A core-shell structured carbon monoxide adsorbent and its preparation method

Abstract

The present invention relates to a core-shell structured carbon monoxide adsorbent, which uses a microsphere with a high specific heat capacity and a non-porous structure as the core and a molecular sieve loaded with cuprous salt as the shell. The composite adsorbent comprises the following raw materials in parts by mass: 5-10 parts of microspheres with a high specific heat capacity and a non-porous structure, 70-90 parts of a molecular sieve loaded with cuprous salt, 5-10 parts of an adhesive, and 1-2 parts of a co-adhesive. The beneficial effects of the present invention are as follows: By using a microsphere with a high specific heat capacity and a non-porous structure as the inert core of the adsorbent, the specific heat capacity of the adsorbent can be increased, thereby controlling the adverse temperature gradient generated during adsorption and desorption. On the one hand, the dynamic adsorption capacity of the adsorbent is increased, and on the other hand, the mass transfer coefficient is improved, making the adsorbent of the present invention have excellent mass transfer performance, higher stability and physical strength, capable of operating stably under harsh environments such as high temperature and high pressure, and having a long service life.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon monoxide adsorbents, and particularly relates to a core-shell structured carbon monoxide adsorbent and a preparation method thereof. Background Art

[0002] In industrial production, the separation and purification of gases are very important processes. In particular, for the separation and purification of some toxic and harmful gases, more efficient and precise methods are required. Currently, the main methods for separating CO are: cryogenic separation, solution absorption, membrane separation, and adsorption separation. Among many methods for separating carbon monoxide from gas mixtures, pressure swing adsorption (PSA), based on the cyclic adsorption of a gas-solid system, is playing an increasingly important role in terms of low energy consumption and process economy. Pressure swing adsorption generally operates based on the differences in the adsorption capacities of each component gas in the mixed gas on the adsorbent during physical adsorption, as well as the variation of the adsorption amount with the adsorption pressure, and realizes adsorption and pressure-reducing desorption by controlling the pressure. Since the interaction force between the adsorbent and the adsorbate is weak, the adsorbents used in PSA have high adsorption capacity and separation selectivity for the target gas, which is very important for separation efficiency and energy conservation. Types of CO adsorbents include zeolite molecular sieves, activated carbon, metal-organic framework materials, π-complexing adsorbents, etc. In the 1970s and 1980s, researchers utilized the principle that transition metal ions such as Cu+ and Ag+ can undergo π-complexing interactions with CO, and loaded and dispersed the metal ions on porous materials with high specific surface areas such as zeolite molecular sieves and activated carbon to prepare special CO adsorbents. Such adsorbents are customarily referred to as π-complexing adsorbents. Since the complexing ability of Cu+ with CO is stronger than that of Ag+, Cu+-loaded adsorbents can obtain higher adsorption capacity and adsorption selectivity. π-Complexing belongs to the category of weak chemical bonds. Therefore, compared with traditional physical adsorption using van der Waals forces or electrostatic forces, the interaction force is stronger and there is higher adsorption selectivity; compared with general chemical adsorption, its weak chemical bond nature enables the desorption process to be easily achieved by reducing the pressure or raising the temperature. π-Complexing adsorption separation combines the strong chemical action of π-complexing with adsorption separation, and has characteristics such as high selectivity, low energy consumption, and low cost. Therefore, it has become an important frontier field for improving traditional separation technologies. The adsorbents applied to the pressure swing adsorption separation of CO process are mainly copper-loaded adsorbents. In the early 1980s, companies such as Nippon Steel (JP61017413A), BP Chemicals (CN85101183A), and Kansai Thermochemical (JP62113711A) all proposed adsorbents loaded with copper ions for the purpose of developing selective CO adsorbents. The core inventive point of this type of technology is to load cuprous ions on carriers such as zeolite / aluminum oxide / silicon oxide through ion exchange method, and utilize the complexing property of cuprous ions with CO to improve the selectivity of the adsorbent for CO. Peking University (CN86102838A) proposed a method for preparing copper-loaded adsorbents by solid-phase thermal dispersion based on the mechanism that salts can be naturally monolayer-dispersed on a high specific surface under heating conditions. The adsorbents prepared by this method have high CO adsorption capacity and selectivity.Nanjing Tech University (CN1185353A) proposed an efficient copper-loaded adsorbent for the removal of trace CO in nitrogen-containing gases. It uses powdered activated carbon as the carrier, and copper chloride and mixed rare earth chlorides are loaded onto it by the impregnation method. Finally, attapulgite is used as the binder to form a shape. The addition of rare earth chlorides improves the capacity and stability of the copper-loaded adsorbent.

