KR20220085021A - A method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide and carbon disulfide produced therefrom, and a separation device comprising the granular adsorbent - Google Patents

Abstract

The present invention relates to a method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide or carbon disulfide prepared thereby, and a separation device comprising the granular adsorbent, and more particularly, to an initial wet process By simultaneously performing the impregnation method and the ultrasonic treatment process, and adjusting the content of the impregnation solution and the average particle size of the adsorbent to an optimized range, the granular adsorbent is manufactured, so that the metal ions are evenly and uniformly impregnated in the adsorbent to significantly improve the adsorption capacity of carbon monoxide and carbon disulfide. can be improved In addition, it does not use a solvent such as a strong acid or a strong base, so the physical property stability is very good, problems such as pressure drop or line contamination do not occur, and the manufacturing process is simple.

Description

A method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide or carbon disulfide prepared thereby, and a separation device comprising the granular adsorbent {A method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide and carbon disulfide produced therefrom, and a separation device comprising the granular adsorbent}

The present invention relates to a method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide or carbon disulfide prepared thereby, and a separation device comprising the granular adsorbent.

LDG (Linz-Donawiz Converter Gas), FOG (Finex Off Gas) and BFG (Blast Furnace Gas), which are by-product gases generated in the steel industry, contain a large amount of carbon monoxide of about 78%, 30%, and 25%, respectively. The annual amount of industrial by-product gas is 20.46 million tons of CO, but it is mainly used for low value-added power generation due to the lack of economical separation technology.

As the sources of carbon monoxide are diversified, research has been conducted on the recovery of carbon monoxide, which can be converted into acetic acid, methanol, formic acid, etc., with high added value. Currently, absorption methods, deep cooling methods, and adsorption methods are being studied as technologies for recovering carbon monoxide. In the case of the absorption process, an organic-inorganic composite is used as an absorbent, but there are problems such as stability problems with respect to moisture and hydrogen sulfide of the absorbent and high energy cost. The deep cooling method also has a large process size, but it is not easy to operate, and the purity compared to the daily recovery rate of absorption and adsorption methods is lowered, and energy cost and plant cost due to low temperature distillation are high. Since the adsorption method uses an adsorbent with high selectivity to carbon monoxide and separation and recovery are performed through a pressure difference, there is an advantage in the recovery of carbon monoxide in terms of energy and cost compared to the above two processes.

Since the by-product gas of the steel industry mainly consists of carbon dioxide, carbon monoxide, and trace amounts of other gases, an adsorbent having a high adsorption amount of carbon monoxide and a high selectivity of carbon monoxide to carbon dioxide is used to recover carbon monoxide from the by-product gas through the adsorption method. In general, research on supporting monovalent copper on zeolite or activated carbon-based adsorbents has been mainly conducted [Non-Patent Document 1]. Research on supporting monovalent copper on boehmite has been actively conducted recently, and these studies also focus on improving the adsorption amount of carbon monoxide and the selectivity of carbon monoxide to carbon dioxide.

As a method of supporting a monovalent copper compound on an adsorbent, a wet impregnation method and a solid-state heat treatment method are mainly known. In the wet loading method, a monovalent or divalent copper compound is dissolved in a solvent and then stirred and mixed with an adsorbent. When a monovalent copper compound is used, it is not soluble in an aqueous solution. However, if a strong basic solvent is used and a divalent copper compound is used, it dissolves well in an aqueous solution, but a reduction process with hydrogen or carbon monoxide is required. In the case of the solid-state heat treatment method, copper is dispersed through heat treatment at a high temperature after physically mixing a monovalent copper compound and an adsorbent.

In particular, all of these methods are difficult to apply to granular adsorbents. In the case of wet loading, the inherent physical properties of the adsorbent may change depending on the solvent used. There are easy downsides. In addition, in the case of the solid-state heat treatment method, it is difficult to apply the granular adsorbent because it is physically mixed using a ball mill grinder. In addition, copper-supported adsorbents mainly support copper through a solid-state heat treatment method, and since most of them are in powder form, an additional process of molding the developed powder adsorbent is required for application to the process.

On the other hand, carbon disulfide is contained in crude oil in various concentrations from below 1 ppm to 300 ppm depending on the production area. Carbon disulfide is a chemical species that must be removed up to 1 to 2 ppm or less because it contaminates a hydrogen-generating catalyst in a petrochemical process and causes corrosion by being converted to hydrogen sulfide.

In petrochemical processes, acid contaminants and hydrogen sulfide are removed by a caustic wash, but carbon disulfide is not effectively removed in this process. Therefore, an additional process is required to remove carbon disulfide. There are three main types of carbon disulfide removal methods: hydrotreater, fractional distillation, and adsorption method. In the case of a hydrotreater, it has the advantage of being able to remove other contaminants as well, but if you do not use the facility you already have, the installation cost is high and there is a difficulty in securing sufficient hydrogen gas. Fractional distillation is inexpensive to install, but has disadvantages in that a significant amount of products can be thrown away together, and operating costs are high. In the case of the adsorption method, the installation cost is intermediate between the above two processes, the energy required for regeneration is the lowest, and it has the advantage of being suitable for producing a very small amount of carbon disulfide level product.

