JPS59212437A - Process for adsorptive separation of unsaturated hydrocarbon - Google Patents

Abstract

PURPOSE:To separate an unsaturated hydrocarbon from a gaseous mixture, by using a solid adsorbent composed of polystyrene or a poly-styrene derivative and a cuprous halide, and optionally a halide of other metal or ammonium halide. CONSTITUTION:An unsaturated hydrocarbon is separated and purified to removed under mild condition from a gaseous mixture, by using a solid adsorbent composed of (A) a cuprous halide (e.g. cuprous chloride), (B) polystyrene or a polystyrene derivative (e.g. a polystyrene resin) and optionally (C) a halide of a univalent or bivalent metal or ammonium (e.g. calcium chloride, magnesium chloride, etc.) other than cuprous halide. EFFECT:The process is simple and advantageous from technical and economic viewpoints.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating unsaturated hydrocarbons from a mixed gas containing the unsaturated hydrocarbons together with nitrogen, oxygen, methane, ethane, carbon dioxide, hydrogen, and the like.

Unsaturated hydrocarbons such as olefins and dienes are important basic materials in the chemical industry.

Produced by pyrolysis of saturated hydrocarbons such as natural gas, refinery gas and petroleum fractions. However, off-gases produced by fluid catalytic cracking equipment and purge gases from various processes can also contain significant amounts of unsaturated hydrocarbons. However, in these cases, unsaturated hydrocarbons are obtained as a gas mixture with nitrogen, oxygen, methane, ethane, carbon dioxide, hydrogen, etc. I cut it. 9 normal for this gas mixture.

1,000 to 20,000 ppm of water is outside the building7.
Therefore, in order to use unsaturated hydrocarbons as raw materials for chemistry, it is necessary to separate them from the mixed waste.

A method for separating unsaturated hydrocarbons from a mixed gas is the cryogenic fractionation method. 1-2.11 is a method of cooling the mixed gas to liquefy and fractionating it at a low temperature, but refrigeration is a method that involves multiple methods. However, a heat recovery system is required, and the equipment is expensive due to the use of high M1.4'Arl. There are drawbacks such as high power consumption. Furthermore, if water and carbon dioxide are included in the mixed gas, a blockage accident may occur in the cryogenic tube system, so it is necessary to remove water and carbon dioxide to 1 pprn or less using pretreatment equipment. be.

According to US Pat. No. 3,6!51,159 Specification 1, it is described that a toluene solution containing copper(I) aluminum chloride has the ability to separate unsaturated hydrocarbons by forming a complex with them. ing. but.

Copper (I) aluminum chloride reacts strongly with water and irreversibly loses its ability to form complexes, so even if the amount of water is 1 ppm, the separation ability not only gradually decreases as the amount of mixed gas processed increases, but also two reactions occur. The disadvantage is that equipment corrosion progresses due to the hydrogen chloride generated. However, since the toluene vapor used as a solvent is included in the recovered unsaturated hydrocarbon, a device to remove this toluene is required, and there are process constraints due to the use of a liquid absorbent. Has disadvantages. Furthermore, since the absorbing liquid contains aluminum chloride, a Fr1edel-Crafts reaction between toluene and unsaturated hydrocarbons using aluminum chloride as a catalyst occurs as a side reaction, resulting in loss of unsaturated hydrocarbons and deterioration of the liquid absorbent.

Two other methods have been proposed, but none of them is completely satisfactory for separating unsaturated hydrocarbons from a mixed gas.

The present inventors have been conducting research on solid adsorbents for gases for many years, and now we have developed a solid adsorbent composed of copper (I) halide and polystyrene or a polystyrene derivative, or copper halide (I). ).

It has been discovered that a solid adsorbent composed of a derivative has the ability to adsorb and release unsaturated hydrocarbons under #1 conditions. Based on this discovery, as a result of intensive research on ω1,
The present invention has been completed by successfully carrying out the separation and purification or separation and removal of unsaturated hydrocarbons from a mixed gas technically and economically, easily and conveniently.

The solid adsorbent in the present invention includes polystyrene strands or polystyrene derivatives together with copper (I) halide, or polystyrene or polystyrene derivatives with copper halide (CI) and monovalent or dihydric ions other than copper (I) halide. It is a solid adsorbent obtained by heating and stirring together with a valent metal halide or ammonium halide in a solvent for several hours, and then removing the solvent by distilling off under reduced pressure.

The solvent used in the preparation of the solid adsorbent in the present invention is
For example, carbon disulfide, dichloromethane.

Chloroporum, tetrachloromethane, dichloroethane,
Trichloroethane, tetrachloroethane.

Benzene, L. Luene, Gysilene, Chlorobenze]/.

Cyclohexane, decalin, acetonitrile, propionitrile, acetone, methyl isobutyl ketone, ethyl acetate, water, hydrogen chloride aqueous solution.

