JPS58104009A - Separation of carbon monoxide from mixed gas - Google Patents

Abstract

PURPOSE:To separate carbon monoxide from a water-containing mixed gas, in high efficiency, by using a solid absorbent composed of copper halide, aluminum halide and polystyrene resin. CONSTITUTION:A polystyrene resin (e.g. polystyrene, styrene-divinylbenzene copolymer, etc.), a cuprous halide (e.g, cuprous chloride) and an aluminum halide (e.g. aluminum chloride) are heated under agitation for several hours in a solvent (e.g. carbon disulfide, methylene chloride, etc.) which dissolves or swells the polystyrene resin, and the solvent is distilled out to obtain a solid (carbon monoxide absorbent). The absorbent is stable against water, absorbs carbon monoxide from a watercontaining mixed gas at about 0-90 deg.C under atmospheric pressure, and released the absorbed carbon monoxide by heating at about 100- 140 deg.C. The absorption and the release can be carried out, e.g. by using packed column, fluidized bed, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides nitrogen, oxygen, methane, carbon dioxide and water-
From a mixed gas containing carbon monoxide along with elements such as -
Relating to a method for separating carbon oxide.

- Carbon oxide is a basic raw material in synthetic chemistry, and is produced from coke and coal using generator furnaces, water gas furnaces, Winkler furnaces, Lurgi furnaces, Kotspers furnaces, etc. It is also produced from natural gas and petroleum hydrocarbons by steam reforming and partial oxidation methods. In these methods, the product is obtained as a mixture of gases such as carbon oxide, hydrogen, carbon dioxide, methane and nitrogen. For example, for water gas - 35-40% carbon oxide, 45-51% hydrogen.

Carbon dioxide 4-5%, methane 0.5-1. (1, nitrogen 4
~9% composition9 usually 1000~20000ppm
contains water. Carbon monoxide, a by-product of steel mills, oil refineries, and petrochemical plants, is similarly obtained as a mixed gas.

In order to use these -carbon oxides as raw materials for synthetic chemicals,
It is necessary to separate carbon monoxide from the mixed gas.

Hydrogen is an important raw material in the chemical industry, and is used in the various mixed gases mentioned above or the waste gas from two petrochemical plants, such as
Separated from the waste gas from the hydrocarbon dehydrogenation process,
Often contains small amounts of carbon monoxide. Since this carbon oxide becomes a catalyst poison for the catalyst of a reaction using hydrogen, it is necessary to separate and remove it. Also, in these waste gases.

It usually contains a small amount of water.

According to British Patent No. 1,318,790, when a toluene solution of copper aluminum tetrachloride (Cu(AlCl2)) is brought into contact with a gas mixture containing 3Qmo1% of carbon monoxide at 25°C, -oxidation occurs. Absorbs carbon and converts it into 80
It is stated that upon warming to °C, 95% of carbon monoxide is recovered. This absorption liquid.

Hydrogen, carbon dioxide, and methane contained in a mixed gas.

Although it has the advantage of being unaffected by nitrogen and oxygen and having a low absorption pressure, it irreversibly reacts with water, resulting in deterioration of absorption capacity and the formation of precipitates.

Generates hydrochloric acid. For industrial implementation, D.

J., Haas6 and Ri, G., Walker et al.
chemical engineering
ress magazine 2. As stated in Vol. 70, No. 5, May 1974, page 76, the water in the mixed gas must be strictly controlled to 1 ppm or less.

Therefore, a strong dehydration process of the mixed gas is required before the absorption process, and strict control is essential. In addition,
Copper aluminum tetrachloride reacts strongly with water and irreversibly loses its ability to absorb carbon monoxide, 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 the hydrochloric acid generated by the two reactions. moreover.

In this method, it is inevitable that toluene vapor will be mixed into the recovered carbon monoxide, and a device to remove this toluene is required, and there are process constraints due to the use of a liquid absorbent. Has disadvantages.

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

The present invention advantageously separates carbon monoxide from a mixed gas containing water by using a solid composed of copper(I) halide, aluminum halide, and polystyrene or a polystyrene derivative as a carbon monoxide absorbent. It enables purification or separation and removal.

