JPS61242908A - Adsorbent for separating and recovering co, production thereof and method for separating and recovering co of high purity using said adsorbent - Google Patents

Abstract

PURPOSE:The titled adsorbent, obtained by supporting a copper compound on a carrier consisting of activated carbon having a specified pore diameter and specific surface area, and capable of separating and recovering CO of high purity from a mixed gas containing the CO. CONSTITUTION:A copper compound is supported on a carrier consisting of activated carbon having a pore distribution of <=0.33ml/g, particularly <=0.20ml/g pore volume having <=10Angstrom diameter and >=0.35ml/g, particularly >=0.40ml/g pore volume having 20-300Angstrom pore diameter and >=1,300m<2>/g specific surface area. A copper (I) compound, e.g. copper (I) chloride, copper (II) compound, e.g. copper (II) chloride or reduced copper (II) compound, is used as the copper compound. The copper compound is supported on the carrier by a method for bringing a solution or dispersion prepared by dissolving or dispersing the compound in a solvent into contact with the carrier, and removing the solvent, etc. The resultant adsorbent is filled in an adsorption column and capable of efficiently separating and recovering CO from a mixed gas containing the CO by the PSA or TSA method.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides a method for separating a mixed gas containing CO by a pressure fluctuation adsorption separation method (hereinafter referred to as PSA method) or/and a temperature fluctuation adsorption separation method (hereinafter referred to as TSA method). It relates to an adsorbent used for the purpose of separating and recovering high-purity CO,
Furthermore, the present invention relates to a method of manufacturing the adsorbent and a method of separating and recovering high-purity CO using the adsorbent.

Conventional technology Typical gases containing CO as a main component include converter gas obtained from converters in steel plants, blast furnace gas obtained from blast furnaces, electric furnace gas obtained from electric furnaces, and gasification of coke. There is a generator gas that can be obtained. Most of these gases are normally used as fuel, but some of these gases contain CO, for example, around 70 MaO1% or more. If CO can be separated and recovered with high purity, it can be used as a raw material for synthesizing formic acid, acetic acid, etc., and for reducing organic compounds, which is extremely useful in the chemical industry.

Conventionally, methods for separating and recovering CO from gas whose main component is CO include cryogenic separation method, copper ammonia method, and Cosorb (
The CO3ORB method is known, but these methods have the problem of high equipment costs and high costs for thermal energy such as electricity and steam, and are not suitable for separating and recovering large amounts of CO. However, these methods were not necessarily suitable for the separation and recovery of medium or small volumes of CO. Furthermore, the CO obtained by separation by these methods contains 0, COZ
It has the disadvantage that it cannot be used as it is for organic synthesis because it contains gas components that can be a hindrance to organic synthesis reactions.

By the way, the PSA method and the TSA method are known as methods for selectively separating a specific gas from a medium or small volume of source gas.

The PSA method is a method for selectively separating a specific gas from a mixed gas.The adsorbent is adsorbed onto an adsorbent at high pressure, and then the adsorbed material is removed by lowering the pressure of the adsorption system. This method desorbs adsorbed substances and separates adsorbed substances and non-adsorbed substances.Industrially, multiple towers filled with adsorbent are installed, and in each adsorption tower, the steps of pressurization → adsorption → washing → deaeration are performed. By repeating a series of operations, the entire device can perform continuous separation and recovery.

Similarly to the above-mentioned PSA method, the TSA method is also a method for selectively separating a specific gas from a mixed gas.The adsorbent is adsorbed onto an adsorbent at a low temperature, and then the temperature of the adsorption system is raised. In this method, the adsorbed substances are desorbed and the adsorbed substances and non-adsorbed substances are separated.

Conventionally, this PSA method was used to remove CO from a mixed gas containing CO.
A method using mordenite-based zeolite as an adsorbent has been proposed as a method for separating and recovering. (Refer to #Kokai No. 59-22825 and JP-A No. 58-4H18) In addition, as a method for separating and recovering CO from a mixed gas containing CO by the PSA method or the TSA method, copper halide (1), Copper (I) oxide, copper (II) salt, copper (II) oxide
) and other copper compounds supported on activated carbon have been proposed. (Unexamined Japanese Patent Publication No. 58-15
8517, JP 59-89414, JP 59-105841, JP 59-13813
(Refer to Publication No. 4) Problems to be Solved by the Invention When carrying out the PSA method or the TSA method, the performance required of the adsorbent packed in the adsorption tower is: (1) selective adsorption of the component of interest relative to coexisting components; ■There is a large difference in the adsorption amount of the target component under pressure or low temperature and under reduced pressure or high temperature.■The adsorbed target component is easily desorbed.■It is difficult for components other than the target component to be adsorbed and desorbed. These performances have a great influence on the purity and yield of the product gas, and are therefore important factors in the PSA method or TSA method.