These include methanol, ethanol, and propatool. Here, hydrogen halides include, for example, hydrogen chloride and hydrogen bromide.

Polystyrene and polystyrene derivatives described in the specification include, for example, polystyrene and styrene and 1 to 6
It is a polystyrene resin such as a copolymer with 0 molar divinylbenzene.

The copper halide (1) used in the present invention is, for example,
These include copper chloride (■), steel bromide (I), and copper iodide Tl).

Describe it in the specification. Monovalent and divalent metal halides other than copper halide (i) are, for example.

These include lithium chloride, trichloride, and magnesium chloride, with calcium chloride and magnesium chloride being particularly suitable.

ammonium halide as described in the specification;

For example. These include ammonium chloride and ammonium bromide.

Regarding the composition of the solid adsorbent used in the present invention, the molar ratio of polystyrene and monomer residues of polystyrene derivatives to copper halide (1) is as follows.

01 to 30, preferably d, 1 to 5, dimension/ζ, monovalent or divalent metal halide other than copper halide (1), or ammonium halide, and copper halide ( The molar ratio with I) is 01-10, preferably 05-3
It is.

Unsaturated hydrocarbons that can be separated by the present invention are:
Examples include monoolefins, polyolefins, and dienes having 2 to 15 carbon atoms.

The adsorption of unsaturated hydrocarbons in the present invention is as follows:
It can be carried out at 0 to 90°C, preferably 1 l-1:0 to 40°C, and the adsorbent is heated to 40 to 140°C, in a suitable size 60 to
The adsorbed unsaturated hydrocarbons can be released by increasing the temperature to 100° C. or by lowering the partial pressure of the unsaturated hydrocarbons. Adsorption of unsaturated hydrocarbons 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 adsorbent according to the present invention is inert to water and carbon dioxide in a mixed gas, and by using this adsorbent, unsaturated hydrocarbons can be directly extracted from a water-containing mixed gas as shown in the examples. can be separated, and there is hardly any decrease in the adsorbent's ability even after repeated use. Furthermore, this adsorbent has a Fr1ed for unsaturated hydrocarbons.
Does not exhibit catalytic activity in the el-Crafts reaction.

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

Next, the present invention will be further explained with reference to examples.

[Example 1] Chlorinated steel (1) was obtained by vacuum drying a special grade reagent manufactured by Koso Chemical Co., Ltd. at 80°C for 12 hours. A first-class reagent made by a company was used after dehydrating it with phosphorus pentoxide and then distilling it.

Polystyrene resin is manufactured by Bio-RadLabor
'Bio-Beads 5M-2 manufactured by Atories Co., Ltd.
°' (a copolymer of 780% styrene and 20% divinylbenzene) was prepared in 6N hydrochloric acid at 55°C for 2 hours.

55℃ in 4N sodium hydroxide aqueous solution 21l-1J
while.

2 hours at 55°C in water, 1 hour at 25°C in methanol, and 1 hour at 25°C in dichloromethane.

After removing impurities by stirring and washing sequentially using a magnetic stirrer, the mixture was heated at SO℃ for 12 hours.
It was used after being vacuum dried.

As the ethylene gas, a cylinder gas manufactured by Takachiho Chemical Co., Ltd. was used, and the water content was adjusted to 0.6 mol% (6000 ppm).

Under dry nitrogen, 1.49 g (15.0 mmol) of copper chloride (I+ and 1.87.7 (18.0 mm per monomer residue) in ioomg of Nironas Clasco
o l) cross-linked polystyrene resin "Bio-Bea
ds 5M-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 Nironas flask, combined with a container containing 1 atm of ethylene gas (water content: 0.6 mol), stirred using a magnetic stirrer, and measured at 20°C. did. The adsorption of ethylene was rapid, with 0.8 m+nol (5 mol% of the copper chloride charge) after 1 minute and 2 mmol (8 mol% of the copper chloride charge) after 60 minutes. adsorbed. next.

A vacuum pump was used to reduce the pressure (4 mmHg) in this Nirosose Clasco at 20° C. for 20 minutes to release the adsorbed ethylene.

After that, this two [''] eggplant flask was combined with a container containing 1 atm of ethylene gas (water content: 0.6 mol%),
Start with 1 oyster using a magnetic stirrer.

Ethylene was adsorbed at 20°C. , adsorption of ethylene is rapid, and after 1 minute 9.8 mmoJ (copper chloride (1)
5 mol%), 6 (after 1 minute], 2m+nol (
After adsorbing the ethylene of the charged salt (fJliil(]', 8 mol% of l), the contact between the solid adsorbent of the present invention and the ethylene gas containing water is repeated 5 times/ζ is ethylene The adsorption amount of ethylene was almost the same as that of the first and second ethylene adsorptions. [Example 2] The same reagents and adsorbents as those described in Example 1 were used.

