JPS59136134A - Manufacture of carbon monoxide adsorbent - Google Patents

Abstract

PURPOSE:To obtain easily a solid body capable of adsorbing and desorbing CO by adding activated carbon to a solution of halide, carboxylate, sulfate, basic salt, ammine complex salt of copper (II) or copper (II) oxide and distilling off the solvent. CONSTITUTION:Copper (II) salt or copper (II) oxide is dissolved in a solvent under stirring to make a solution and activated carbon is added to the solution. The solvent is distilled off under reduced pressure to obtain a solid body capable of adsorbing and desorbing CO. As copper (II) salt; a halide, carboxylate, sulfate or ammine complex salt is used, and as the solvent; water, hydrochloric acid aqueous solution, formic acid, acetic acid, benzene, toluene, propionitrile or the like is used. If the solid body is treated with a reductive gas e.g. CO, H2 or the like, the ability of CO adsorption and desorption is further increased.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention adsorbs -carbon oxide from a mixed gas containing carbon monoxide together with nitrogen, methane, carbon dioxide, hydrogen, etc., and then removes the adsorbed carbon by changing the pressure or temperature. The present invention relates to a method for producing solids capable of desorbing carbon oxide.

Carbon monoxide is important as a basic raw material in synthetic chemistry.

Usually obtained as a mixed gas. From this mixed gas, −
There are two methods for separating and removing carbon oxide: a method using a carbon oxide absorbent or adsorbent, and a cryogenic separation method.9
The present invention relates to an adsorbent used for the former.

Until now, as a liquid carbon monoxide absorbent.

Hydrochloric acid acidic copper (I) chloride aqueous solution, ammonia alkaline copper (I) formate aqueous solution, etc. are known. However, among these, the former has the problem of corrosiveness of the device. Since the latter has the ability to absorb not only carbon monoxide but also carbon dioxide, a carbon dioxide removal device is required to obtain high purity carbon monoxide, and loss of ammonia is a problem.

In addition, a toluene solution of copper(I) aluminum chloride has advantages such as being unaffected by hydrogen, carbon dioxide, methane, and nitrogen contained in the mixed gas, and having a low absorption pressure for carbon oxide. It reacts irreversibly with other substances, resulting in deterioration of absorption capacity and formation of precipitates, and generates hydrochloric acid.

Therefore, before the absorption process, the moisture in the mixed gas should be reduced to 1
A powerful dehydration process is required to reduce the amount to ppm or less, and strict management is essential. Furthermore, if this absorption liquid is used, it is inevitable that toluene vapor, which is a solvent, will be mixed into the recovered carbon monoxide, and a device to remove this toluene is required. It has disadvantages such as being subject to process constraints.

On the other hand, solid carbon monoxide adsorbents are largely unknown so far. According to U.S. Pat. No. 4,019,879, after adsorbing copper (II) ions to zeolite,
Copper (i) zeolite obtained by reduction operation at high temperature has carbon monoxide adsorption ability. However.

This adsorbent has the disadvantages that the preparation temperature is as high as at least 300° C. and that the dependence of the adsorbed amount of -carbon oxide on pressure and temperature is relatively small.

All carbon monoxide absorbents and adsorbents known to date contain copper(1) ions or copper(I) salts, and contain copper(II) ions or copper(l'I) salts. Things were unknown. Copper (I) ions and copper (I) salts are unstable and can be easily decomposed by air.
ions or oxidized to copper (JA) compounds, yet easily reduced by two weak reducing agents.

It is well known that copper is a metal.

The production and use of absorption liquids and adsorbents containing copper(I) ions or copper(I) salts require special precautions, conditions, and equipment.

The present inventors have been researching carbon monoxide adsorbents for many years, but from the perspective of the prior art.

Surprisingly, they discovered that by adding activated carbon to a copper (II) salt or copper oxide (old solution) and then distilling off the solvent, a solid with a high carbon oxide adsorption/desorption ability could be obtained, and As a result of research, nine inventions were completed.

The present invention realizes simple and economically advantageous production of a solid carbon monoxide adsorbent that allows carbon monoxide to be directly separated from a mixed gas.