However, in the method of using mordenite-based zeolite as an adsorbent, which utilizes the physical adsorption/desorption phenomenon of the adsorbent, the amount of CO adsorbed is relatively small, so the pressure swing must be switched more frequently. , there are disadvantages in terms of operation and valve life; C02 must be removed in advance before adsorption operation;
2. Co-adsorption of Go is unavoidable, resulting in low product purity, and a large amount of cleaning is required to clean the inside of the tower using product CO gas to remove adsorbed N, resulting in a low recovery rate of Go product. There are issues such as what happens.

On the other hand, in a method using an adsorbent in which the copper compound is supported on activated carbon, which utilizes the chemical adsorption/desorption phenomenon of the adsorbent, C01N2. , CO, etc. from a mixed gas containing
When attempting to separate O, 002. There are problems such as the fact that it is difficult to separate and recover CO with a high purity that can be used for organic synthesis, and the amount of CO adsorbed by the adsorbent is not necessarily large. It has not yet reached the point where it can be adopted on an industrial scale.

In view of this situation, the present invention was achieved as a result of intensive research to find an industrially advantageous adsorbent that can efficiently separate and recover high-purity CO from a mixed gas containing CO.

Means for Solving the Problems The adsorbent for CO separation and recovery of the present invention has a pore diameter of 10λ or less, a pore volume of 0.33ml/g or less, and a pore diameter of 20Å.
A copper compound is supported on a carrier made of activated carbon having a pore distribution with a pore volume of 0.35 sl/g or more and a specific surface area of 1300 m''/g or more.

In addition, the method for producing the adsorbent for CO separation and recovery of the present invention has a pore diameter of 10 Å or less and a pore volume of 0.33 ml/g or less,
Pore diameter 20Å~300 people pore volume 0.35ml/
A solution or dispersion in which a copper compound is dissolved or dispersed in a solvent is brought into contact with a carrier made of activated carbon having a pore distribution of 1,300 m''/g or more and a specific surface area of 1,300 m''/g or more, and then the solvent is removed. It is characterized by:

Furthermore, in the method for separating and recovering high-purity CO of the present invention, when separating and recovering high-purity CO from a mixed gas containing CO by the PSA method and/or TSA method, the method uses an adsorbent with a pore diameter of 1O5. The pore volume below is 0.33ml
/g or less, the pore diameter is 20 Å to 300 people, and the pore volume is 0.
．． has a pore distribution of 35 ml/g or more, and 130 ml/g or more;
The present invention is characterized by using an adsorbent for CO separation and recovery, which is made by supporting a copper compound on a carrier made of activated carbon having a specific surface area of 0 m'/g or more.

The present invention will be explained in detail below.

Lat! The adsorbent for CO separation and recovery of the present invention uses activated carbon as a carrier, which has a special pore distribution and specific surface area, unlike general activated carbon, and supports a copper compound thereon.

That is, in the present invention, the carrier has a pore diameter of 1
The pore volume of 0λ or less is 0.33 ml/g or less, the pore diameter is 20 Å to 300 people, and the pore volume is 0.35 tl/g or more, and the pore size is 1300 m'/g or more. Activated carbon with a specific surface area is used. A particularly preferable pore distribution is that the pore volume with a pore diameter of 10λ or less is 0.20 ml/
g or less, the pore diameter is 20 Å to 300 people, and the pore volume is 0.
It is 4011/g or more. Also, the specific surface area is 1400m
Even if an adsorbent is manufactured using activated carbon with a pore distribution or specific surface area outside the above range, it is more desirable to have a value of 100% or more than 100% of the above range. I can't.