The carbon monoxide absorbent used in the present invention includes polystyrene or polystyrene derivatives, copper (I) halogenide, and aluminum halogenide [phase].

After heating and stirring in a solvent for several hours, the solvent is removed by a method such as reduction or distillation, and the solid solvent obtained is, for example, carbon disulfide, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, These include tetrachloroethane, tetrachloroethylene, cyclohexane and decalin.

Polystyrene and polystyrene derivatives described in the specification include, for example, polystyrene and styrene and 1 to 4
It is a polystyrene resin such as a copolymer with 0 mo1% divinylbenzene.

The copper chloride used in the present invention is, for example.

These include copper(I) chloride, steel(I) fluoride, and copper(I) bromide.

The aluminum chloride used in the present invention is.

Examples include aluminum chloride (t), aluminum fluoride (t), and aluminum bromide (t).

Regarding the composition of the carbon monoxide absorbent used in the present invention, the molar ratio of monomer residues of polystyrene and polystyrene derivatives to copper(I) chloride is o, i ~
30. Preferably it is 1 to 3, and copper (1)
The molar ratio of aluminum and aluminum [phase] is 0.0
1-10. Preferably it is 0.5-1.

The absorption of carbon monoxide in the present invention is 0 to 90 at normal pressure.
℃, preferably from 20 to 40 degrees Celsius, by increasing the temperature of the absorbent to 100 to 200 degrees Celsius, preferably from 100 to 140 degrees Celsius, or by lowering the -carbon oxide partial pressure. Carbon can be released.

- The absorption of carbon oxide can be carried out even at a temperature of 90° C. or higher by setting the pressure of the mixed gas to 1 atm or higher.

The carbon monoxide absorbent according to the invention is stable to water. For example, as seen in Examples 1 to 3, first,
After the absorbent is brought into contact with a nitrogen stream containing water for 10 minutes, it is brought into contact with high-purity carbon monoxide, and almost no decrease in the absorption capacity of carbon monoxide is observed. However, as seen in Comparative Example 1, the carbon monoxide absorbent obtained using toluene as a solvent during preparation rapidly exhibits carbon monoxide absorption capacity when contacted with a nitrogen stream containing water. decreases. From this, it is clear that the carbon monoxide absorption performance according to the present invention is excellent.

Since the carbon monoxide absorbent according to the present invention is a solid, devices such as packed column type, packed column type and fluidized bed type can be used as carbon monoxide absorption and release devices.

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

1 [Example 1] Aluminum chloride (t) was obtained by dehydrating and purifying a special grade reagent manufactured by Kishida Chemical Industry Co., Ltd. using a vacuum sublimation method.

Carbon disulfide was used by dehydrating a first class reagent manufactured by Kanto Kagaku Co., Ltd. with phosphorus pentoxide and then distilling it. Chlorinated steel (I) is
A special grade reagent manufactured by Koso Chemical Co., Ltd. was purified by reprecipitation using a concentrated hydrochloric acid-water system, washed with ethanol and ether, and dried in vacuum before use.

Polystyrene resin is manufactured by Bio-Rad Lab
Bio-Beads SM manufactured by oratories
-2 (styrene gQm01% and divinylbenzene 2Q
Mo1% copolymer heath.

20 to 50 methoxy) in a 7N aqueous hydrochloric acid solution at 55°C.
2 hours, IN hydroxide solution at 55°C.
12 hours in water at 55°C, 2 hours in methanol at 25°C.
°C for 91 h, 25 °C for 1 h in methanol/methylene chloride (1:3) mixed solvent, and f in methylene chloride.
2j, at 5°C for 1 hour, after removing impurities by stirring and washing sequentially using a magnetic stirrer, and then at ioo°C for 12 hours.

It was used after being vacuum dried.

For carbon monoxide gas and nitrogen gas, cylinder gases manufactured by Takachiho Chemical Co., Ltd. (purity 99.95%) and Suzuki Shokan Co., Ltd. (purity 99.999%) were used immediately before use. Co., Ltd.)
It was dried and purified by passing it through a packed tower.