The carbon monoxide adsorbent obtained by the present invention is:

A solid obtained by stirring copper (1 salt or copper oxide ([)) in a solvent to form a solution, adding activated carbon to the solution, and then removing the solvent by methods such as reduced pressure and distillation.
Alternatively, it is a solid obtained by further treating this with a reducing gas.

In the present invention, the copper (')...ride salt is:

For example, chloride steel (■), copper fluoride (formerly copper bromide (■)).

and copper(II) iodide. - Examples of carboxylic acid salts of copper (II) include steel acetate (old) and copper (II) formate. Examples of basic salts of copper (II) include.

For example, basic copper carbonate (formerly), basic copper acetate (formerly).

and basic silver (II) phosphate. Examples of copper (former ammine salts) include copper (II) hexaammine chloride. Copper oxide (') can also be used instead of these copper (1) salts.

The activated carbon used in the present invention is shaped like compacted coal, granular coal made of crushed coal, and powdered coal. The raw materials for activated carbon are wood and coconut shells.

Coal, petroleum pitch, etc. are used, and a chemical activation method, a gas activation method, etc. can be applied to this activation method.

Examples of the solvent used in the present invention include water, aqueous hydrochloric acid, formic acid, acetic acid, benzene, and toluene.

These include propionitrile, aqueous acetonitrile, ammoniacal formic acid aqueous solution, and primary or secondary alcohols having 1 to 7 carbon atoms.

In the present invention, the mixed state of the copper (TI) salt and copper oxide (TI) with the solvent may be partially suspended.

Activated carbon and @ in the production of carbon monoxide adsorbent according to the present invention
(The weight ratio with 1 salt or copper oxide (1■) is.

0.5 to 60.0, preferably 20 to 10.0. The weight ratio of the solvent to copper (one salt, one copper(II) oxide) is 1 to 200, preferably 3 to 30.

In the present invention, the atmosphere during the production of the copper (1 salt) or oxidized steel (old solution) and the addition of activated carbon thereto is, for example, nitrogen, helium, argon, and air.

The stirring time of copper ([) salt or copper oxide (old) and solvent in the present invention is 1 minute to 10 hours, preferably 1 to 3 hours.
The stirring time and stirring temperature are 10 to 80°C, preferably 20°C.
~30°C.

In the present invention, the temperature of copper (II) salt or copper oxide (TI) is 10 to 80°C, preferably 20 to 30°C. ) It is desirable to stir the solution.

The degree of reduced pressure during solvent removal in the present invention is 10-6 ~
10 mmHg, preferably 10 to 110 m1H,
What is the temperature?

The temperature is 10-500°C, preferably 80-250°C.

As shown in the examples, the carbon monoxide adsorbent produced by the above method rapidly adsorbs carbon monoxide when brought into contact with a mixed gas of 1 atm at 0 to 40°C. The adsorbed carbon monoxide can be easily desorbed and released by raising the temperature of the -carbon oxide adsorbent to 60° C. or higher, or by reducing the -carbon oxide partial pressure.

Furthermore, as shown in Examples 4 and 5, when the carbon oxide adsorbent is treated in a reducing gas under mild conditions,
Its carbon oxide adsorption/desorption capacity can be increased. Here, the reducing gas is, for example, carbon oxide and hydrogen, and the treatment temperature is 30 to 250°C, preferably 10 to 250°C.
The temperature is 0 to 200°C, and the treatment time is 3 minutes to 20 hours, preferably 20 minutes to 1 hour.

The carbon monoxide adsorbent produced by the present invention is:

It is stable against moisture in the mixed gas, and can directly separate -carbon oxide from the water-containing mixed gas. Also, 2 separated carbon monoxide.

- Contains no solvent vapors from the carbon oxide adsorbent and does not require equipment to recover solvent vapors. Furthermore, the carbon monoxide adsorbent prepared according to the present invention does not generate corrosive gases.

Since the carbon monoxide adsorbent produced according to the present invention is solid, it is easy to handle, and can be used in two packed column formats.
and fluidized bed type devices can be used as devices for carbon monoxide separation.

The procedure of the present invention is simple, a wide variety of raw materials can be used, and a useful carbon monoxide adsorbent can be easily prepared.

The present invention will be further explained in detail by way of examples.