Put the solid adsorbent into a 100ml Nironas flask.

Combined with a container containing 1 atm of ethylene gas (water content 0.6 mol%) and stirred using a magnetic stirrer,
Measured at 20°C. Ethylene adsorption is rapid, and after 60 minutes, 1.2 mrr+ol (8
(mol%) of ethylene was adsorbed. After that, 90 at 1 atm.
When heated to ℃, 1.2 mrnol (prepared copper chloride (
8 moles of I) of ethylene was released.

After that, this two-necked eggplant flask was again combined with a container containing 1 atm of ethylene gas (water content 0.6 mol%),
Ethylene was adsorbed at 20° C. while stirring using a magnetic stirrer. Ethylene adsorption is rapid, with 0.8 mrnol (5 mol% of the charged copper(I) chloride) after 1 minute.
, 60 minutes later, 1.2 rnmol (copper chloride (1
) of 8 mol %) of ethylene was adsorbed.

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 first and second ethylene adsorption.

[Example 3] Magnesium chloride is a genuine chemical] A special grade reagent manufactured by Nigyo Co., Ltd. was used. The other reagents used were the same as those described in Example 1.

1,43 jj (1,5,0 mmol) of magnesium chloride/1 in +100111/i under dry nitrogen. , 1.49g (15.0mmol
) of copper chloride (1) and 1.87. ! 7 (18.0 mmol per monomorphic residue) of cross-linked Boristire/resin”
13io-Beads 5M-2'' and 20ml of carbon disulfide were added, stirring using a magnetic stirrer.

The mixture was heated to reflux. After that, the pressure was reduced (4 mrn, H
g) to sufficiently distill off carbon disulfide to prepare a solid adsorbent, put this solid adsorbent into a two-necked eggplant flask, and add 1 atm of ethylene gas (water content: 06 mol). While combining with the container containing it and stirring using a magnetic stirrer,
Ethylene was adsorbed at 20°C. The adsorption of ethylene was rapid, with 1 mmol (7 moles of copper(I) chloride charged) after 1 minute and 1.7 mmol (7 moles of copper(I) chloride charged) after 60 minutes.
Ethylene (11 mol%) of the charged copper(I) chloride was adsorbed.

Next, the inside of Nironas Clasco was reduced in pressure (4 mmHg) at 20° C. for 20 minutes using a vacuum pump to release the adsorbed ethylene.

Then, this three-day eggplant flask was combined with a container containing 1 atm of ethylene gas (water content: 0.6 mol), and the mixture was stirred using a magnetic stirrer.

Ethylene was adsorbed at 20°C. Ethylene adsorption is rapid, and after 1 minute, 1.1 mmol (prepared TFL chloride (
7 mol% of 1,)), and 1.7 mmol (
Ethylene (11 mol%) of the charged copper(I) chloride was adsorbed.

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 first and second ethylene adsorption.

[Example 4] Propylene was generated from special grade E chemical propylene (50% thixylene solution) manufactured by Tokyo Chemical Industry Co., Ltd., and purified by passing through a column packed with activated carbon. The same adsorbent as described in Example 1 was used.

Put the solid adsorbent into a 100 ml three-day eggplant flask.

Combined with a container containing propylene gas at 1 atm.

The measurement was carried out at 20° C. while stirring using a magnetic stirrer. Adsorption of propyleno is rapid, 2.3 mm after 1 minute.
ol (15 mol% of the copper chloride charge (1)), 5.1rnmol (34 mol% of the steel chloride charge (1) after Go)
) of propylene adsorbed 31 Next, the inside of this 2L1 eggplant flask was reduced in pressure (4 Hg) at 20° C. for 20 minutes using a vacuum pump to release the adsorbed propylene.

Thereafter, this three-day eggplant flask was combined with a container containing pyrene at 1 atm, and while stirring using a magnetic stirrer, pyrene was adsorbed at 20°C. Adsorption of propylene is rapid, with 2.3 mmol (15 mol% of the charged copper chloride (1)) after 1 minute and 5.0 mmol after 60 minutes.
l rnn + ol (34 mol% of chloride/41(1)) of propylene was adsorbed.After that, the contact between propylene gas and the solid adsorbent of the present invention was repeated five times, but the propylene adsorption I4A' was.

The values were almost the same as those of the first and second propylene adsorptions.

Claims (1)

[Claims] A solid adsorbent composed of copper (I) halide and crosslinked polystyrene resin, or...
), monovalent or divalent metal halide other than copper (I) halogenide, etc. The method is characterized by the use of a solid adsorbent composed of ammonium halogenide and polystyrene resin. A method for separating unsaturated fang 11 hydrocarbons from a mixed gas.