Japanese Patent Application Laid-Open No. 1565-1983 mentioned earlier in the section of "Prior Art"
Publication No. 17, Japanese Unexamined Patent Application Publication No. 1983- [No. 414, Japanese Unexamined Patent Publication No. 1983
General activated carbon, such as those listed in Examples in Publication No. 105841 and Japanese Unexamined Patent Application Publication No. 53-138134,
The pore volume with a pore diameter of 10λ or less is, for example, 0.34 to 0.
．． The pore diameter is about 70 ml/g, the pore volume is about 20 Å to 300 ml/g, for example, about 0.34 to 0.10 ml/g, and the specific surface area is about 1300 to 1100 ng/g, so in the present invention The activated carbon used as a carrier is
It can be said that it has more pores with larger diameters than these general activated carbons. Such activated carbon can be used depending on the type of raw material, type and amount of binder
It is obtained by selecting activation conditions etc. appropriately.

Here, the pore volume is determined by the nitrogen gas measurement method at liquid nitrogen temperature, and in each isotherm, the relative pressure p/p,
Point x where the relationship with adsorption amount X becomes horizontal to the relative pressure axis
s and assuming that pore filling is completed by capillary condensation,
It was determined as pore volume vs=xs/ρ. ρ is the density of adsorbed gas. Further, the specific surface area is measured by a nitrogen gas adsorption method at liquid nitrogen temperature and determined using the BET formula.

The shape and particle size of the activated carbon having the above-mentioned specific pore distribution and specific surface area are not particularly limited; It is preferable to use the selected one after drying it if necessary.

The copper compound supported on the above-mentioned specific activated carbon carrier may be a copper(I) compound, a copper(II) compound or a copper(
II) A reduced product of the compound is used.

Note that, in some cases, aluminum halides such as aluminum chloride, aluminum fluoride, and aluminum bromide may be used in combination with these copper compounds.

Here, copper (I) compounds include copper halides (1) such as copper chloride (1), copper fluoride (1), copper bromide (I); copper oxide (1); copper cyanide (1); ; Copper formate (1), copper acetate (
1), Shu forged steel (1), copper sulfate (1), sulfur forged steel (I
), copper(I) oxyacid or arI11 salt; copper(1) sulfide; dichlorocopper(I) salt, tetrachlorocopper(I)
) acid salt, dicyanocopper(I) acidate, tetracyanocopper(I)
) Complex salts such as acid salts; etc. are exemplified. Especially copper chloride (1)
is suitable.

Copper(II) compounds include copper chloride (■) and copper fluoride (■).
II), copper halides (■) such as copper bromide (■); copper oxide (■); copper cyanide (■): copper formate (II), copper acetate (■), Shu-forged steel (■), sulfuric acid Copper (II), copper nitrate (
Copper (I), such as phosphorus forged steel (■), copper carbonate (II)
I) oxyacid or organic acid salt; copper hydroxide (■); copper (II) sulfide; ) refluorocopper (II) salt, tetrafluorocopper (■) # salt, trichlorocopper (II) salt,
Tetrachlorocopper(rI) salt, tetracyanocopper(II)
Examples include complex salts such as acid salts, detrahydrooxocuprate(II) salts, hexahydroocune cuprate(II) salts, and ammine complex salts.

When a copper (II) compound is supported on a carrier, a reduced product of the copper (II) compound may also be used. This reduced product is a mixture of a copper (CI) compound and a copper (IT) compound, or a monovalent and I
It is presumed to be a compound with an atomic valence between I and I.

The amount of copper compound supported on the carrier is selected from a wide range, but is usually 1 to 15 mmol/g, preferably 2
-10 m-mol/g. If the supported amount is too small, the CO adsorption capacity will be insufficient, while if the supported amount is too large, the separation efficiency will tend to decrease.

The above-mentioned adsorbent is produced by contacting a carrier made of the specific activated carbon with a solution or dispersion in which a copper compound is dissolved or dispersed in a solvent, and then removing the solvent.

The solution or dispersion is brought into contact by impregnation, spraying, or the like. At this time, in addition to simply contacting the carrier with a solution or dispersion of a copper compound by means such as impregnation or spraying, the solution or dispersion of a copper compound may be brought into contact with a vacuum-degassed carrier, or After the solution or dispersion is brought into contact, it may be degassed under reduced pressure conditions.