[0003] The above copper-loaded carbon monoxide adsorbents are mostly prepared from materials such as metal oxides, activated carbon, and molecular sieves, and are mostly single homogeneous adsorbents. However, these materials are easily affected by external factors such as temperature and pressure during the adsorption process, thus affecting their adsorption performance and service life. Moreover, due to being single homogeneous adsorbents, their heat capacity is fixed and their thermal stability is poor. During use, the temperature changes significantly and the dynamic adsorption capacity is low. In addition, the mass transfer coefficient is low: as the molecules diffuse towards the center of the adsorbent, the longer the path, the greater the diffusion resistance will become. Therefore, a new type of adsorbent is needed, which has higher stability and physical strength, can work stably under harsh environments such as high temperature and high pressure, has a long service life, and has more excellent mass transfer performance. In the present invention, an inert core, such as a microporous structure microsphere, is introduced into the adsorbent to increase the specific heat capacity of the adsorbent. On the one hand, it increases the dynamic adsorption capacity of the adsorbent, and on the other hand, it improves the mass transfer coefficient, thereby improving the stability and efficiency of the adsorbent.

[0004] The inventor's previous patent CN202310752660.4 disclosed a composite adsorbent with a core-shell structure for pressure swing adsorption separation of carbon monoxide, which uses an effective component with an adsorption capacity for CO and an inert material with a large specific heat capacity but no adsorption capacity for CO as the core, and a molecular sieve loaded with cuprous salt as the shell. The presence of the inert core can control the adverse temperature gradient generated during adsorption and desorption, and reduce the temperature change during the adsorption and desorption process. However, in order to make the composite adsorbent have good stability and lifespan, the molecular sieve used as the shell needs to be subjected to Cu(II) exchange, and then the Cu(II)-exchanged molecular sieve and cuprous salt are compounded under the auxiliary heating conditions of 350 - 500 °C and 10 - 50 kPa to obtain a copper-based adsorbent precursor. The preparation method is complicated and the cost is high. Therefore, it is of great practical significance to develop an adsorbent that has both a high specific heat capacity and a dynamic adsorption capacity, and has a simple preparation process and low cost. Summary of the Invention

[0005] Traditional adsorbents are vulnerable to external factors under environments such as high temperature and high pressure, thus affecting the adsorption performance and service life. At the same time, the physical strength of the adsorbent itself is weak and it is easily affected by factors such as mechanical wear and leads to failure. Compared with the prior art, the main purpose of the present invention is to solve the technical problems that traditional adsorbents are vulnerable to external factors under high temperature and high pressure environments, resulting in decreased adsorption performance, low dynamic adsorption capacity, low mass transfer coefficient, short service life, etc. At the same time, it also solves the problem that the physical strength of the adsorbent itself is weak and is easily affected by mechanical wear. The present invention uses microspheres with high specific heat capacity and non-porous structure as the inert core to control the adverse temperature gradient generated during adsorption and desorption, and improve the dynamic adsorption capacity and stability of the adsorbent; uses molecular sieve loaded with cuprous salt as the shell, and adds adhesives to improve the physical strength of the adsorbent, thereby extending the service life of the adsorbent.

[0006] In order to achieve the object of the present invention, the present invention mainly adopts the following technical means:

[0007] 1. Using microspheres with high specific heat capacity and non-porous structure as the inert core of the adsorbent can increase the specific heat capacity of the adsorbent, thereby controlling the adverse temperature gradient generated during adsorption and desorption, and improving the dynamic adsorption capacity of the adsorbent.

[0008] 2. Using molecular sieve loaded with cuprous salt as the shell of the adsorbent, combining it with the non-porous microsphere core, enhancing the adsorption performance of the adsorbent, and improving the stability and efficiency of the adsorbent.