Currently, zeolites 13X, 4A, and 5A are commercialized for the purpose of removing sulfur compounds, but carbon disulfide is not removed due to its low adsorption power compared to other hydrocarbons. An adsorbent with high selectivity is required to remove carbon disulfide, and special adsorbents such as zeolite in which metal ions are exchanged for Ba are used abroad, but low adsorption capacity still remains a problem to be solved.

Xue, C., Hao, W., Cheng, W., Ma, J., & Li, R. (2019). CO Adsorption Performance of CuCl/Activated Carbon by Simultaneous Reduction—Dispersion of Mixed Cu(II) Salts. Materials, 12(10), 1605.

In order to solve the above problems, an object of the present invention is to provide a method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide, in which the carbon monoxide adsorption capacity is significantly improved by performing the initial wet impregnation method and the ultrasonic treatment process at the same time.

Another object of the present invention is to provide a granular adsorbent for separating carbon monoxide or carbon disulfide, which does not use a solvent such as a strong acid or a strong base and has excellent physical stability.

Another object of the present invention is to provide a separation device comprising the granular adsorbent.

The present invention comprises the steps of preparing an impregnation solution containing a metal precursor and a solvent; preparing a mixed solution by mixing the impregnating solution and the granular adsorbent; preparing a granular adsorbent in which the metal precursor is partially or entirely impregnated inside or on the surface of the granular adsorbent by sonicating the mixed solution simultaneously with the initial wet impregnation method; drying the granular adsorbent impregnated with the metal precursor; and heat-treating the dried granular adsorbent under an inert gas to prepare a granular adsorbent in which the metal precursor is reduced to metal ions.

In addition, the present invention is a granular adsorbent; And it provides a granular adsorbent for carbon monoxide or carbon disulfide separation comprising a; and metal ions impregnated in part or entirely in the interior or surface of the granular adsorbent.

The present invention also provides a separation device comprising the granular adsorbent.

The granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention performs an initial wet impregnation method and an ultrasonic treatment process at the same time, and adjusts the content of the impregnation solution and the average particle diameter of the adsorbent to an optimized range to prepare a granular adsorbent. The metal ions are evenly and uniformly impregnated in the inside, so that the adsorption capacity of carbon monoxide in the by-product gas and carbon disulfide in the liquid sulfur compound can be significantly improved.

In addition, the granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention does not use a solvent such as a strong acid or strong base, so it has very excellent physical stability, does not cause problems such as pressure drop or line contamination, and has a simple manufacturing process There is this.

The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.

1 schematically shows a configuration diagram of an apparatus for manufacturing a particulate adsorbent for separating carbon monoxide or carbon disulfide according to the present invention.
2 shows the results of analysis of the amount of CO adsorption according to the adsorption equilibrium pressure for the particulate adsorbents prepared in Examples 1 and 2 and Comparative Examples 1 to 3 according to the present invention.
3 shows the results of analysis of the amount of CO adsorption according to the adsorption equilibrium pressure for the particulate adsorbents prepared in Examples 1, 3 to 6 and Comparative Example 4 according to the present invention.
4 is a graph showing the results of analysis of breakthrough ability over time after flowing a mixed gas using the adsorption tower filled with the particulate adsorbent prepared in Example 5 and the commercial granular adsorbent of Comparative Example 4 according to the present invention.

Hereinafter, the present invention will be described in more detail by way of one embodiment.

The present invention relates to a method for manufacturing a granular adsorbent for separating carbon monoxide or carbon disulfide, a granular adsorbent for separating carbon monoxide or carbon disulfide prepared thereby, and a separation device comprising the granular adsorbent.

As described above, conventionally, as a method of supporting a monovalent copper compound on an adsorbent, it was prepared using a wet supporting method or a solid-state heat treatment method. However, these methods are difficult to apply to granular adsorbents, and the intrinsic properties of the adsorbent may be changed or destroyed depending on solvents such as strong acids or strong bases.

Therefore, in the present invention, the initial wet impregnation method and the ultrasonic treatment process are essentially simultaneously performed, and the content of the impregnation solution and the average particle size of the adsorbent are adjusted to an optimized range to prepare a granular adsorbent for carbon monoxide or carbon disulfide separation. Ions are evenly and uniformly impregnated to significantly improve the adsorption capacity of carbon monoxide in by-product gas or carbon disulfide in liquid sulfur compounds. In addition, it does not use a solvent such as a strong acid or a strong base, so the physical property stability is very good, problems such as pressure drop or line contamination do not occur, and the manufacturing process is simple.

Specifically, the present invention comprises the steps of preparing an impregnation solution containing a metal precursor and a solvent (S1); preparing a mixed solution by mixing the impregnation solution and the granular adsorbent (S2); preparing a granular adsorbent in which the metal precursor is partially or entirely impregnated inside or on the surface of the granular adsorbent by ultrasonically treating the mixed solution at the same time as the initial wet impregnation method (S3); drying the granular adsorbent impregnated with the metal precursor (S5); and heat-treating the dried granular adsorbent under an inert gas to prepare a granular adsorbent in which the metal precursor is reduced to metal ions (S6); providing a method for producing a granular adsorbent for carbon monoxide or carbon disulfide separation comprising a; do.