Examples of solvents include water, hydrochloric acid, acetic acid, formic acid, ammoniacal formic acid aqueous solution, aqueous ammonia, and halogen-containing solvents (
Chloroform, carbon tetrachloride, ethylene dichloride, trichloroethane, tetrachloroethane, tetrachloroethylene, methylene chloride, fluorinated solvents, etc.), sulfur-containing solvents (carbon disulfide, dimethyl sulfoxide, etc.), nitrogen-containing solvents (propionitrile, acetonitrile, diethylamine, etc.) , dimethylformamide, N-methylpyrrolidone, etc.), hydrocarbons (hexane, benzene, toluene, xylene, ethylbenzene, cyclohexane, decalin, etc.), alcohols (methanol, ethanol, propatool, butanol, amyl alcohol, cyclohexanol, ethylene glycol) , propylene glycol, etc.), ketones (
Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, isophorone, cyclohexanone, etc.), esters (methyl acetate, ethyl acetate, amyl acetate, methyl propionate, amyl propionate, etc.), ethers (isopropyl ether, dioxane, etc.), cellosolves (cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, etc.), carpitols, etc. are used.

After contacting the carrier with the solution or dispersion of the copper compound,
Remove the solvent under an air atmosphere or an inert gas atmosphere such as nitrogen or argon. The solvent can be removed not only by simple heat drying but also by vacuum drying.

When a copper (I) compound is used, an adsorbent exhibiting sufficient CO adsorption ability can be obtained by this drying, but a heat treatment may be further performed in an inert gas or reducing gas atmosphere.

On the other hand, when a copper (II) compound is used, the CO adsorption capacity is often insufficient just by the above-mentioned drying. Therefore, when a copper (II) compound is used, it is desirable to activate the adsorbent after drying by further heat-treating it in an atmosphere of air, inert gas, or reducing gas. In particular, it is preferable to carry out the heat treatment under an inert gas or reducing gas atmosphere. The heating temperature is 100℃ in air.
~200°C1 It is appropriate to set the temperature to 280 to 500°C in an inert gas such as nitrogen or argon, and 150 to 250°C in a reducing gas such as CO, H, etc.
The desired activation cannot be achieved sufficiently outside this temperature range.

Through this heat treatment, the copper (■) compound supported on the carrier is partially reduced, resulting in a mixture of copper (I) and copper (II) compounds, or a valence intermediate between monovalent and ■ valence. It is estimated that this compound will have the following properties:

The adsorbent obtained in the above manner is packed into an adsorption tower, and CO is separated and recovered from a mixed gas containing CO by the PSA method or the TSA method.

When separating and recovering CO by the PSA method, the adsorption pressure in the adsorption step is atmospheric pressure or higher, for example 0~6 kg.
/cm2'G, and the degree of vacuum in the vacuum degassing step is below atmospheric pressure, for example 200 to 10 To
It is desirable to set it to rr.

When separating and recovering CO by the TSA method, it is desirable that the adsorption temperature in the adsorption step is, for example, about 0 to 40°C, and the degassing temperature in the degassing step is, for example, about 60 to 180°C.

It is also possible to use the PSA method and the TSA method in combination, performing adsorption at atmospheric pressure or higher under low temperature conditions and degassing at atmospheric pressure or lower under high temperature conditions.

In addition, since the TSA method is disadvantageous compared to the PSA method in terms of energy consumption, it is desirable to adopt the PSA method or a combined PSA-TSA method from an industrial perspective.

As the mixed gas containing CO that can be applied to the method of the present invention, for example, converter gas generated from a converter in a steel mill is used. Converter gas usually contains CO as the main component, as well as 02. , methane and other hydrocarbons, water and small amounts of N
2. Contains S, NH5, etc. In addition to converter gas, blast furnace gas, electric furnace gas, generator gas, etc. can also be used as raw material gas.

In addition, in the present invention, prior to the CO separation and recovery step,
It is desirable to provide a step for adsorption and removal of impurities such as sulfur compounds and NH5, a moisture removal step and an 02 removal step, which may poison the adsorbent or shorten its lifespan. However, it is not enough to provide a CO2 removal process or a N2 removal process.

For industrial operations when the PSA method is employed, a plurality of adsorption towers filled with the above-mentioned adsorbent may be used, and each operation illustrated below may be sequentially repeated in each adsorption tower.

