found that the released gas was ethylene and no other components were detected.

Claims (1)

[Claims] 1. A method for producing a solid capable of adsorbing and desorbing ethylene by adding a solvent to copper halide (2), aluminum halide, and polystyrene or a polystyrene derivative, stirring the mixture, and then distilling off the solvent.