Hereinafter, each step will be described in detail.

(S1) preparing a mixed solution

The step (S1) may be a step of preparing an impregnation solution containing a metal precursor and a solvent. In step (S1), the metal precursor may be a precursor including at least one metal selected from the group consisting of copper, nickel, chromium, molybdenum, palladium, rubidium, and barium. Preferably, it may be a precursor comprising copper, nickel, or a mixture thereof, and most preferably a copper precursor.

In particular, the copper precursor may be impregnated with the granular adsorbent to be converted into copper ions through heat treatment, and the changed copper ions may have excellent adsorption capacity with carbon monoxide, thereby remarkably improving carbon monoxide selectivity. In general, copper monovalent ions with excellent adsorption performance are used in conventional adsorbents for carbon monoxide separation. However, CuCl precursor containing copper monovalent ions is not soluble in water and only dissolves in strong acid (HCl). Since it is manufactured, the manufacturing method thereof is limited, and there is a problem of poor stability due to strong acid. In addition, since the copper precursor is not sufficiently impregnated in the adsorbent, there is a disadvantage in that the manufacturing cost is high by using an excessive amount of the copper precursor.

However, in the present invention, the copper precursor including copper divalent ions is uniformly impregnated inside or on the surface of the granular adsorbent by simultaneously treating the incipient wet impregnation and the ultrasonic treatment process, and then undergoes a reduction process using heat treatment to reduce copper A divalent ion can be reduced to a copper monovalent ion.

Accordingly, the copper precursor is a copper precursor containing copper divalent ions instead of copper monovalent ions in order to improve the limitations of the existing copper monovalent ions, CuCl ₂ , Cu(HCOO) ₂ and Cu(NO ₃ ) ₂ At least one selected from the group consisting of may be used, and preferably a mixture of CuCl ₂ and Cu(HCOO) ₂ may be used. In particular, when a mixture of CuCl ₂ and Cu(HCOO) ₂ is used as the copper precursor, a reduction reaction occurs in the mixed solution compared to when CuCl ₂ or Cu(HCOO) ₂ is used alone, respectively, and monovalent copper ions are mixed It is recommended to use a mixture of CuCl ₂ and Cu(HCOO) ₂ as it can be formed in solution.

The solvent may be at least one selected from the group consisting of water, toluene, ethyl acetate and acetonitrile, preferably water, toluene, or a mixture thereof, and most preferably water.

(S2) preparing a mixed solution

The step (S2) may be a step of preparing a mixed solution by mixing the impregnation solution and the granular adsorbent.

The granular adsorbent has an average particle diameter larger than that of a conventional micro-sized powder adsorbent, can significantly improve the pressure drop that occurs when the adsorbent is used in a packed tower, and is easy to regenerate after using the adsorbent. In addition, it has a large pore surface area and has a small pore size, so it has an advantage of excellent adsorption ability to adsorb small molecular weight such as carbon monoxide instead of impurities having high molecular weight.

That is, the granular adsorbent has a high adsorption capacity for carbon monoxide and has excellent stability so that problems such as pressure drop or line contamination do not occur even when directly applied to the process.

The granular adsorbent may be at least one selected from the group consisting of activated carbon, activated alumina, activated zeolite, activated clay, activated bentonite, activated diatomaceous earth, and activated silica. Preferably, it may be at least one selected from the group consisting of activated carbon, activated alumina and activated zeolite, more preferably activated carbon, activated alumina, or a mixture thereof, and most preferably activated carbon.

The granular adsorbent may have an average particle diameter of 250 to 5000 μm, preferably 300 to 2000 μm, more preferably 400 to 1000 μm, and most preferably 450 to 800 μm. Also, the pore size may be 0.1 to 50 nm, preferably 0.2 to 40 nm, more preferably 0.3 to 10 nm, and most preferably 0.5 to 3 nm. At this time, if the average particle diameter of the adsorbent is less than 250 μm or the pore size is less than 0.1 nm, the particle size is too small to agglomerate the adsorbents and dispersibility may be poor. If it exceeds nm, the adsorption capacity may be reduced due to deterioration of the development of micropores.

In the step (S2), the impregnation solution may be mixed with 0.5 to 1.5 ml, preferably 0.75 to 1.25 ml, and most preferably 0.9 to 1.1 ml per unit mass of the granular adsorbent. When the content of the impregnation solution is less than 0.5 ml, all of the impregnation solution is evaporated before the metal precursor in the impregnation solution is evenly distributed in the granular adsorbent, so that the bulk metal precursor may be non-uniformly impregnated. Conversely, if it exceeds 1.5 ml, the metal precursor in the impregnation solution may be excessively impregnated into the granular adsorbent, and the average particle size of the adsorbent may become excessively large.

