JPS62114646A - Preparation of carbon monoxide adsorbent - Google Patents

Abstract

PURPOSE:To enhance carbon monoxide adsorbing capacity, by immersing activated carbon in a hydrochloric acid solution of copper (I) halide or copper (I) oxide and taking out the imipregnated activated carbon and drying the same to form a carbon monoxide adsorbent. CONSTITUTION:A hydrochloric acid solution of copper (I) halide such as copper (I) chloride, copper (I) bromide or copper (I) iodide or copper (I) oxide is prepared. In this case, the concn. of hydrogen chloride of hydrochloric acid is pref. 15-25wt% and 10-40g of copper (I) halide or copper (I) oxide is pref. added to 100ml hydrochloric acid. Activated carbon is immersed in said hydrochloric acid solution and taken out from said solution to be dried at about 200-300 deg.C in an inert gas atmosphere under atmospheric pressure or reduced pressure to obtain a carbon monoxide adsorbent. This adsorbent rapidly adsorbs carbon monoxide at 0-40 deg.C under atmospheric pressure and easily releases carbon monoxide if the temp. thereof is raised to 40 deg.C or more.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention adsorbs carbon monoxide from a mixed gas containing carbon monoxide, and changes the pressure or temperature to remove the adsorbed carbon monoxide. The present invention relates to a method for producing a solid adsorbent that can be desorbed.

[Conventional technology]

Carbon monoxide 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, Kotsunos furnaces, etc.
Produced from natural gas and stone-derived hydrocarbons by steam reforming and partial oxidation. In these methods, the product is obtained as a mixture of gases such as carbon-11, hydrogen, carbon dioxide, methane and nitrogen. For example, in the case of water gas, carbon monoxide 35-40%, hydrogen 45-51%
, carbon dioxide 4-5%, methane [1.5-1.0%, nitrogen 4-9%, usually 1000-2000 p
Contains pm water.

Carbon monoxide, which is produced as a by-product in steel mills, oil refineries, and petrochemical plants, can also be obtained as a mixed gas.

In order to use these carbon monoxides as synthetic chemical raw materials, it is necessary to separate them from the mixed gas.

On the other hand, hydrogen is also an important raw material in the chemical industry, and is separated from the various gas mixtures mentioned above or from the waste gas of petrochemical plants, such as the waste gas from the hydrocarbon dehydrogenation process. Often contains carbon. Since this carbon monoxide acts as a catalyst poison for the catalyst of reactions using hydrogen, it is necessary to separate and remove it. Furthermore, these gases usually contain a small amount of water.

A liquid absorbent is usually used to separate and remove carbon monoxide from a mixed gas. The copper coin cleaning method involves adding a mixed gas to an ammoniacal aqueous solution of copper (I) formate or a hydrochloric acid suspension of copper (I) chloride at room temperature. The method is to pressurize to 20°at+n and absorb it to separate and remove carbon monoxide, then heat this copper group under reduced pressure to release and separate carbon monoxide, regenerating the copper group. However, it has disadvantages such as difficulty in handling liquid absorbent, difficulty in operation management to prevent equipment corrosion, solution loss, and precipitation formation, and high construction cost due to high pressure.

According to British patent no. By absorbing carbon oxide and heating it to 80 degrees Celsius, 95% of the carbon monoxide can be recovered. This absorption liquid absorbs the hydrogen and carbon dioxide contained in the mixed gas.
Although it has advantages such as being unaffected by methane, nitrogen, and oxygen and having a low absorption pressure, it irreversibly reacts with water, resulting in deterioration of absorption capacity and formation of precipitates, and generates hydrochloric acid. For industrial implementation, the water in the gas mixture must be 1
It must be strictly controlled to below ppm. Therefore, a strong dehydration process of the i/IIL gas is required before the absorption process, and strict control is essential. Copper aluminum tetrachloride reacts strongly with water and irreversibly loses its ability to absorb carbon monoxide, so even if it is 1 ppm
Even when a mixed gas containing water is brought into contact, the deactivation amount gradually increases as the amount of mixed gas processed increases, and equipment corrosion progresses due to the hydrochloric acid produced by the reaction with water. Contains disadvantages. In addition, when this absorption liquid is used, it is inevitable that toluene vapor 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.