[0009] 3. Adding adhesives to combine the microsphere core and the copper-based adsorbent precursor, thereby improving the physical strength of the adsorbent and extending the service life of the adsorbent.

[0010] 4. Modifying the non-porous microspheres used as the core with an amino silane coupling agent to increase their affinity with the molecular sieve, which is beneficial to the long-term operation of the adsorbent and improves the service life of the adsorbent.

[0011] Specifically, the present invention provides the following technical solutions:

[0012] A core-shell structured carbon monoxide adsorbent uses microspheres with high specific heat capacity and non-porous structure as the core and molecular sieve loaded with cuprous salt as the shell. The composite adsorbent comprises the following raw materials in parts by mass: 5-10 parts of microspheres with high specific heat capacity and non-porous structure, 70-90 parts of molecular sieve loaded with cuprous salt, 5-10 parts of adhesives, and 1-2 parts of co-adhesives.

[0013] Further, the particle size of the non-porous structure microspheres is 1-10 mm, preferably 1-3 mm; the porosity < 10%, the density is 2-4 g / cm 3 , the mass specific heat capacity is 0.7-0.9 J / g·°C; or the volume specific heat capacity is 1.5-3.5 J / cm 3·°C. The non-porous structure microspheres are selected from at least one of aluminum oxide microspheres, magnesium oxide microspheres, glass microspheres, ceramic microspheres, silicon dioxide microspheres, and polystyrene microspheres.

[0014] Furthermore, the non-porous structure microspheres are modified with a silane coupling agent, and the silane coupling agent is an amino silane coupling agent, specifically selected from at least one of γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-diethenyltriaminepropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane.

[0015] The method for modifying the non-porous structure microspheres with a silane coupling agent includes the following steps: dispersing the non-porous structure microspheres in an alcohol aqueous solution, adding the silane coupling agent, stirring and heating at 50 - 60 °C for 1 - 2 h under ultrasonic conditions, washing, and drying to obtain the non-porous structure microspheres modified with the silane coupling agent. Further, the dosage of the silane coupling agent is 5 - 8 wt% of the mass of the non-porous structure microspheres, the ultrasonic conditions are 90 - 150 kHz and the power is 200 - 300 W. The alcohol aqueous solution is a mixed solution of ethanol and water, where the volume ratio of alcohol is 50 - 60%; the washing is with absolute ethanol.

[0016] The non-porous structure microspheres modified with a silane coupling agent have a better affinity with the molecular sieve loaded with cuprous salt, which is beneficial to the structural stability of the composite adsorbent and improves its service life.

[0017] Furthermore, the cuprous salt is at least one of CuCl, CuBr, and CuI; the molecular sieve loaded with cuprous salt is prepared by a preparation method including the following steps: after feeding X-type and / or Y-type molecular sieve and a salt of Cu(I) according to a mass ratio of 1:0.7 - 0.9, mixing and grinding to prepare the molecular sieve loaded with cuprous salt. The mixing and grinding method is high-energy ball milling, ultra-centrifugal grinding, or planetary ball milling. High-energy ball milling is preferably used, with 2 - 3 mm tungsten carbide balls, a ball-to-material ratio of 5 - 10:1, a ball milling time of 3 - 5 h, and a ball milling speed of 200 - 300 rpm. The cuprous salt and the molecular sieve can be well compounded together by high-energy ball milling.

[0018] Further, the binder is selected from at least one of clay and silicone resin. Preferably, the binder is natural clay with a particle size of 20 - 50 μm. Further, the clay is selected from at least one of kaolin, metakaolin, montmorillonite, sericite, bentonite, and sepiolite; the silicone resin is selected from polymethyl silicone resin and polyethyl silicone resin; preferably, it is methyl MQ type silicone resin, and more preferably, the M:Q ratio of methyl MQ type silicone resin is 0.5 - 0.7, and the weight average molecular weight is 5000 - 10000 g / mol. Preferably, the binder is a mixture of kaolin and methyl MQ type silicone resin in a mass ratio of 5 - 7:1. The inventors found that the core - shell structure composite adsorbent prepared with the above - compounded binder has a more stable core - shell structure, high strength, and does not affect the adsorption and separation of carbon monoxide, significantly improving the stability of the composite adsorbent.