(S3) preparing a granular adsorbent impregnated with a metal precursor

In the step (S3), the metal precursor is partially or entirely impregnated inside or on the surface of the granular adsorbent by sonicating the mixed solution into the adsorbent at the same time as incipient wet impregnation to prepare a granular adsorbent It may be a step to

In the conventional wet loading method, the adsorbent may be destroyed by the magnetic bar used for mixing before the metal precursor in the impregnation solution is all impregnated into the granular adsorbent, and the metal precursor is diffused into the small pores of the adsorbent. There is a problem that the impregnation rate is slow because it takes a very long time. In particular, the conventional wet loading method used an excess amount of solvent compared to the amount of the adsorbent used. When an excess amount of the solvent is used, the concentration of the metal precursor may decrease, and the decrease in the concentration is the rate at which the metal precursor is delivered into the adsorbent. There was a limit to the improvement of the impregnation amount and impregnation rate of the metal precursor.

In the present invention, the amount of impregnation and the impregnation rate of the metal precursor can be remarkably improved by performing the initial wet impregnation method and the ultrasonic treatment at the same time. In particular, when the initial wet impregnation method is applied, the concentration of the metal precursor can be increased by using a small amount of solvent to increase the mass transfer rate of the metal precursor inside the pores of the adsorbent, and the impregnation is performed until the solvent is all vaporized. As this progresses, the amount of metal precursor impregnated in the adsorbent can be precisely controlled.

In addition, the ultrasonic treatment can improve the dispersibility of the metal precursor by inducing the metal precursor to be quickly and evenly impregnated in part or all of the inside or the surface of the granular adsorbent, and bulk (bulk) due to excessive impregnation of the metal precursor This may be done to prevent one metal precursor from being impregnated into the granular adsorbent. Preferably, the metal precursor may be uniformly impregnated into the entire inside of the granular adsorbent through the ultrasonic treatment.

In the step (S3), the initial wet impregnation method and the ultrasonic treatment are simultaneously performed at a temperature of 10 to 100 °C, preferably 30 to 90 °C, more preferably 40 to 80 °C, and most preferably 55 to 75 °C. It can be carried out until the solvent in the mixed solution is completely vaporized and only the granular adsorbent impregnated with the metal precursor remains. In this case, if the reaction time is less than 10° C., the material transfer rate of the metal precursor to the granular adsorbent is slow, so that sufficient impregnation may not be achieved, and the dispersibility of the metal precursor may be remarkably reduced. Conversely, if it exceeds 100 °C, the solvent may be completely vaporized before reaching the micropores in the process of reaching the micropores present in the granular adsorbent through the solvent, and the dispersibility of the metal precursor is significantly reduced can be

(S5) drying the granular adsorbent impregnated with the metal precursor

In the step (S5), a step of drying the granular adsorbent impregnated with the metal precursor may be performed in order to completely remove a solvent that may be partially present in the pores of the adsorbent before the heat treatment. The drying in step (S5) may be performed at a temperature of 100 to 250 °C for 1 to 24 hours. Preferably it can be carried out at a temperature of 110 to 200 ℃ 3 to 18 hours, most preferably at a temperature of 120 to 150 ℃ 6 to 12 hours.

(S6) step of preparing a granular adsorbent

The step (S6) may be a step of heat-treating the dried granular adsorbent under an inert gas to prepare a granular adsorbent in which the metal precursor is reduced to metal ions. The heat treatment in step (S6) may be performed at 200 to 600° C. under an inert gas for 1 to 12 hours. Preferably, it can be carried out at a temperature of 300 to 500 °C for 7 to 10 hours, and most preferably at a temperature of 350 to 450 °C for 7.5 to 8.5 hours. In particular, if the heat treatment temperature is less than 200 °C or the time is less than 6 hours, the metal precursor is not completely reduced to metal ions and remains as an unreacted metal precursor in the adsorbent, thereby reducing carbon monoxide adsorption capacity. Conversely, if the heat treatment temperature exceeds 600° C. or the time exceeds 12 hours, the active site inside the granular adsorbent may be removed to reduce adsorption capacity.

The inert gas may be at least one selected from the group consisting of nitrogen, argon, helium, krypton and xenon, preferably nitrogen, argon, or a mixture thereof, and most preferably nitrogen.

The metal ion may be at least one selected from the group consisting of a copper ion, a nickel ion, a chromium ion, a molybdenum ion, a palladium ion, a rubidium ion, and a barium ion. Preferably, it may be a copper ion, a nickel ion, or a mixture thereof, Most preferably, it may be a copper ion.

The metal ion may be impregnated with 3.5 to 4.5 mmol, preferably 3.8 to 4.3 mmol, more preferably 3.9 to 4.1 mmol, and most preferably 4 mmol per unit mass of the granular adsorbent. The unit of the unit mass of the granular adsorbent may be g. At this time, if the impregnation amount of the metal ion is less than 3.5 mmol, the carbon monoxide adsorption capacity may be remarkably reduced. On the contrary, if it exceeds 4.5 mmol, the metal precursor exists in a bulk state and the dispersibility is lowered, and the adsorption effective site is reduced and the adsorption capacity is reduced. this may be lowered.