The above copper aluminum tetrachloride (Cu(A/C/,)
A carbon monoxide separation method using a solid adsorbent composed of copper(I) halide and activated carbon is known as a carbon monoxide separation method that solves the disadvantages of the carbon monoxide separation method using a toluene solution ( JP-A-58-156517)
. In this method, carbon monoxide is rapidly absorbed when the solid adsorbent is brought into contact with a mixed gas containing carbon monoxide at around room temperature, and then the absorbent is heated to a certain temperature or Carbon monoxide can be easily released by reducing the partial pressure.

A known method for manufacturing the carbon monoxide adsorbent used in this separation method is to add activated carbon to a solution or suspension of copper II halide + copper oxide (moon), and then distill off the solvent. (Japanese Patent Application Laid-Open No. 59-105841).

[Problem that the invention seeks to solve]

However, in the above-mentioned manufacturing method of carbon monoxide adsorbent,
■ Problems such as requiring a large amount of energy to distill off the solvent and the need for large-scale solvent treatment equipment when implementing it industrially, as well as copper (I) halide or copper oxide (I)
) If the solution is highly concentrated and large, a large amount of unreacted halogenated steel (I) or copper oxide (I) will precipitate after the solvent is distilled off, so in practice, a solution with high concentration and large amount cannot be used. Therefore, activated carbon cannot sufficiently support carbon monoxide adsorption components such as copper halide) or copper(I) oxide, resulting in the problem that the resulting adsorbent does not have sufficient carbon monoxide adsorption properties.

The present invention aims to provide a simple method for producing an adsorbent having sufficient carbon monoxide adsorption capacity.

[Failure to solve the problem]

In order to solve these problems, the inventors conducted extensive research on a new method for producing a carbon monoxide adsorbent, and as a result, they discovered that copper (I) halide or copper oxide fil was immersed in a hydrochloric acid solution. The inventors have discovered that an adsorbent with excellent carbon monoxide adsorption ability can be obtained by removing activated carbon from the solution and then drying it, leading to the completion of the present invention.

That is, the present invention is a method for producing a carbon monoxide adsorbent, which is characterized in that activated carbon is immersed in a hydrochloric acid solution of copper (I) halide or copper (I) oxide, taken out from the solution, and then dried. It's a method.

[Effect]

In the method for producing a carbon monoxide adsorbent of the present invention, activated carbon is immersed in a hydrochloric acid solution of copper (I) chloride or copper (I) oxide, taken out from the solution, and then dried. In order to produce a carbon monoxide adsorbent, the hydrochloric acid adhering to the activated carbon taken out from the solution is the only solvent to be removed during drying. Therefore, in the method for manufacturing the carbon monoxide adsorbent of the present invention, only a small amount of energy is required to remove the hydrochloric acid solvent from activated carbon treated with a hydrochloric acid solution of copper halide (ene or copper oxide). There is an advantage that the hydrochloric acid treatment equipment required for the drying process can be small-scale.

The copper halide +I+ used in the production method of the present invention is, for example, copper chloride (moon, copper (I) bromide, copper (I) iodide, etc.).

On the other hand, the activated carbon used in the manufacturing method of the present invention is activated using a method such as a chemical activation method or a gas activation method using wood, coconut shell, coal, petroleum pitch, cellulose fiber, chemical fiber, etc. as raw materials. , and is not limited in shape at all,
Powder, granule, fiber, or any of these molded into an arbitrary geometric shape can be used.

The hydrogen chloride concentration of the hydrochloric acid used in the production method of the present invention is 1 to 5.
A hydrochloric acid solution of copper(I) halide or copper(I) oxide in an amount of [15 to 601, preferably 10 to 409% by weight] per 100 tIlt of hydrochloric acid is 0 to 25% by weight, preferably 15 to 25% by weight. It is a solution obtained by adding copper (I) halide or oxidized steel (katana).

The temperature of the hydrochloric acid solution of halogenated steel (I) or oxidized steel (I) used in the production method of the present invention is 10 to 150°C, preferably 50 to 120°C. Further, the time for immersing the activated carbon in the solution is 1 minute to 10 hours, preferably 30 minutes to 3 hours, and it is preferable to stir the solution while the activated carbon is being immersed.

In the production method of the present invention, the activated carbon taken out from the hydrochloric acid solution of copper (I) halide or copper (I) oxide is dried in an inert gas atmosphere such as nitrogen or argon under normal pressure or reduced pressure, preferably α01~ It is carried out at a temperature of 20 to 500°C, preferably 80 to 200°C, under a reduced pressure of 10 Hg.