[0019] Further, the adhesion aid is selected from at least one of polyvinyl alcohol, hydroxypropyl methylcellulose, phenolic resin, acrylic resin, dextran, sodium silicate, and gum arabic. Preferably, it is a compound of hydroxypropyl methylcellulose and sodium silicate in a mass ratio of 4 - 7:1. The adhesion aid and the clay binder are used in combination, which can significantly improve the strength and wear resistance of the composite adsorbent. The inventors also unexpectedly found that the above - compounded adhesion aid of hydroxypropyl methylcellulose and sodium silicate not only improves the strength of the core - shell structure of the composite adsorbent but also improves the dispersion uniformity of the shell coating, making the catalyst stability more excellent.

[0020] The most probable pore diameter of the carbon monoxide adsorbent of the present invention is 3.5 - 4 nm, such as 3.7 nm, 3.8 nm, 3.9 nm; the pore diameter of the adsorbent is relatively small, which is beneficial to the dispersion of the active components. The specific surface area (BET) of the core - shell adsorbent is 300 - 350 m 2 / g.

[0021] The present invention also provides a preparation method of the pressure swing adsorption separation carbon monoxide adsorbent with the core - shell structure, including the following steps: Mixing the microspheres with no - pore structure, the molecular sieve loaded with cuprous salt, the binder, and the adhesion aid in a rolling ball machine by mechanical rolling ball method to obtain a core - shell structure adsorbent precursor. The core - shell structure adsorbent precursor is first heat - treated in a protective atmosphere at 350 - 500 °C for 1 - 3 h, and then reduced in a reducing atmosphere at 150 - 220 °C for 5 - 10 h to obtain the pressure swing adsorption separation carbon monoxide adsorbent with the core - shell structure.

[0022] Further, the process parameters of the mechanical rolling ball method are a power of 200 - 300 W and a rotation speed of 90 - 130 rpm; the protective atmosphere is nitrogen and / or argon; the reducing atmosphere is in a CO and / or H2 atmosphere, such as water gas. According to the industrial site conditions, carbon monoxide or hydrogen or a mixture of the two can be used for reduction.

[0023] The excellent effects of the present invention are as follows:

[0024] The beneficial effects of the present invention are as follows: 1. After adding the inert core, the specific heat capacity of the adsorbent is increased, thereby reducing the temperature change during the adsorption and desorption processes and increasing the dynamic adsorption capacity of the adsorbent. 2. The binder binds more firmly, improving the physical strength of the adsorbent and thus extending the service life of the adsorbent. 3. Preparation is carried out using a copper-based adsorbent precursor, enabling the adsorbent to have better adsorption performance and stability. Compared with traditional carbon monoxide adsorbents, the adsorbent of the present invention has higher stability and physical strength, can operate stably under harsh environments such as high temperature and high pressure, and has a long service life. At the same time, due to the addition of the inert core and the preparation method using a copper-based adsorbent precursor, the temperature change of the adsorbent of the present invention during the adsorption and desorption processes is small, thereby improving the adsorption efficiency and controllability. 4. By modifying the non-porous microspheres with a silane coupling agent, the affinity between the core and the shell is enhanced, which is more conducive to the stable long-term operation of the adsorbent. Description of the Drawings

[0025] Figure 1 is the most probable pore size distribution diagram of the carbon monoxide adsorbent obtained in Example 1;

[0026] Figure 2 is the carbon monoxide breakthrough curve of the core-shell adsorbent in Example 1 and the adsorbent in Comparative Example 1 at 25 °C and an adsorption pressure of 7 kg. Detailed Embodiments

[0027] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be described in detail below. The following examples facilitate a better understanding of the present invention but do not limit the present invention. The experimental methods in the following examples are all conventional methods unless otherwise specified.

[0028] Example 1

[0029] (S1) Disperse 10 parts by mass of alumina microspheres (porosity 5%, density 2.3 g / cm3, particle size 2.5 mm) in 120 parts by mass of an ethanol aqueous solution (volume ratio of ethanol to water is 6:4), add 0.5 part by mass of coupling agent KH-540, stir and heat at 50 °C for 1 h under ultrasonic conditions (120 kHz, 300 W), filter, wash, and dry to obtain coupling agent-modified alumina microspheres.