In particular, although not explicitly described in the following Examples or Comparative Examples, in the method for producing the granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention, the granular adsorbent has an average particle diameter of 450 to 800 μm, When the pore size was 0.5 to 3 nm, a granular adsorbent was prepared by varying the content of the following impregnation solution and the amount of metal ion impregnation. The respective adsorption and separation performances of carbon monoxide and carbon disulfide were analyzed for 150 hours after mixing the prepared granular adsorbent with by-product gas and liquid sulfur compound, respectively.

As a result, unlike in other conditions and in other numerical ranges, when all of the following conditions were satisfied, the carbon monoxide selectivity in the by-product gas and the carbon disulfide selectivity in the liquid sulfur compound showed high values, respectively, and even compared to the existing carbon monoxide adsorbent. Significantly improved bonding and separation performance was exhibited. In addition, it was confirmed that, after carrying out the adsorption test for 150 hours, the metal ions in the granular adsorbent were not separated and maintained in a uniformly dispersed form.

① the granular adsorbent has an average particle diameter of 450 to 800 μm and a pore size of 0.5 to 3 nm, ② the impregnation solution is mixed with 0.75 to 1.25 ml per unit mass of the granular adsorbent, and ③ the metal ions are the It may be impregnated in an amount of 3.8 to 4.3 mmol per unit mass of the granular adsorbent.

However, when any one of the three conditions was not satisfied, the carbon monoxide and carbon disulfide selectivity of the granular adsorbent was low, respectively, and as a result of analyzing the granular adsorbent whose reaction was completed after 150 hours, the granular adsorbent It was confirmed that the adsorption and separation performance for carbon monoxide and carbon disulfide was deteriorated due to the loss of some of the metal ions in the interior.

In particular, although not explicitly described in the following Examples or Comparative Examples, in the method for producing the granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention, the granular adsorbent prepared under different conditions is prepared Using this, the adsorption and separation performance of carbon monoxide was analyzed at 1 to 10 atm for 300 hours.

As a result, unlike other conditions and other numerical ranges, when all of the following conditions were satisfied, the amount of carbon monoxide adsorption and desorption per unit g of adsorbent maintained remarkably high levels of 2.8 g and 2.7 g, respectively, for a long time, and a high purity of 99.96% or more It was confirmed that only carbon monoxide with

① the metal precursor is a copper precursor, the copper precursor is a mixture of CuCl ₂ and Cu(HCOO) ₂ , ② the solvent is water, ③ the granular adsorbent is activated carbon, and ④ the granular adsorbent has an average particle size. 450 to 800 μm, a pore size of 0.5 to 3 nm, ⑤ mixing 0.9 to 1.1 ml of the impregnating solution per unit mass of the granular adsorbent, ⑥ preparing a granular adsorbent impregnated with the metal precursor The initial wet impregnation method and ultrasonic treatment are carried out at the same time until the solvent in the mixed solution is completely vaporized at a temperature of 55 to 75 ° C, leaving only the granular adsorbent impregnated with the metal precursor, ⑦ The drying is carried out from 120 to It is carried out at a temperature of 150 ° C. for 6 to 12 hours, ⑧ the heat treatment is performed at 350 to 450 ° C. for 7.5 to 8.5 hours, and ⑨ the metal ions are impregnated at 3.8 to 4.3 mmol per unit mass of the granular adsorbent. can

However, when any one of the above 9 conditions was not satisfied, the amount of carbon monoxide adsorption and desorption per unit g of the adsorbent was very low at 1 g and 0.8 g, respectively, and could not be maintained for a long time, and the purity of carbon monoxide was as low as 87.4%. was confirmed to be recovered.

1 schematically shows a configuration diagram of an apparatus for manufacturing a particulate adsorbent according to the present invention. Referring to FIG. 1 , the reactor 120 for the initial wet impregnation method and the ultra sonicator 110 for ultrasonic treatment are located at the same time, and the granular adsorbent 122 and the impregnation solution 121 are located inside the reactor 120 . ) is present, and water 111 for ultrasonic treatment is located outside the reactor 120 .

When the initial wet impregnation and the ultrasonic treatment are simultaneously performed inside the reactor 120 of FIG. 1, the granular adsorbent 122 is completely immersed in the impregnation solution 121, and then the initial wet impregnation and the ultrasonic treatment are performed at the same time. As shown in FIG. 1, the solvent in the impregnation solution starts to slowly evaporate, and the solvent is completely evaporated until only the adsorbent remains as shown in FIG. 1 .

On the other hand, the present invention is a granular adsorbent; And it provides a granular adsorbent for carbon monoxide or carbon disulfide separation comprising a; and metal ions impregnated in part or entirely in the interior or surface of the granular adsorbent.

The granular adsorbent may be at least one selected from the group consisting of activated carbon, activated alumina, activated zeolite, activated clay, activated bentonite, activated diatomaceous earth, and activated silica. Preferably, it may be at least one selected from the group consisting of activated carbon, activated alumina and activated zeolite, more preferably activated carbon, activated alumina, or a mixture thereof, and most preferably activated carbon.