The carbon monoxide adsorbent obtained by the production method of the present invention can be
Rapid adsorption of carbon monoxide at 0 to 40°C, and easy release of adsorbed carbon monoxide by raising the temperature of this adsorbent to 60°C or higher or lowering the partial pressure of carbon monoxide. I can do it.

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

〔Example〕

Example 1 A carbon monoxide adsorbent was prepared according to the manufacturing method of the present invention as follows. First, under dry nitrogen, copper(I) chloride s 9.6y (
Add 200% hydrochloric acid with a hydrogen chloride concentration of 20% by weight, heat the inside of the flask to 100°C while stirring using a magnetic stirrer, and add copper(I) chloride.
was dissolved in the hydrochloric acid.

Next, in the hydrochloric acid solution in this flask, commercially available coal-based granular activated carbon (average particle size 1.0 II
After stirring for 2 hours while keeping the contents of the flask at 100° C., the soaked activated carbon was taken out from the hydrochloric acid solution under dry nitrogen, and under a reduced pressure of 5 BHg. 3 at 120℃
Perform drying for an hour and get carbon monoxide adsorbent.

The above carbon monoxide adsorbent 10y was placed in an eggplant-shaped flask with a content of f*100-, and again kept at 120°C for 1 hour while being evacuated under a reduced pressure of 5111+1Hg, and then left under reduced pressure until it reached room temperature. . The eggplant-shaped flask is then combined with a container containing 1 atm of carbon monoxide, and
Carbon monoxide was brought into contact with the adsorbent at 20°C, and carbon monoxide adsorption was measured by the gas buret method.

The adsorption of carbon monoxide is rapid, with 12,0
mmox of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was 1a 8 mmol, almost reaching the equilibrium adsorption amount.

Next, using a vacuum pump, the inside of the eggplant-shaped flask containing this carbon monoxide adsorbent was heated to 5<em>Hg at 20°C.
After evacuation for 10 minutes under a reduced pressure of contacted with an adsorbent.

The adsorption of carbon monoxide is rapid, with 11,7
mmol of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was I FL 2 mmol, almost reaching the equilibrium adsorption lid.

Thereafter, even if the above operation was repeated, no change in the carbon monoxide adsorption rate or adsorption itK was observed.

Example 2 10 r of carbon monoxide adsorbent prepared in the same manner as in Example 1 was placed in an oval-shaped flask with an internal volume of 100 -, and 5IOIHg
The mixture was kept at 120° C. for 1 hour while being evacuated under reduced pressure, and then left to stand under reduced pressure until it reached room temperature. Next, this eggplant-shaped flask was combined with a container containing 1 atm of carbon monoxide, and carbon monoxide was brought into contact with the adsorbent at 20° C., and the amount of carbon monoxide adsorbed was measured by the gas burette method.

The adsorption of carbon monoxide is rapid, with 12,0
mmol of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was 1 a 8 mmol, almost reaching the equilibrium adsorption amount.

Next, this adsorbent was heated to 120° C. at 1 atm, and the amount of carbon monoxide released was measured by the gas buret method.

Carbon monoxide is released quickly, the amount released is 11 after 10 minutes.
．． It reached 5 rnmol. Analysis of the released gas using a gas chromatograph revealed that the released gas was only carbon monoxide and no other components were detected.

After that, the eggplant-shaped flask containing the adsorbent that released carbon monoxide was cooled while passing dry nitrogen, and then 1 at.
The carbon monoxide was brought into contact with the adsorbent at 20°C.

The adsorption of carbon monoxide is rapid; after 3 minutes, j Q,
A mm01 of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was 1 & A mmo'l, almost reaching the equilibrium adsorption amount.

When this adsorbent is heated to 120°C at 1 atm, -m
The carbon dioxide is released quickly, and the amount released is 16.6% after 10 minutes.
mmol was reached.

Thereafter, even if the above operation was repeated, no change was observed in the adsorption rate and amount of carbon monoxide.

Example 3 A carbon monoxide adsorbent was prepared according to the manufacturing method of the present invention as follows. First, copper oxide +112 a A f (0,
2+n+n1. ), add 200% of hydrochloric acid with a hydrogen chloride concentration of 20% by weight, and heat the inside of the flask to 100°C while stirring using a magnetic stirrer.
) was dissolved in the hydrochloric acid.