[Example 1] As copper chloride (n), a special grade reagent manufactured by Koso Chemical Co., Ltd. was used. Purified water manufactured by Tokyo Yakuhin Kogyo Co., Ltd. was used. Activated carbon is BAC, G-7 manufactured by Kureha Chemical Industry Co., Ltd.
OR, LOT, and A310117 were heated and kept at 180° C. for 4 hours under reduced pressure (6 mmHg), and then stored under dry nitrogen. - Carbon oxide gas and nitrogen gas were manufactured by Takachiho Chemical Co., Ltd. (purity 99.95%).
) and Suzuki Shokan Co., Ltd. (purity 99.999%) were dried and purified by passing them through a packed column of Molecuiler Sheep 3A (manufactured by Nikka Seiko Co., Ltd.) immediately before use.

2.6 g (15,0 mtnol) of copper(II chloride) in an iooml Nironas flask under dry nitrogen.
), 15+++ liters of purified water was added, and the mixture was left at 20° C. for 1 hour while stirring using a magnetic stirrer. Add 1 og of activated carbon to this eggplant flask under dry nitrogen,
After stirring for 1 hour, reduce the pressure inside the eggplant flask (
6 miHg), heated and kept at 100°C, water was sufficiently removed, and black grains were obtained. This is - carbon oxide adsorbent.

A carbon monoxide adsorbent was placed in a 100 ml Nironas flask, and a mixed gas of carbon monoxide and nitrogen at latm (carbon oxide partial pressure 0.9 atm, nitrogen partial pressure 0.1 atm)1.
The containers containing 51 were combined and stirred using a magnetic stirrer to adsorb carbon monoxide at 20°C. 1 BA-106T manufactured by Iwaki Co., Ltd. for the initial 10 minutes of adsorption
A type air pump was used to circulate the gas mixture over the adsorbent. -The amount of carbon oxide adsorption was measured at 20°C by the gas bead method.

Carbon monoxide adsorption is rapid, with 3.3. mmo
+ carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was 4.3 mmol, which almost reached the equilibrium adsorption amount.

Next, use a vacuum pump to pump 1
Apply vacuum (0.4 mmHg) at 20° C. for 0 min.

The adsorbed carbon monoxide was released.

Thereafter, this Nirona flask was heated with a mixed gas of carbon monoxide and nitrogen at latm (-carbon oxide partial pressure 0.9 atm).

Combined with a container containing nitrogen partial pressure 0.1 atm) 1.51.

-Carbon oxide was adsorbed at 20°C while circulating the adsorbent over the adsorbent using an air pump and stirring using a magnetic stirrer. - Carbon oxide adsorption is rapid.

After 3 minutes, 3.3 mmol of carbon monoxide was adsorbed and 60
After a few minutes, the amount of carbon monoxide adsorbed was 4.3 mmol, which had almost reached the equilibrium adsorption amount.

Thereafter, the inside of this Nironas flask was further reduced in pressure (0.4 mrrtHg) at 20°C for 10 minutes using a vacuum pump.
) to release the adsorbed carbon monoxide.

Thereafter, even if this adsorption/release operation was repeated, no change was observed in the -carbon oxide adsorption rate and adsorption amount.

[Example 2] Copper(II) chloride described in Example 1 15', Omm
Copper bromide manufactured by Yoneyama Pharmaceutical Co., Ltd. (old) was used instead of ol.

Further, the same reagents as described in Example 1 were used except that methanol, a special grade reagent manufactured by Hanei Yonegaku Pharmaceutical Co., Ltd., was used instead of 15 mg of purified water.

Under dry nitrogen, 3.49 (15.0 mmol) of copper bromide (11) was placed in a 100 mg Nironas flask, 5 m, 1 of methanol was added, and while stirring using a magnetic stirrer, the mixture was stirred at 20°C. I left it for a while. Add logs of activated charcoal to this eggplant flask under dry nitrogen.

After stirring for 1 hour, reduce the pressure inside the eggplant flask (
6 Hg) and heated and kept at 100°C to sufficiently remove methanol and obtain black grains. This is - carbon oxide adsorbent.

The amount of carbon monoxide adsorbed was measured by the same operation as in Example 1, and it was found that 2.8 mmol of carbon monoxide was adsorbed after 3 minutes and 5.7 mmol+ of carbon monoxide after 60 minutes.