(a) A step of flowing the raw material gas into an adsorption tower to adsorb CO;
and a step in which the exhaust gas is used for pressurization (m) of another column shortly before the CO concentration in the exhaust gas becomes equal to the CO concentration in the raw material gas; (b) after the adsorption step, the adsorption column and vacuum deaeration are performed; A depressurization step in which the pressure in the former adsorption tower is reduced to near atmospheric pressure in parallel flow, and a corresponding step (1) in which the pressure in the latter adsorption tower is increased (1); A cleaning step in which a part of the product gas is introduced into the column in parallel flow to clean the remaining impurity gas inside the column, and a step in which the gas discharged at this time is used for pressurization (II) in another column; (d) Vacuum A product recovery process in which the CO adsorbed on the adsorbent is degassed in a countercurrent flow from the adsorbent by reducing the pressure, and the product gas is recovered.

(e) Pressure increasing (I
) step, (f) pressurization step (II) in which the pressure is increased in parallel flow using the washed exhaust gas from another adsorption tower, (g) step (m) in which the pressure is increased by the exhaust gas near the end of the adsorption step in another adsorption tower, in sequence. Just do it repeatedly.

By sequentially repeating the above operations in each adsorption tower in this way, highly pure CO gas can be continuously separated and recovered at a high recovery rate.

Effect The adsorption/desorption phenomenon caused by the solid adsorbent of the present invention is mainly caused by a reversible chemical reaction between the copper compound supported on the carrier and CO (
complex formation reaction and dissociation reaction).
(no chemical reaction with CO2 takes place), which is secondarily based on physical adsorption onto the pore surfaces of the activated carbon support and desorption therefrom.

The activated carbon used as a carrier in the present invention has many pores with larger diameters than general activated carbon, so even if the raw material gas contains CO2 and N, CO and NL will not enter the carrier pores during the adsorption process. It is thought that the amount of physically adsorbed impurities is small, and that these impurities physically adsorbed in the pores of the carrier are easily desorbed by the cleaning gas.

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

Separation and recovery of CO was performed using an apparatus whose flow sheet is shown in FIG.

In Figure 1, (1) is an adsorption tower, (2a), (2b)
.

(2c) and (2d) are valves, (3) is a vacuum pump, (4) is a product tank, (a) is a raw material gas, (b) is a product CO gas, and (C) is a purge gas.

Example 1 The pore volume with a pore diameter of 10λ or less is 0.12 ml/g,
Pore diameter 20Å~300 people pore volume 0.47ml/
Activated carbon having a pore distribution of 1,500 rn''/g and a specific surface area of 1,500 rn''/g was prepared and dried in the air at 110° C. for 6 hours.

Put 50 g of the above dry activated carbon into a 5θ01 Erlenmeyer flask, and add copper chloride (I) to 1501 ethanol.
Add a solution in which 87 g of I) was dissolved, and use an aspirator to
After degassing for a minute, it was left to stand for 4 hours. Next, while heating to 100°C with a mantle heater, the solvent was distilled off in a N gas stream, and further N was added in an electric furnace.

After heat treatment was performed at 350° C. for 2 hours in an air stream, the mixture was cooled to room temperature to obtain an adsorbent for CO separation and recovery.

The activated carbon obtained above was placed in an adsorption tower (26 φ x 300 mm
H), and supplying a raw material gas of 2 kg/cm'LG with a composition of CO: 71.4 vo1% N2: 12.7 vo1% COZ: 15.13 vo1%, and CO at 20'O. It was adsorbed. The amount of CO adsorbed at this time was 28.8 cc/cc.Then, after reducing the pressure to atmospheric pressure, the inside of the column was washed with 900 ml of Go, and then degassed for 5 minutes at a pressure of 50 Torr using a vacuum pump. The gas was released.

The amount of CO released at this time was 14.7 cc/cc, and the recovered gas composition was as follows: CO: f99.93vo1% COz: 0.07vo1% Nz: trace.

When adsorbed again under the same conditions as above, the released CO'l
The same amount of cd as l was adsorbed. Thereafter, even if this adsorption-degassing process was repeated, the adsorption amount, release amount, and purity of CO did not change.