[0030] (S2) Mix 10 parts by mass of NaY molecular sieve with 7 parts by mass of cuprous chloride, and perform high-energy ball milling (3 mm tungsten carbide balls, ball-to-material ratio 10:1, ball milling time 3 h, ball milling speed 200 rpm) to prepare a molecular sieve loaded with cuprous salt.

[0031] (S3) Add 10 parts by mass of the alumina microspheres obtained in step (S1), 5 parts by mass of kaolin, 1 part by mass of methyl MQ silicone resin (M:Q = 0.6, weight average molecular weight 8000 g / mol), 1.6 parts by mass of hydroxypropyl methylcellulose, and 0.4 parts by mass of sodium silicate to a ball mill using the mechanical ball rolling method, and add 80 parts by mass of the molecular sieve loaded with cuprous salt obtained in step (S2). The conditions of the ball mill are 250 W and a rotation speed of 100 rpm, and perform ball rolling coating to obtain a composite adsorbent precursor;

[0032] (S4) In nitrogen, heat the composite adsorbent precursor obtained in step (S3) at 400 °C for 2 hours;

[0033] (S5) Reduce the material obtained in step (S4) under a hydrogen atmosphere at 100 kPa and 150 °C for 6 h to prepare the product core-shell structured carbon monoxide adsorbent.

[0034] Figure 1 is the most probable pore size distribution diagram of the carbon monoxide adsorbent obtained in Example 1. As can be seen from the figure, the most probable pore size is about 3.9 nm, which proves that the pore size of this adsorbent is small and is conducive to the dispersion of the active components. The specific surface pore distribution of this core-shell adsorbent is: BET: 312.3 m 2 / g.

[0035] Example 2

[0036] Other conditions and operations are the same as those in Example 1, except that in step (S1), 0.5 part by mass of coupling agent KH-540 is replaced by 0.8 part by mass of KH-550; in step (S2), the amount of cuprous chloride used is changed to 9 parts by mass; in step (S3), the amount of kaolin used is changed to 7 parts by mass.

[0037] Example 3

[0038] Other conditions and operations are the same as those in Example 1, except that in step (S2), high-energy ball milling is replaced by planetary ball milling, with alternating forward and reverse rotations, a rotation speed of 200 rpm, and a ball milling time of 5 h.

[0039] Example 4

[0040] Other conditions and operations are the same as those in Example 1, except that step (S1) is cancelled, and in step (S3), alumina microspheres unmodified by a coupling agent are directly used.

[0041] Example 5

[0042] Other conditions and operations are the same as those in Example 1, except that in step (S3), the amount of kaolin used is changed to 6 parts by mass, and methyl MQ silicone resin is not added.

[0043] Example 6

[0044] Other conditions and operations are the same as those in Example 1, except that in step (S3), the dosage of hydroxypropyl methylcellulose is 0.825 parts by mass, and the dosage of sodium silicate is 0.125 parts by mass.

[0045] Example 7

[0046] Other conditions and operations are the same as those in Example 1, except that in step (S3), the addition amount of hydroxypropyl methylcellulose is 2 parts by mass, and sodium silicate is not added.

[0047] Example 8

[0048] Other conditions and operations are the same as those in Example 1, except that in step (S3), sodium silicate is replaced with phenolic resin of equal mass.

[0049] Comparative Example

[0050] 10 parts by mass of NaY molecular sieve and 7 parts by mass of cuprous chloride are mixed and ground to prepare an adsorbent precursor. 15 parts by mass of pseudo-boehmite are added in a ball rolling machine by the mechanical ball rolling method, and 85 parts by mass of the adsorbent precursor are formed into balls, and then heated at 700 °C for 2 hours to prepare a carbon monoxide adsorbent loaded with cuprous.