The metal ion may be at least one selected from the group consisting of a copper ion, a nickel ion, a chromium ion, a molybdenum ion, a palladium ion, a rubidium ion, and a barium ion. Preferably, it may be a copper ion, a nickel ion, or a mixture thereof, Most preferably, it may be a copper ion.

The metal ion may be impregnated in an amount of 3.5 to 4.5 mmol per unit mass of the granular adsorbent.

In particular, although not explicitly described in the following Examples or Comparative Examples, in the granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention, the average particle diameter of the granular adsorbent is 450 to 800 μm, and the pore size is In the case of 0.5 to 3 nm, when the metal ions are impregnated at 3.5 to 4.5 mmol per unit mass of the granular adsorbent, all of these conditions are not satisfied, whereas when the granular adsorbent is filled in the tower, no pressure drop occurs. It was confirmed that line contamination due to dust did not occur.

However, when any one of the respective ranges of the average particle diameter and pore size of the granular adsorbent and the impregnation condition of the metal ions was not satisfied, the pressure drop was excessively generated, and the line was contaminated due to heavy dust.

In particular, although not explicitly described in the following Examples or Comparative Examples, in the granular adsorbent for carbon monoxide or carbon disulfide separation according to the present invention, the average particle diameter of the granular adsorbent is 450 to 800 μm, and the pore size is In the case of 0.5 to 3 nm, the metal ion is a copper ion, the metal ion is entirely impregnated inside the granular adsorbent, and all of these conditions are met when impregnated at 3.8 to 4.3 mmol per unit mass of the granular adsorbent. Unlike the unsatisfactory, the carbon monoxide adsorption performance and the carbon disulfide adsorption performance were significantly improved at the same time.

However, when any one of the respective ranges of the average particle diameter and pore size of the granular adsorbent and the type and impregnation condition of the metal ion is not satisfied, either the carbon monoxide adsorption performance or the carbon disulfide adsorption performance shows low performance. At the same time, an improved effect could not be expected.

The granular adsorbent may have an average particle diameter of 250 to 5000 μm, preferably 300 to 2000 μm, more preferably 400 to 1000 μm, and most preferably 450 to 800 μm. Also, the pore size may be 0.1 to 50 nm, preferably 0.2 to 40 nm, more preferably 0.3 to 10 nm, and most preferably 0.5 to 3 nm.

Most preferably, the metal ion is a copper ion, and the metal ion is entirely impregnated inside the granular adsorbent, and may be impregnated in an amount of 3.8 to 4.3 mmol per unit mass of the granular adsorbent.

The granular adsorbent may have a carbon monoxide adsorption amount of 28 to 53 ml/g _adsorbent , preferably 29.683 to 51.413 ml/g _adsorbent , at a temperature of 25° C. and a pressure of 101.325 kPa.

In addition, the present invention provides a separation device comprising the granular adsorbent.

The separation device may be a gas or liquid separation device, preferably a carbon monoxide and carbon disulfide separation device.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited by the following examples.

Examples 1 to 6 and Comparative Examples 1 to 4

As the granular adsorbent, activated carbon from Company A having an average particle diameter of 750 μm and a pore size of 2 nm and activated carbon from Company B having an average particle diameter of 800 μm and a pore size of 2.5 nm were used, respectively. As the copper precursor, a mixture of CuCl ₂ and Cu(HCOO) ₂ in a 1:1 weight ratio was used. First, a copper precursor impregnation solution was prepared by mixing a mixture of CuCl ₂ and Cu(HCOO) ₂ in water. Then, at the mixing ratio as shown in Table 1 below, activated carbon, which is a granular adsorbent, was added enough to be immersed in the impregnation solution, and then stirred to prepare a mixed solution. Then, the mixed solution was sonicated at 60° C. for 1 hour with a sonicator at the same time as the initial wet impregnation. At this time, the copper precursor impregnation solution was added only enough to submerge the granular adsorbent, activated carbon, and after the initial wet impregnation and ultrasonic treatment started, the solvent in the mixed solution started to evaporate, so that water was completely evaporated and only the granular adsorbent to which the copper precursor was adsorbed carried out until the remainder. The granular adsorbent to which the copper precursor is adsorbed is dried at 120 ° C. for 7 hours and then heat treated at 400 ° C. for 8 hours while flowing nitrogen to reduce the copper precursor to copper ions. Alternatively, a granular adsorbent for separating carbon disulfide was prepared.

Experimental Example 1: Analysis of the amount of carbon monoxide adsorption according to the impregnation method

The carbon monoxide adsorption amount according to the impregnation method was analyzed for the particulate adsorbents prepared in Examples 1 and 2 and Comparative Examples 1 to 3, and the results are shown in Table 2 and FIG. 2 .

2 shows the results of analysis of the amount of CO adsorption according to the adsorption equilibrium pressure for the particulate adsorbents prepared in Examples 1 and 2 and Comparative Examples 1 to 3;

2 and Table 2, in the case of Examples 1 and 2, copper ions are uniformly impregnated inside the granular adsorbent, so that the CO adsorption amount for the adsorption equilibrium pressure is at least 1.8 compared to Comparative Examples 1 to 3 It was confirmed that it showed a significantly excellent value from a fold to a maximum of 2.6 times.