100m1 under dry nitrogen! 2 in the Nilonas flask
．． 8 P (21 mmol) of aluminum chloride a),
2.11p (21 mmol) copper(I) chloride and 2,6y polystyrene resin Bio-Beads
SM-2 (25 mmol per monomer residue) was added, carbon disulfide 1611LA' was added, and the mixture was heated to reflux while stirring using a magnetic stirrer. After that, the pressure was reduced (4 m
m Hg) to sufficiently remove carbon disulfide to obtain ocher to reddish brown resin grains. This is a carbon oxide absorbent.

Put carbon monoxide absorbent in a 100m/Nilonas flask, combine it with a container containing latm carbon monoxide gas,
Stir using a magnetic stirrer.

Carbon monoxide was absorbed at 18°C, and the amount of absorbed carbon oxide was measured at 18°C by the gas buret method. -The absorption of carbon oxide is rapid; 16.0 mmol of carbon monoxide is absorbed after 4 minutes, and the amount of carbon monoxide absorbed after 60 minutes is 20 mmol.
．． 7 mmol, which almost reached the equilibrium absorption amount. next,
A vacuum pump was used to reduce the pressure (7 mm Hg) in the Nironas flask at 18° C. for 10 minutes to release the absorbed carbon monoxide.

Thereafter, this two-necked eggplant flask was combined with a container containing carbon monoxide gas (t 1 atm), and carbon monoxide was absorbed at 18° C. while stirring using a magnetic stirrer. - Carbon oxide absorption is rapid, 9.8 mmol after 3 minutes
Carbon monoxide was absorbed, and the amount of carbon monoxide absorbed after 60 minutes was 11.2 mm01, which almost reached the equilibrium absorption amount. Next, use a vacuum pump to vacuum the inside of this Nironas flask for 10 minutes.
Vacuum (7 mm Hg) was applied at 18° C. for minutes to release the absorbed carbon monoxide.

Then again, this two-necked eggplant flask'lr 1 atm
The mixture was combined with a container containing carbon monoxide gas, and the carbon monoxide was absorbed at 18° C. while stirring using a magnetic stirrer. - Carbon oxide absorption is rapid.

Absorbs 9.8 mmol of -carbon oxide in a 3 minute diameter,
The carbon monoxide absorption amount after 60 minutes was 11.2 mmol, which almost reached the equilibrium absorption amount.

Then, separately, 3aZwkg (2.1 mmol)
1 atm of nitrogen gas containing water (concentration of water 50
70 ppm) lOl was prepared. The container containing this nitrogen gas was connected to a 100 m Nironas flask, and was circulated using a BA-106T air pump manufactured by Iwaki Co., Ltd., over the absorbent stirred with a magnetic stirrer at 18°C. It was allowed to pass for 10 minutes. Next, use a vacuum pump to evacuate the inside of this Nirona flask.

Vacuum (7 mm Hg) was applied at 18"G for minutes to release the absorbed carbon monoxide.

After that, again, Nironas flask 1 atm (7)
- bonded to carbon oxide and absorbed "''1'-carbon oxide. The absorbent quickly absorbs carbon monoxide and 60
The amount of carbon monoxide absorbed after 1 minute was 10.8 mmol.

The equilibrium absorption amount was reached. - The absorption rate and amount of carbon oxide hardly changed from the values before contacting the absorbent with a gas containing 5070 ppm of water.

[Example 2] The same operation as in Example 1 was performed, except that instead of the carbon disulfide described in Example 1, primary methylene chloride manufactured by Takahashi Fujiyoshi Shoten was dehydrated with phosphorus pentoxide and then distilled. I did it. That is, under dry nitrogen, 2.5F (19 mmol) of aluminum chloride (IQ), 1.8F (19 mmol) of copper(I) chloride, and 2.3F of polystyrene resin Bio
-Beads 5M-2 (22 mmo per monomer residue
1), 10R1 of methylene chloride was added, and the mixture was heated to reflux while stirring using a magnetic stirrer. Thereafter, while stirring using a magnetic stirrer at room temperature for 4 hours, the mixture was reduced in pressure (4 mm Hg) to sufficiently remove methylene chloride to obtain reddish-brown resin particles.

This is - a carbon oxide absorbent.