Comparative example! As a carrier, the pore diameter is 10A or less and the pore volume is 0.4:
2 ml/g, pore diameter 20 Å to 300 A, pore volume 0.21 ml/g, and 1300 Å
Commercially available activated carbon (A
An adsorbent was produced in the same manner as in Example 1, except that the adsorbent was used (manufactured by Alumni Co., Ltd.).

This adsorbent was packed into a column and an experiment was conducted under the same conditions as in Example 1. The results were as follows.

CO adsorption Ik24.13 cc/cc CO release amount 14.0 cc/cc Recovery gas composition CO: E18.0vo1% CO2: 1.9 vo1% N2. : Q, 1vo1% Comparative Example 2 As a carrier, the pore volume with a pore diameter of 10λ or less is 0.13
A commercially available activated carbon having a pore distribution with a pore diameter of 20 Å to 300 ml/g, a pore volume of 0.173 ml/g, and a specific surface area of 132 G-m"7 g. manufactured by Company B).

An adsorbent was produced in the same manner as in Example 1 except for the use of the adsorbent, and the adsorbent was packed into a column and an experiment was conducted under the same conditions as in Example 1. The results were as follows.

CO adsorption ft 213.5 cc/cc CO release fil 15.3 cc/cc Recovery gas composition CO: 97.2 vo1% CO2,: 2.7 vo1% N2. :0.1
Malo 1% Comparative Example 3 As a carrier, the pore volume with a pore diameter of 10λ or less is 0.34
Commercially available activated carbon (C
An adsorbent was produced in the same manner as in Example 1, except that the adsorbent was used (manufactured by J.D. Co., Ltd.), and the adsorbent was packed into a column and an experiment was conducted under the same conditions as in Example 1. The results were as follows.

CO adsorption amount 22.4 cc/ccCO release amount
12. θcc/cc Recovery gas composition CO: 98.5vo1% CO2: 1.4ma01% Nz: 0.1vo1% Comparing the CO purity in Comparative Examples 1 to 3 above and Example 1, Example 1 9943vo1% Comparative example 1 98.0 Malo 1% Comparative Example 2 fl17.2 vo1% Comparative Example 3
H, 5 va 1%, and at first glance there does not seem to be much difference in terms of CO purity, but from the perspective of the impurity mixing rate in the product gas, Example 1: 0.07 va 1% Comparative Example 1: 2.0 Malo 1% Comparative Example 2 2.8 Malo 1% Comparative Example 3 1.5 Malo 01% Comparative Examples 1 to 3 contain 29 times, 40 times, and 21 times more impurities than Example 1, respectively. It shows that it is. This difference directly affects whether or not the product CO can be used for organic synthesis, and it can be seen how excellent Example 1 is.

Example 2 Example 1 except that water was used in the melt and the heat treatment temperature was 400°C.
A CO adsorbent was produced in the same manner as in Example 1, and the adsorption operation was performed under the same conditions as in Example 1. The results were as follows.

CO adsorption amount 30.0 cc/ccCO release fl
12.9cc/cc Recovery gas composition CO: 99.48vo1% CO2,: 0.54vo1% N2. : trace Example 3 A CO adsorbent was produced in the same manner as in Example 1, except that the heat treatment was carried out at 250°C for 11 hours in H2 air flow, and the adsorption operation was carried out under the same conditions as in Example 1. Ta. The results were as follows: CO adsorption amount 24.4 cc/cc CO release amount
12.5 cc/cc recovered gas composition CO: 99.9 vol% COz: 0.1 vol% NZ: trace Example 4 As activated carbon, the pore volume with a pore diameter of lOλ or less is 0.3
2 ml/g, pore diameter 20 Å to 300 pore volume is 0.3E1 ml/g, and 135
A CO adsorbent was produced in the same manner as in Example 1, except that activated carbon having a specific surface area of 0 m' /H was used, and the adsorption operation was carried out under the same conditions as in Example 1. The results were as follows.

CO adsorption amount 22.8 cc/ccCO release amount
9.8 cc/cc Recovery gas composition CO: 99.81vol% CO2: 0.19vol% N2. : trace Example 5 The pore volume with a pore diameter of 10 Å or less is 0.12 ml/g,
Pore diameter 20Å~300 people pore volume 0.47ml/
Activated carbon having a pore size distribution of 1500 m''/g and a specific surface area of 1500 m''/g was prepared and dried in the atmosphere at 110° C. for 6 hours.