The adsorbent was then heated to 120° C. at 1 atm, and -carbon oxide was rapidly released, reaching 5.7 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 3] The reagents used were the same as in Example 1.

Under dry nitrogen, 2.6 g (15.0 mmol) of copper (III) chloride was placed in a 100 m6 Nironas flask, 15 me of purified water was added, and the mixture was stirred using a magnetic stirrer. It was left at ℃ for 1 hour. Activated carbon log was added to this eggplant flask under air, and after stirring for 1 hour, the inside of the eggplant flask was depressurized (6 mrn
Hg) and heated and kept at 180°C to thoroughly remove water and obtain black grains. This is - carbon oxide adsorbent.

When the amount of adsorbed carbon monoxide was measured by the same operation as in Example 1, 6.9 mmol of carbon monoxide was adsorbed after 3 minutes and 8.6 mmol after 60 minutes.

Next, when this adsorbent was heated to 120° C. at 1 atm, -carbon oxide was rapidly released, and the released amount reached 8.6 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 4] A solid adsorbent prepared by the same operation as described in Example 1 was heat-treated at 120°C for 30 minutes under -carbon oxide, and was used as a -carbon oxide adsorbent.

The amount of carbon monoxide adsorbed was measured by the same operation as in Example 1, and 5.0 mmol of carbon monoxide was adsorbed after 3 minutes and 5.8 mmol after 60 minutes.

Next, when this adsorbent was heated to 120° C. at 1 atm, -carbon oxide was rapidly released, and the released amount reached 5.8 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 5] A solid adsorbent prepared by the same procedure as that described in Example 1 was heat-treated at 180°C for 1 hour under hydrogen, and this was used as a -carbon oxide adsorbent. When the adsorption amount of -carbon oxide was measured by the same operation as in Example 1, it was 5.0 mmol after 3 minutes and 7.9 mn after 60 minutes.
101 carbon monoxide was adsorbed. .

Next, the adsorbent with 1. When heated to 120° C. in ATM, -carbon oxide was rapidly released, and the amount released reached 7.9 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 6] By the same operation as described in Example 4, 2.6 g
(1,5,0 mmol) of copper chloride (■), and 10
A carbon monoxide adsorbent consisting of g activated carbon was prepared.

When the adsorption amount of -carbon oxide was measured by the same operation as in Example 1, 5.0 mmol of carbon monoxide was adsorbed after 3 minutes, and the adsorption amount of carbon monoxide after 60 minutes was 5.8 mmol.
It became +, and the equilibrium adsorption amount was almost reached.

Next, this adsorbent was heated to 120° C. at 1 atm.

Measure the amount of gas released using the gas bead method.4.
- Carbon oxide is released quickly, with the amount released being 5.5% after 10 minutes.
It reached 8 mmol. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

Next, separately, 27m1li' (1,,5mmol
) of water at 1 atm nitrogen gas (concentration of water 7
,400 ppm) 5 liters were prepared. 1. Container containing this ♀1 gas. It was connected to an OOme three-day eggplant flask and circulated using a BA-106T type air pump manufactured by Iwaki Co., Ltd.

1 at 20℃ on top of the adsorbent stirred with a magnetic stirrer.
It was allowed to pass for 0 minutes.

Then, while stirring this adsorbent using a magnetic stirrer at 20°C, a mixed gas of Iatm carbon monoxide and nitrogen (- carbon oxide partial pressure 0.9 atm, nitrogen partial pressure 0.1 a
tm) was connected to a container containing 1.51 J and circulated over the adsorbent using an air pump to adsorb -carbon oxide.

The adsorption was rapid, with 5.8 mmol of carbon monoxide adsorbed after 60 minutes. That is, the adsorption rate and amount of -carbon oxide hardly changed from the values before contacting the adsorbent with a gas containing 7,400 ppm of water.

[Example 7] Copper(II) chloride described in Example 1 15.0 mmol
The same reagents as described in Example 1 were used, except that anhydrous copper sulfate manufactured by Yoneyama Pharmaceutical Co., Ltd. was used instead.