Next, the same activated carbon as in Example 1, which had been dried in the same manner as in Example 1, was immersed in 10 rQ of the same activated carbon as in Example 1 under dry nitrogen in the hydrochloric acid solution in this flask, and stirred for 2 hours while keeping the contents of the flask at 100°C. Afterwards, the soaked activated carbon is removed from the hydrochloric acid solution under dry nitrogen; 5. Under reduced pressure of Hg, 1
Drying was performed at 20° C. for 3 hours to obtain a carbon monoxide adsorbent.

The above carbon monoxide adsorbent 102 was placed in an oval-shaped flask with an internal volume of 100 mm, and again kept at 120°C for 1 hour while being evacuated under a reduced pressure of 5 Hg, and then left under reduced pressure until it reached room temperature. did. Next, this eggplant-shaped flask was heated to 1 at
The adsorbent was connected to a container containing carbon monoxide 3e, and carbon monoxide was brought into contact with the adsorbent at 20° C., and the amount of carbon monoxide adsorbed was measured by the gas buret method.

The adsorption of carbon monoxide is rapid, with 11,4
mm0IL of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was 17.9 mmol, almost reaching the equilibrium adsorption amount.

Next, the inside of the eggplant-shaped flask containing this carbon monoxide adsorbent was evacuated for 10 minutes at 20°C under a reduced pressure of 5 mHg using a vacuum pump to release the adsorbed carbon monoxide. This eggplant flask was connected to a container containing 3 tons of carbon monoxide at 1 atm, and the carbon monoxide was brought into contact with the adsorbent at 20°C.

The adsorption of carbon monoxide is rapid, with 11,1
mmal of carbon monoxide was adsorbed, and the amount of carbon monoxide adsorbed after 60 minutes was j 7.4 mmal, almost reaching the equilibrium adsorption amount.

Thereafter, even if the above operation was repeated, no change was observed in the adsorption rate and amount of carbon monoxide.

Example 4 10 tons of carbon monoxide adsorbent prepared in the same manner as in Example 3 was placed in an oval-shaped flask with an internal volume of 100-
After being kept at 120°C for 1 hour while being evacuated under a reduced pressure of
It was left under reduced pressure until it reached room temperature. Next, this eggplant-shaped flask was combined with a container containing 3 tons of carbon monoxide at 1 atm, and the carbon monoxide was brought into contact with the adsorbent at 20° C., and the amount of carbon monoxide adsorbed was measured by the gas buret method.

The adsorption of carbon monoxide is rapid, with 11,4
mmol of carbon monoxide was adsorbed, and the carbon monoxide adsorption after 60 minutes was 17.9 mmol, almost reaching the equilibrium adsorption amount.

Next, this adsorbent was heated to 120° C. at 1 atm, and the amount of carbon monoxide released was measured by the gas buret method.

Carbon monoxide is released quickly, with the amount released being 15% after 10 minutes.
．． 5 mmol [reached. Analysis of the released gas using a gas chromatograph revealed that the released gas was only carbon monoxide and no other components were detected.

Then carbon monoxide? After cooling the eggplant-shaped flask containing the released adsorbent while passing through dry nitrogen, 1 a
The carbon monoxide was brought into contact with the adsorbent at 20°C.

Carbon monoxide adsorption is rapid, with 10,1
mmQ'l of carbon monoxide is adsorbed, and the amount of carbon monoxide 3/amount after 60 minutes is 15.8 mmol, Q]
Almost equilibrium adsorption 1 was reached.

When this adsorbent is heated to 120°C at 1 atm, carbon monoxide is rapidly released, with the amount released being 15.8% after 10 minutes.
mm) reached 1.

Thereafter, even if the above operation was repeated, no change was observed in the adsorption rate and amount of carbon monoxide.

〔Effect of the invention〕

The present invention provides a completely new method for producing a carbon monoxide adsorbent, which enables reduction in energy requirements and downsizing of necessary equipment.

Furthermore, the hydrochloric acid FD solution of copper (I) halide or copper oxide (Il) used in the method for producing the carbon monoxide adsorbent of the present invention can be repeatedly reused, and according to the present invention,
A highly economically advantageous carbon monoxide adsorbent has been produced.

Sub-agent: 1) Akira Sub-agent Ryo Hagi Hara - Sub-agent Atsuo Yasunishi

Claims (1)

[Claims] A method for producing a carbon monoxide adsorbent, which comprises immersing activated carbon in a hydrochloric acid solution of copper (I) halide or copper (I) oxide, taking it out from the solution, and then drying it.