Put 50 g of the above dry activated carbon into a 5001 Erlenmeyer flask, and add chlorinated steel (I) to 150 ml of hydrochloric acid.
A solution containing 40 g of the solution was added, and the mixture was degassed using an aspirator for 1 minute, and then allowed to stand for 4 hours. Next, while heating to 200°C with a mantle heater, N2. After distilling off the solvent in a gas stream, the mixture was cooled to room temperature to obtain an adsorbent for CO separation and recovery.

The adsorbent obtained above was packed into an adsorption tower, and adsorption operation was performed under the same conditions as in Example 1. The results were as follows.

CO adsorption amount 25.2 cc/ccCO release amount
13.2 cc/cc Recovered gas composition CO: 99.89% CO, 0.11vol% N2. :
trace Example 6 An experiment was conducted under the same conditions as Example 5 except that 30 g of copper (I) oxide was used in place of copper (I) chloride. The results were as follows.

CO adsorption amount 28.3 cc/ccCO release amount
11.5 cc/cc recovered gas composition CO2 99.9vol %CO2,
: 0.1 vo1% NIL: trace Effects of the Invention In the present invention, even in a mixed gas containing CO as well as N2 and COz, not only the co-adsorption of Nz is small but also the co-adsorption of CO2 is suppressed. Adsorbed N2 and C0
Since impurities such as 2 and 2 are easily removed by supplying a small amount of cleaning gas, it is possible to obtain product CO with a high enough purity that it can be used for organic synthesis as it is. It also has the feature that the amount of CO adsorbed in the adsorption step and the amount of CO released in the degassing step are large.

Therefore, the present invention allows highly purified CO to be separated and recovered from converter gas and other CO-containing gases on an industrial scale, and is of great significance in the chemical industry.

[Brief explanation of drawings]

FIG. 1 is a flow sheet showing an example of a CO separation and recovery device. (1) ... adsorption tower, (2a), (2b), C
20), (2d)... Valve, (3)... Vacuum pump, (4)... Product tank, (a)... Raw material gas, (b)... Product CO gas, ( C)...Purge gas

Claims (1)

[Claims] 1. Pore volume with pore diameter of 10 Å or less is 0.33 ml/g
Below, the pore volume with a pore diameter of 20 Å to 300 Å is 0.3
has a pore distribution of 5 ml/g or more and 1300 m
An adsorbent for CO separation and recovery, which is made by supporting a copper compound on a carrier made of activated carbon having a specific surface area of ^2/g or more. 2. Activated carbon has a pore diameter of 10 Å or less and a pore volume of 0.2
0 ml/g or less, the pore volume of the pore diameter is 20 Å to 300 Å is 0.40 ml/g or more, and the activated carbon has a specific surface area of 1300 m^2/g or more. The adsorbent according to scope 1. 3. The adsorbent according to claim 1, wherein the copper compound is a copper (I) compound. 4. The adsorbent according to claim 1, wherein the copper compound is a copper (II) compound or a reduced product thereof. 5. Pore volume with pore diameter of 10 Å or less is 0.33 ml/g
Below, the pore volume with a pore diameter of 20 Å to 300 Å is 0.3
has a pore distribution of 5 ml/g or more and 1300 m
C, characterized in that a solution or dispersion of a copper compound dissolved or dispersed in a solvent is brought into contact with a carrier made of activated carbon having a specific surface area of ^2/g or more, and then the solvent is removed.
A method for producing an adsorbent for O separation and recovery. 6. A patent characterized in that a solution or dispersion in which a copper compound is dissolved or dispersed in a solvent is brought into contact with a carrier, the solvent is removed, and further heat treatment is performed in an atmosphere of air, an inert gas, or a reducing gas. The manufacturing method according to claim 5. 7. When separating and recovering high-purity CO from a mixed gas containing CO by pressure fluctuation type adsorption separation method and/or temperature fluctuation type adsorption separation method, as an adsorbent, pore volume of 0.33 ml with pore diameter of 10 Å or less is used. /g or less, pore diameter 20
CO separation and recovery in which a copper compound is supported on a carrier made of activated carbon, which has a pore distribution of 0.35 ml/g or more with a pore volume of Å to 300 Å and a specific surface area of 1300 m^2/g or more. A method for separating and recovering high-purity CO, characterized by using a commercially available adsorbent.