Carbon monoxide absorbent was placed in a 100 mJ Nironas flask, combined with a container containing latm -carbon oxide gas, and while stirring using a magnetic stirrer, carbon monoxide was absorbed at 18°C, and -carbon oxide gas was absorbed. The absorption amount was measured at 18°C by the gas burette method. The absorbent quickly absorbs carbon monoxide.

The amount of carbon monoxide absorbed after 60 minutes was 20.5 mmol.

The equilibrium absorption amount was reached.

Next, the pressure inside the Nironas flask was reduced to 7 mm Hg at 18° C. for 10 minutes using a vacuum pump.

The absorbed carbon monoxide was released.

Thereafter, this Nironas flask was combined with a container containing carbon monoxide gas at t 1 atm, and carbon monoxide was absorbed at 18° C. while stirring using a magnetic stirrer. - The absorption of carbon oxide was rapid, and the amount of carbon monoxide absorbed after 60 minutes was 6.5 mmol, almost reaching the equilibrium absorption amount.

Next, the pressure inside the Nironas flask was reduced (7 mmHg) at 18° C. for 10 minutes using the vacuum pump 7.

The absorbed carbon monoxide was released. 1. Thereafter, this Nironas flask was combined with a container containing oxidized carbon gas, and carbon oxide was absorbed at 18° C. while stirring using a magnetic stirrer. -The absorption of carbon oxide is rapid, and the amount of carbon monoxide absorbed after 60 minutes is Q, 5
mmol, which almost reached the equilibrium absorption amount.

After that, separately, 33.311P (1,9 mmol
latm nitrogen gas containing water (concentration of water 442
0 ppm) 101 was prepared. The container containing this nitrogen gas was connected to a 100 d two-neck eggplant flask, and the nitrogen gas containing water was circulated using an Iwaki Co., Ltd. gBA-106T air pump, and the absorbent was stirred with a magnetic stirrer. The top was passed for 10 minutes at 18°C. Next, use a vacuum pump to vacuum the inside of this Nironas flask for 10 minutes.
Vacuum (7 mm Hg) was applied at 18° C. for minutes to release the absorbed carbon monoxide.

Thereafter, the mixture was again combined with carbon oxide gas in the Nironas flask to absorb carbon oxide. The absorbent quickly absorbed carbon monoxide, and the amount of carbon monoxide absorbed after 60 minutes was Q, gmmol, almost reaching the equilibrium absorption amount. - The absorption rate and amount of carbon oxide is 44%
Almost no change was observed between the value before contact with the gas containing 20 ppm of water.

[Example 3] A carbon monoxide absorbent was prepared by a method similar to that described in Example 2.

A carbon monoxide absorbent was placed in a 100m Nironas flask and combined with a container containing latm carbon monoxide gas.
Stir using a magnetic stirrer.

Carbon monoxide was absorbed at 18°C, and -carbon oxide gas was measured at 18°C by the gas bead method.

The absorbent quickly absorbed carbon monoxide, and the amount of carbon monoxide absorbed after 60 minutes was 20.5 mmol, almost reaching the equilibrium absorption amount.

When this absorbent is heated to 145° O in l atm.

- Carbon oxide is released rapidly, the amount released is 137% after 5 minutes
It reached mmol. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

Thereafter, the Nirona flask was connected to 1 atm of carbon monoxide gas to absorb carbon oxide. 1 absorbent
Upon heating to 145<0>C in ATM, -carbon oxide was rapidly released, and the amount released reached 1&7 mmol after 5 minutes.

Thereafter, the Nirona flask was again combined with LATM carbon monoxide gas to absorb carbon oxide. The absorbent quickly absorbed carbon monoxide, and the amount of carbon monoxide absorbed after 60 minutes was 1 3.7 mmol, almost reaching the equilibrium absorption amount. When the absorbent is heated to 145°C at latm,
- Carbon oxide is rapidly released.

The amount released reached 5 min diameter K1 & 7 mmox.

Next, separate latm nitrogen gas containing 33.3 to (1.9 mmol) of water (water concentration 4420 ppm).
) 401 was prepared. 1 container containing this 1 nitrogen gas
001: Combined with a two-neck eggplant flask of 1゜d, 2 Iwaki Co., Ltd. l! i
Nitrogen gas containing water was circulated using a BA-106T air pump and passed over the absorbent stirred with a magnetic stirrer for 10 minutes at 18°C.