On the other hand, in Comparative Examples 1 to 3, since only the wet impregnation method or the initial wet impregnation method was carried out alone, copper ions were mostly not impregnated inside the granular adsorbent even after a long period of impregnation, resulting in a very low CO adsorption amount.

Experimental Example 2: Analysis of the amount of carbon monoxide adsorption according to the content of the impregnation solution and the type of adsorbent

For the particulate adsorbents prepared in Examples 1 to 5, the amount of carbon monoxide adsorbed according to the content of the impregnation solution and the type of adsorbent was analyzed, and the results are shown in FIG. 3 .

3 shows the results of analysis of the amount of CO adsorption according to the adsorption equilibrium pressure for the particulate adsorbents prepared in Examples 1, 3 to 6 and Comparative Example 4. According to the results of FIG. 3 , in the case of Examples 4 to 6, the average particle diameter of the granular adsorbent was 750 to 800 μm, and the pore size was 2 to 2.5 nm, compared to Examples 1, 3 and Comparative Example 4 In this case, it was confirmed that the CO adsorption amount was significantly improved when the copper content in the granular adsorbent contained 3.5 to 4.5 mmol Cu/1g AC. In particular, it was found that the copper content in the granular adsorbent was 4 mmol Cu/1g AC and the best CO adsorption amount was exhibited in Example 5. Through this, it was confirmed that the average particle size and pore size of the granular adsorbent were satisfied, and the amount of CO adsorption could be improved and optimized by controlling the copper content in the granular adsorbent.

Experimental Example 3: Analysis of the amount of carbon disulfide detected

The carbon disulfide content was analyzed by a conventional method using the granular adsorbent prepared in Example 5. As an experimental method, a mixed solution containing 200 ppm of a sulfur compound mainly containing carbon disulfide (36 wt% of normal paraffins, 61 wt% of total isoparaffins, 1.8 wt% of naphthenes, 0.7 wt% of aromatics and 0.5 wt% of olefins) 0.5 g of the granular adsorbent was added to 5 mL and left at 4 °C for 72 hours.

As a result, after removing the granular adsorbent from the mixed solution, the concentration of sulfur compounds in the solution was measured. As a result, it was confirmed that only carbon disulfide was detected at 5 ppm or less. Through this, when the granular adsorbent was used, carbon disulfide was selectively adsorbed to the granular adsorbent in a large amount in the liquid sulfur compound.

Through this, it was found that the granular adsorbent can selectively adsorb not only gaseous carbon monoxide but also liquid carbon disulfide, and separation and removal of these components are possible.

Experimental Example 4: Analysis of carbon monoxide breakthrough ability

For the granular adsorbent prepared in Example 5 and the commercial granular adsorbent not impregnated with copper of Comparative Example 4, the carbon monoxide breakthrough ability was analyzed for the mixed gas of Table 3 below containing carbon monoxide, and the results are shown in FIG. shown in

As an experimental method, the particle-type adsorbent prepared in Example 5 and the commercial particle-type adsorbent not impregnated with Cu of Comparative Example 4 were respectively filled in a 0.7 cm-diameter tower by 4.5 cm, followed by a flow rate of 30 ml/min. While flowing the gas according to the composition of Table 3 for 40 minutes, different carbon monoxide breakthrough capabilities were analyzed over time.

4 is a graph showing the results of analysis of breakthrough ability over time after flowing the mixed gas using the adsorption tower filled with the particulate adsorbent prepared in Example 5 and the commercial granular adsorbent of Comparative Example 4;

According to the results of FIG. 4, in Comparative Example 4, as a result of conducting a breakthrough experiment using a granular adsorbent not impregnated with Cu, it took 4.38 minutes for carbon monoxide to break through. On the other hand, in the case of Example 5, 19.53 minutes were consumed to break through carbon monoxide. Through this, it was found that the particulate adsorbent of Example 5 had a higher amount of CO adsorption compared to the commercial particulate adsorbent of Comparative Example 4. In addition, when the granular adsorbent of Example 5 was filled in the tower, no pressure drop occurred, and no line contamination by dust was observed.

On the other hand, when the breakthrough experiment was conducted using the commercial particle-type adsorbent of Comparative Example 4, the breakthrough times of carbon monoxide and carbon dioxide were similar, so that the two could not be separated. On the other hand, in the breakthrough experiment using the particulate adsorbent of Example 5, the breakthrough times of carbon monoxide and carbon dioxide were significantly different, so that the two could be easily separated.

Through this, the granular adsorbent showed a higher adsorption capacity for carbon monoxide compared to conventional commercial adsorbents, and it was possible to selectively adsorb carbon monoxide compared to carbon dioxide, and it was found that separation and removal of these components were possible.