Under dry nitrogen, put 2.4 jj (15.0 mmol) of anhydrous copper sulfate in a 100 mg Nironas flask, add 15 ml of purified water, and leave at 20°C for 1 hour while stirring using a magnetic stirrer. did. Activated carbon 11 was added to this eggplant flask under dry nitrogen, and stirring was continued for 1 hour, and then the pressure inside the eggplant flask was reduced (6 mmH
g) and heated and kept at 100°C to thoroughly remove water to obtain black grains. This is - carbon oxide adsorbent.

The amount of carbon monoxide adsorbed was measured by the same operation as in Example 1, and 0.5 mmol of carbon monoxide was adsorbed after 3 minutes and 1.2 mmol after 60 minutes.

Next, when this adsorbent was heated to 120° C. at 1 atm, -carbon oxide was rapidly released, and the released amount reached 1.2 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 8] Copper oxide manufactured by Merck Co., Ltd. (former) was used instead of copper chloride (former 15.0 mmol) described in Example 1, except that 28% ammonia water manufactured by Takahashi Fujiyoshi Shoten was used instead of purified water (15 m). The same reagents as in Example 1 were used.

1.2 in a 1ooml Nironas flask under dry nitrogen! i' (15,0 mmol) of copper oxide (
15 ml of ammonia water was added, and the mixture was stirred using a magnetic stirrer and left at 20°C for 1 hour.

Add 10 g of activated carbon to this eggplant flask under dry nitrogen.

After stirring for 1 hour, reduce the pressure inside the eggplant flask (
6 mmHg) and heated and kept at 100°C to sufficiently remove ammonia water and obtain black grains. This is - carbon oxide adsorbent.

When the adsorption amount of -carbon oxide was measured by the same operation as in Example 1, it was 0.9 mm, ol, 6 after 3 minutes.
After 0 minutes, 1.8 mmol of carbon monoxide was adsorbed.

This adsorbent was then heated to 120° C. at 1 atm, and -carbon oxide was rapidly released, and the released amount reached 1.8 mmol after 10 minutes. The released gas was carbon oxide; no other components were detected.

[Example 9] Copper chloride (TI) described in Example 1 15.0 mmol
Instead, use anhydrous copper sulfate manufactured by Yoneyama Pharmaceutical Co., Ltd.

Further, the same reagents as described in Example 1 were used except that 35% hydrochloric acid manufactured by Takahashi Fujiyoshi Shoten was used instead of 15 ml of purified water.

Under dry nitrogen, 2.49 (15.0 mmol) of anhydrous copper sulfate was placed in a 1QQmg Nironas flask, 15 ml of 35-thihydrochloric acid was added, and the mixture was stirred using a magnetic stirrer and stirred at 20°C. I left it for a while. 10 activated carbon under dry nitrogen in this eggplant flask! After adding j and stirring for 1 hour, reduce the pressure inside the eggplant flask (6 m
iHg) and heated and kept at 100°C to sufficiently remove water and hydrogen chloride to obtain black grains. This is - carbon oxide adsorbent.

The amount of carbon monoxide adsorbed was measured by the same operation as in Example 1. After 3 minutes, 3.0 mmol+ of carbon monoxide was adsorbed, and after 60 minutes, 5.8 mmol of carbon monoxide was adsorbed.

This adsorbent is then heated to 120° C. at 1 atm, and -carbon oxide is rapidly released, with an amount of 1.

It reached 5.8 mmol after minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

[Example 10] Copper chloride (formerly 15.0 mmol) described in Example 1 was replaced with copper (II) oxide manufactured by Merck & Co., and purified water 15.0 mmol was used.
m/? Instead, add 35% hydrochloric acid manufactured by Takahashi Fujiyoshi Shoten to purified water (
The same reagents as in Example 1 were used, except that the reagents were diluted to 5N using a reagent (manufactured by Tokyo Yakuhin Kogyo Co., Ltd.).

i, 2. in a 100 ml double flask under dry nitrogen. Copper(II) oxide in V (15,0 mmo+)
15 ml of 5N hydrochloric acid was added thereto, and the mixture was stirred using a magnetic stirrer and left at 20°C for 1 hour. Add 10g of activated carbon to this eggplant flask under dry nitrogen,
After stirring for an hour, the inside of the eggplant flask was depressurized (6
mmHg) and heated and kept at 100°C to sufficiently remove water and hydrogen chloride to obtain black grains. This is - carbon oxide adsorbent.