Thereafter, the two-necked eggplant flask was again combined with LATAM carbon monoxide gas to absorb carbon oxide. The absorbent quickly absorbed carbon monoxide, and the amount of carbon monoxide absorbed after 60 minutes was 19.0 mmol, almost reaching the equilibrium absorption amount. - The absorption rate and amount of carbon oxide hardly changed from the values before contacting the absorbent with a gas containing 4420 ppm of water.

[Comparative Example 1] The same operation as in Example 1 was performed, except that instead of the carbon disulfide described in Example 1, -grade toluene manufactured by Takahashi Fujiyoshi Shoten was dehydrated with metallic sodium and then distilled. .

In a 100d Nironas flask under dry nitrogen,
3.2j' (24 mmol) of aluminum chloride A[D
and 2,4 (24 mmol) of copper chloride (1) and 2.8P polystyrene resin Bio-Beads
SM-2 (271Q!Do:L per monomer residue) was added, 10 d of toluene was added, and the mixture was heated and kept at 40° C. for 6 hours while stirring using a magnetic stirrer. Thereafter, while stirring using a magnetic stirrer for 4 hours at 30° C., toluene was sufficiently removed under reduced pressure (4 mmHg) to obtain ocher to reddish brown resin particles, that is, a carbon monoxide absorbent.

A carbon monoxide absorbent was placed in a 100IE/Nilonas flask, combined with a container containing latm carbon monoxide gas, and stirred using a magnetic stirrer.

Carbon monoxide was absorbed at 18°C. -The absorption of carbon oxide is rapid, and the amount of carbon monoxide absorbed after 60 minutes is 20.2 mm.
OL and Nasho, #1 reached the equilibrium absorption amount.

Next, use a vacuum pump to pump 1
Vacuum (7 mm Hg) was applied at 18° C. for 0 min to release the absorbed carbon monoxide.

After that, add this two-necked eggplant flask to 1 atm (7)
- Combined with a container containing carbon oxide gas and allowed to absorb carbon monoxide at 18° C. while stirring using a magnetic stirrer. - The absorption of carbon oxide was rapid, and the amount of carbon monoxide absorbed in a 60-minute diameter was 9.4 mmol, which almost reached the equilibrium absorption amount.

Next, a vacuum pump was used to reduce the pressure (7 mm Hg) in the Nironas flask at 18° C. for 10 minutes.

The absorbed carbon monoxide was released.

Thereafter, this Nirona flask was again combined with a container containing 1 atm of carbon monoxide gas, and carbon monoxide was absorbed at 18° C. while stirring using a magnetic stirrer. - Carbon oxide absorption is rapid.

The amount of carbon monoxide absorbed after 60 minutes was 9.4 mmol.

The equilibrium absorption amount was reached.

After that, separately, 43.2sP (2.4mm 01
) of water at 1 atm of nitrogen gas (concentration of water 57701) pIll>101 was prepared. 100 containers containing this nitrogen gas! 1 Iwaki Co., Ltd. 1iljBa-106T type nib-
Nitrogen gas containing water was circulated using a pump and passed over the absorbent stirred with a magnetic stirrer for 10 minutes at 18°C. Next, use a vacuum pump to reduce the pressure (7 mmHg) in the Nironas flask at 18°C for 10 minutes.
) to release the absorbed carbon monoxide.

Thereafter, the two-necked eggplant flask was again combined with 1 atm of carbon monoxide gas to absorb carbon oxide. The absorbent absorbs carbon monoxide quickly, and what is the amount of carbon monoxide absorbed after 60 minutes? Ommo1 and na9. The equilibrium absorption amount was reached. That is, by contacting nitrogen gas containing 5770 ppm of water, the amount of carbon monoxide absorbed by the absorbent is approximately 261
Diminished.

Patent applicant Hidefumi Hirai X: 62

Claims (1)

[Scope of Claims] ...Rogenide m (I), no-rogenide aluminum (1). It is characterized by using a solid absorbent composed of polystyrene or a polystyrene derivative and prepared using a non-aromatic solvent that dissolves or swells the polystyrene or polystyrene derivative. A method of separating carbon monoxide from a water-containing gas mixture.