100: Configuration diagram of a granular adsorbent manufacturing apparatus
110: ultra sonicator
111: water in the ultrasonicator
120: reactor
121: impregnating solution
122: granular adsorbent

Claims (20)

preparing an impregnation solution containing a metal precursor and a solvent;
preparing a mixed solution by mixing the impregnating solution and the granular adsorbent;
preparing a granular adsorbent in which the metal precursor is partially or entirely impregnated inside or on the surface of the granular adsorbent by sonicating the mixed solution simultaneously with the initial wet impregnation method;
drying the granular adsorbent impregnated with the metal precursor; and
heat-treating the dried granular adsorbent under an inert gas to prepare a granular adsorbent in which the metal precursor is reduced to metal ions;
A method for producing a granular adsorbent for carbon monoxide or carbon disulfide separation comprising a.
According to claim 1,
The metal precursor is a precursor comprising at least one metal selected from the group consisting of copper, nickel, chromium, molybdenum, palladium, rubidium and barium.
3. The method of claim 2,
The metal precursor is a copper precursor, and the copper precursor is at least one selected from the group consisting of CuCl ₂ , Cu(HCOO) ₂ and Cu(NO ₃ ) ₂ Method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide.
According to claim 1,
The method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the solvent is at least one selected from the group consisting of water, toluene, ethyl acetate and acetonitrile.
According to claim 1,
The granular adsorbent is at least one selected from the group consisting of activated carbon, activated alumina, activated zeolite, activated clay, activated bentonite, activated diatomaceous earth and activated silica.
According to claim 1,
The granular adsorbent has an average particle diameter of 250 to 5000 μm and a pore size of 0.1 to 50 nm.
According to claim 1,
In the step of preparing the mixed solution, the impregnating solution is 0.5 to 1.5 ml per unit mass of the granular adsorbent.
The method of claim 1,
In the step of preparing the granular adsorbent impregnated with the metal precursor, the initial wet impregnation method and ultrasonic treatment are simultaneously performed to completely vaporize the solvent in the mixed solution at a temperature of 10 to 100 ° C. A method for producing a granular adsorbent for carbon monoxide or carbon disulfide separation, which is carried out until only the remaining.
According to claim 1,
In the drying step, drying is performed at a temperature of 100 to 250° C. for 1 to 24 hours. A method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide.
According to claim 1,
In the step of preparing the granular adsorbent, the heat treatment is performed at 200 to 300° C. for 6 to 12 hours.
According to claim 1,
The method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the metal ion is impregnated in an amount of 3.5 to 4.5 mmol per unit mass of the granular adsorbent.
According to claim 1,
The granular adsorbent has an average particle diameter of 450 to 800 μm, and a pore size of 0.5 to 3 nm,
The impregnation solution is mixed with 0.75 to 1.25 ml per unit mass of the granular adsorbent,
The method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the metal ion is impregnated in an amount of 3.8 to 4.3 mmol per unit mass of the granular adsorbent.
According to claim 1,
the metal precursor is a copper precursor, the copper precursor is a mixture of CuCl ₂ and Cu(HCOO) ₂ ,
The solvent is water,
The granular adsorbent is activated carbon,
The granular adsorbent has an average particle diameter of 450 to 800 μm, and a pore size of 0.5 to 3 nm,
The impregnation solution is mixed with 0.9 to 1.1 ml per unit mass of the granular adsorbent,
In the step of preparing the granular adsorbent impregnated with the metal precursor, the initial wet impregnation method and the ultrasonic treatment are simultaneously performed to completely vaporize the solvent in the mixed solution at a temperature of 55 to 75 ° C. Continue until only the adsorbent remains,
The drying is performed at a temperature of 120 to 150 ° C. for 6 to 12 hours,
The heat treatment is performed at a temperature of 350 to 450 ° C. for 7.5 to 8.5 hours,
The method for producing a granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the metal ion is impregnated in an amount of 3.8 to 4.3 mmol per unit mass of the granular adsorbent.
granular adsorbent; and
A granular adsorbent for carbon monoxide or carbon disulfide separation comprising a; metal ions impregnated in part or entirely in the interior or surface of the granular adsorbent.
15. The method of claim 14,
The granular adsorbent is at least one selected from the group consisting of activated carbon, activated alumina, activated zeolite, activated clay, activated bentonite, activated diatomaceous earth and activated silica,
The metal ion is at least one selected from the group consisting of copper ions, nickel ions, chromium ions, molybdenum ions, palladium ions, rubidium ions and barium ions.
15. The method of claim 14,
The granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the metal ion is impregnated in an amount of 3.5 to 4.5 mmol per unit mass of the granular adsorbent.
17. The method of claim 16,
The granular adsorbent has an average particle diameter of 450 to 800 μm and a pore size of 0.5 to 3 nm. A granular adsorbent for separating carbon monoxide or carbon disulfide.
18. The method of claim 17,
The metal ion is a copper ion,
The metal ion is entirely impregnated inside the granular adsorbent, and the granular adsorbent for carbon monoxide or carbon disulfide separation is impregnated in an amount of 3.8 to 4.3 mmol per unit mass of the granular adsorbent.
15. The method of claim 14,
The granular adsorbent is a granular adsorbent for separating carbon monoxide or carbon disulfide, wherein the adsorption amount of carbon monoxide is 28 to 53 m/g of the _adsorbent at a temperature of 25° C. and a pressure of 101.325 kPa.
A separation device comprising the granular adsorbent of any one of claims 14 to 19.

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