The amount of carbon monoxide adsorbed was measured by the same operation as in Example 1, and 1.5 mmol+ of carbon monoxide was adsorbed after 3 minutes and 3.9 mmol after 60 minutes.

Next, when this adsorbent was heated to 120° C. at 1 atm, -carbon oxide was rapidly released, and the released amount reached 3.9 mmol after 10 minutes. Analysis of the released gas using a gas chromatograph revealed that the released gas was carbon monoxide and no other components were detected.

Patent Applicant Eishi Wiki Voluntary Procedural Amendment It (G month 211'+ 1, Japanese 5B, fact 1'1 Patent Application No. 11739, 1988 2, title of invention Method for manufacturing carbon monoxide adsorbent 3) , Relationship with the person making the amendment, ft. Patent applicant Hidefumi Hirai 4, 1-14-10, Yutenji, Meguro-ku, Tokyo; Agent: 550-5, 1-25-30 Edobori, Nishi-ku, Osaka;
? Column for detailed description of the invention of in positive object clear eta.

6. Contents of amendment (1) [and powdered charcoal] on page 5, lines 181j to 19 of the specification. 4 Where is it? 1-OJ:tF
Powdered charcoal or cylindrical activated bamboo charcoal.

(2) On page 5, line 20, the phrase ``J3 and petroleum-based pitches are used,'' was replaced with ``oil-based t etc. are used,
5(3), the following sentence is inserted between page 8, line 7 and date of line 8.

[J, tJJ, sea urchins under reduced pressure as shown in Example 11, 71 J, - sea urchins in an inert gas as shown in Example 13, or in air at 70-250°C as shown in Example 13. , preferably by heat treatment at 110-200°C, J,
Therefore, its ability to adsorb and desorb carbon oxides can be avoided. Inert gases include, for example, nitrogen d3 and argon. Processing time is 10 minutes - 20 hours, preferably 7L
is 20 minutes to 2 hours.

As shown in Example 15, the carbon monoxide adsorbent produced according to the present invention is stable against the compounds contained in the mixed gas, and can be directly removed from the mixed gas containing them. , - carbon oxide can be separated. here.

Compounds containing hydrogen sulfide, r,
l! These include carbonyl, J, and sulfur dioxide. (4) "A reagent was used." on page 9, line 7.
There is a [reagent (-chloride salt: Cu C12・2+
120) was used. ” he corrected.

(5) Add the following sentence next to the 8th line of page 21.

[(Example '11) A solid adsorbent prepared by a procedure similar to that described in Example 11i1J1 was prepared by 0. /I mm t-10,
It was heat-treated at 120° C. for 30 minutes and used as a carbon oxide adsorbent.

When the adsorption amount of -carbon oxide was measured by the same operation as in Example 1, it was 3.8 ml 1 ol after 3 minutes.
After 6 g, 8.1 mmol of -carbon oxide was adsorbed.

Next, add 1 olm of this adsorbent to 120°C.

- Carbon oxide was rapidly released, and the release level reached t3.1 mmol after 10 minutes. As a result of analyzing the released gas using Gask[]71-Graph, the released gas contained carbon monoxide C.

Other components were detected and were 4T.

[Example 12] A solid adsorbent prepared by the same procedure as described in Example 11 was heated at 180° C. for 1111 hours under nitrogen.
Process.

This was used as a carbon oxide adsorbent.

Using the same operation as in Example 1, the adsorption amount of -carbon oxide was measured, and after 3 minutes, it was 4.1 mmol,
After 60 minutes, 8.5 mmol of -carbon oxide was adsorbed.

Next, this adsorbent was heated to 120°C in a larm.

- carbon oxide is rapidly ti'i discharged, ejection skewer t-1:,
-10 minutes later (2 tons reached 8.5 mmol1)
Ta. Analyze the released gas using Gasc 11-1 Heclaf.1. :
Yuri, 100000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000100166666666666666666666666666666

Other components Ij were not detected.

(Implementation +11113) Prepared by the same procedure as described in Example 1,
: The solid adsorbent was heat treated in air at 180°C'r for 1 hour.

This was used as a carbon oxide adsorbent.

- Carbon oxide adsorption M was measured by the same operation as in Example 1. After 3 minutes, 3.5 mmol,
After 60 minutes, 4.8 mm0+ of -carbon oxide was adsorbed.