[0051] Figure 2 It is the breakthrough curve of carbon monoxide for the core-shell adsorbent of Example 1 and the adsorbent of Comparative Example 1 at 25 °C and an adsorption pressure of 7 kg. The dynaSorb BT instrument is used to test the mass transfer coefficient of the adsorbent (the mass transfer coefficient is measured using 5% CO + 95% H2). Its meaning is the curve of the CO concentration in the effluent component changing with time. Due to the existence of mass transfer resistance, when the front of the fluid flow passes through a certain point in the bed, the contact time between the two phases is short and the equilibrium state cannot be reached, and the concentration wave front has moved forward. And due to factors such as the flow velocity distribution of the mobile phase and the type of adsorption isotherm, an "S"-shaped mass transfer front is formed, which is mirror-similar to the breakthrough curve. The area formed by the breakthrough starting point and the breakthrough ending point in the breakthrough curve is called the "mass transfer zone". The greater the mass transfer resistance, the longer the mass transfer zone; the smaller the slope of the mass transfer zone, the flatter the amplitude of the breakthrough curve. From Figure 2 It can be seen that the mass transfer coefficient of the core-shell structure adsorbent of Example 1 is 0.058 s -1 , while the mass transfer coefficient of the non-core-shell structure of the comparative example is very low, only 0.021 s -1 . When the adsorption capacity remains the same, the increase in the mass transfer coefficient (the slope of the breakthrough curve becomes larger and the mass transfer coefficient is higher) makes the pressure swing adsorption process easier to carry out.

[0052] Effect Example

[0053] The following performance tests were carried out on the composite adsorbents obtained in the above examples and comparative examples, and the results are shown in Table 1 below.

[0054] 1. Mechanical strength: Refer to Part 3 of GB / T 30202.3-2013, compressive strength. Use the ZQJ-II intelligent particle strength tester (manufactured by Dalian Intelligent Tester Factory, supervised by the National Chemical Catalyst Testing Center). Randomly select 20 composite adsorbent microspheres to test the compressive strength and take the average value.

[0055] 2. Abrasion rate: Refer to GB / T 10505.2-1989, the determination method of the abrasion rate of 3A molecular sieve. Calculate it according to the formula abrasion rate = (mass difference of the sample before and after abrasion / mass of the sample before abrasion) × 100%.

[0056] 3. CO dynamic adsorption capacity test: The test is carried out under the conditions of 70 °C and an adsorption pressure of 7 kg (using 25% CO + 75% H2 for determination). The instrument used is dynaSorb BT. Carry out the adsorption and desorption procedures on the composite adsorbents of the examples and comparative examples to test the dynamic adsorption capacity of CO and the change of bed temperature.

[0057] Table 1 Test results of the performance of carbon monoxide adsorbents

[0058]

[0059] It can be seen that in the present invention, by using a high specific heat capacity non-porous microsphere inert core as the core and loading cuprous salt molecular sieve as the shell, the temperature change of the adsorbent during the pressure swing adsorption process is significantly reduced, and thus the dynamic adsorption capacity of the adsorbent is significantly improved. The introduction of the core-shell structure, on the one hand, reduces the loss rate during the operation of the adsorbent, and on the other hand, improves the phenomenon that the dynamic adsorption capacity of the adsorbent decreases due to temperature change during the pressure swing adsorption process, thereby greatly extending the service life of the adsorbent.

Claims

1. A core-shell structured carbon monoxide adsorbent, characterized in that, It uses microspheres with a high specific heat capacity and a non-porous structure as the core, and molecular sieves loaded with cuprous salts as the shell. The composite adsorbent comprises the following raw materials in parts by mass: 5-10 parts of microspheres with a high specific heat capacity and a non-porous structure, 70-90 parts of molecular sieves loaded with cuprous salts, 5-10 parts of binder, and 1-2 parts of co-binder; the particle size of the non-porous structure microspheres is 1-10 mm, the porosity is <10%, and the density is 2-4 g / cm 3 , the mass specific heat capacity is 0.7-0.9 J / g·°C; or the volume specific heat capacity is 1.5-3.5 J / cm 3 ·°C; the non-porous structure microspheres are modified by a silane coupling agent, and the silane coupling agent is an amino silane coupling agent; the cuprous salt is at least one of CuCl, CuBr, and CuI; the molecular sieve is an X-type and / or Y-type molecular sieve.

2. The carbon monoxide adsorbent according to claim 1, characterized in that, The particle size of the non-porous structure microspheres is 1-3 mm.