Next, add the c(7) adsorbent to 120°C.
When heated to 1J.

- Carbon oxide is rapidly released, and released (116N is 4.8 mmol per ship for 10 minutes).As a result of analyzing the released gas using a gask 1171 graph, the released gas 11:
-Nifified carbon (・Yes.

No other components were detected.1゜[Example 1/I] Activity 1SJ (13AC, G-7OR) described in Example 1
) instead of fibrous activated carbon (Higashi) 1 Boseki Co., Ltd., activated tq1diJ fabric was used, KF-I E500> was used, and the same reagents as described in Example 1 were used except for IC. lU
j use/, : ,.

C under dry nitrogen, '100 ml 1.1-17. Nonce + rllll-,.

0.5! J (3,0 mmol) of tF4 chloride (1
1) People i't, L'j! I'! Add 50ml of J water/
Using lζ1 eclipse stirring 1 Ku (kaki: 1, U゛tsutsu,
It was rotated for 1 hour at 20°C. This eggplant frass:] fiber under dry nitrogen inside! Add 1F activated 11 charcoal 20 (1) (,1
After continuing t for a period of time, reduce the pressure inside Nasunorasu (0.06 mm 1I (J > 1.Zt, ?l:,
Heat and keep warm at 100'C.

Water was distilled off under reduced pressure over a period of 4 minutes, yielding 17 black solids. This is a carbon oxide adsorbent.

By the same operation as in Example 1, the adsorption amount of -carbon oxide was measured, and after 3 minutes, 0.3 mmol of -carbon oxide was adsorbed, and (after 30 minutes, the adsorption amount of -carbon monoxide was 1 monme). t
1.2 mm (+1 roar, (Jpo carapace adsorption suspension reached.

Next, this adsorbent was heated to 120° C. at 1 atm, and the gas release device was measured using the million sub-1-lett method.

- Carbon oxide is rapidly released, with a released amount LL 'I 1 after 0 minutes, . It reached 2 m 111+11. As a result of analyzing the released gas with Gask L171~Grano, the release force is one tube! ! There is 1 atom carbon and no component of 1 song is detected.
]is.

(Example '15) IR+ f+ garlic cave M similar to that described in Example 1
The solid adsorbent was heated to 120" under -carbon oxide (
Heat treated and stretched for 30 minutes, then mixed with carbon oxide adsorbent (
2゛(used.

When the amount of -carbon oxide adsorption was measured by the same operation as in Example 1, it was found that after 3 minutes, it was 5.0 mmol, 6
After 0 minutes, 5.8 mmol of -carbon oxide was adsorbed.

The adsorbent was then heated to 1 atm C120''.

- Carbon oxide is rapidly released, and the released amount reaches 5.3 mmol after 10 minutes/C0.Then, this solid adsorbent is placed under arsenic at the 1st diameter of 1all11.

Leave it at 20°C for 16 hours.

When the oxidized 1diJ basic absorption 7391 was measured using the same procedure as in Example 1 using 1 thread in -, after 3 minutes, the cal:
1. ．． 6 Ill m(jl.

5.8 m mol per 10 minutes, 5.8 m mol after 60 minutes. Q m III (adsorbed 11 carbon monoxides.

Next, reduce the pressure (Q, 4 u Ll(]) in this 2 I'' eggplant flask at 20°C for 10 minutes using an empty pump.
Ic.

Carbon monoxide was released by adsorption.

Thereafter, the -carbon oxide adsorbed product was measured using the same procedure as in Example 1, and after 3 minutes, 5. Onl m(11
.

6. After 60 minutes. Qmmol of carbon oxide was adsorbed.

Therefore, no difference was observed in the carbon monoxide adsorption capacity of the solid adsorbent before and after it was exposed to hydrogen chloride.

Claims (1)

[Claims] Halide salts, carboxylates, and sulfates of copper' (■). A method for producing a solid capable of adsorbing and desorbing carbon oxide by adding activated carbon to a solution of a basic salt, an ammine complex salt, or copper (n) oxide, and then distilling off the solvent, and this solid A method of increasing carbon monoxide adsorption/desorption ability by treating carbon monoxide with a reducing gas.