3. The carbon monoxide adsorbent according to claim 1, wherein The non-porous structure microspheres are selected from at least one of aluminum oxide microspheres, magnesium oxide microspheres, glass microspheres, ceramic microspheres, silicon dioxide microspheres, and polystyrene microspheres.

4. The carbon monoxide adsorbent according to claim 1, characterized in that, The amino silane coupling agent is selected from at least one of γ-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-diethenyltriaminepropylmethyldimethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-aminoethyl-3-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane.

5. The carbon monoxide adsorbent according to claim 1, wherein The method for modifying the non-porous structure microspheres with a silane coupling agent includes the following steps: dispersing the non-porous structure microspheres in an alcohol aqueous solution, adding a silane coupling agent, stirring and heating at 50-60 °C for 1-2 h under ultrasonic conditions, washing, and drying to obtain non-porous structure microspheres modified with a silane coupling agent; further, the dosage of the silane coupling agent is 5-8 wt% of the mass of the non-porous structure microspheres, the ultrasonic conditions are 90-150 kHz, and the power is 200-300 W; the alcohol aqueous solution is a mixed solution of ethanol and water, where the volume ratio of alcohol is 50-60%; the washing is with absolute ethanol.

6. The carbon monoxide adsorbent according to claim 1, wherein The molecular sieve loaded with cuprous salt is prepared by a preparation method including the following steps: after feeding the molecular sieve and cuprous salt according to a mass ratio of 1:0.7-0.9, mixing and grinding to prepare a molecular sieve loaded with cuprous salt.

7. The carbon monoxide adsorbent according to claim 6, wherein The mixing and grinding methods are high-energy ball milling, ultra-centrifugal grinding, and planetary ball milling.

8. The carbon monoxide adsorbent according to claim 7, wherein The mixing and grinding method is high-energy ball milling, using 2-3 mm tungsten carbide balls, with a ball-to-material ratio of 5-10:1, a ball milling time of 3-5 h, and a ball milling speed of 200-300 rpm.

9. The carbon monoxide adsorbent according to claim 1, wherein The binder is selected from at least one of clay and silicone resin; the silicone resin is selected from polymethyl silicone resin and polyethyl silicone resin.

10. The carbon monoxide adsorbent according to claim 9, characterized in that, The binder is natural clay with a particle size of 20-50 μm.

11. The carbon monoxide adsorbent according to claim 9, characterized in that, The clay is selected from at least one of kaolin, metakaolin, montmorillonite, sericite, bentonite, and sepiolite.

12. The carbon monoxide adsorbent according to claim 9, wherein The silicone resin is methyl MQ type silicone resin.

13. The carbon monoxide adsorbent according to claim 12, wherein, The M:Q ratio of the methyl MQ type silicone resin is 0.5-0.7, and the weight average molecular weight is 5000-10000 g / mol.

14. The carbon monoxide adsorbent according to claim 9, characterized in that, The binder is a mixture of kaolin and methyl MQ type silicone resin according to a mass ratio of 5-7:

1.

15. The carbon monoxide adsorbent according to claim 1, wherein, The adhesion aid is selected from at least one of polyvinyl alcohol, hydroxypropyl methylcellulose, phenolic resin, acrylic resin, dextran, sodium silicate, and gum arabic.

16. The carbon monoxide adsorbent according to claim 15, wherein The adhesion aid is a compound of hydroxypropyl methylcellulose and sodium silicate according to a mass ratio of 4-7:

1.

17. The preparation method of the carbon monoxide adsorbent according to any one of claims 1-6, characterized in that, Including the following steps: obtaining a core-shell structure adsorbent precursor by mechanically rolling the non-porous structure microspheres, the molecular sieve loaded with cuprous salt, the binder, and the adhesion aid in a rolling ball machine; the core-shell structure adsorbent precursor is first heat-treated at 350-500 °C for 1-3 h in a protective atmosphere, and then reduced at 150-220 °C for 5-10 h in a reducing atmosphere to obtain a pressure swing adsorption separation carbon monoxide adsorbent with a core-shell structure.

18. The preparation method according to claim 17, wherein, The process parameters of the mechanical rolling ball method are a power of 200 - 300 W and a rotational speed of 90 - 130 rpm; the protective atmosphere is nitrogen and / or argon; the reducing atmosphere is under a CO and / or H2 atmosphere.

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