3D printing ink, monolithic adsorbent and preparation method and application of monolithic adsorbent

Abstract

The invention provides 3D printing ink, a monolithic adsorbent as well as a preparation method and application of the monolithic adsorbent, and belongs to the field of preparation of molecular sieve adsorbents. The invention provides a 3D printing ink, which comprises the following components by mass: 40-75% of a molecular sieve; 15 to 40 percent of cuprous chloride; 10%-40% of a binder; 1-7% of an organic auxiliary agent; the 3D printing ink does not contain water; and the adhesive is a solid organic adhesive. According to the 3D printing ink, natural clay or silicon oxide or aluminum oxide inorganic binders are not used, only the solid organic binder is used, the solid organic binder is heated to a molten state when the integral adsorbent is prepared, printing preparation can be carried out, it is fully guaranteed that the printing ink has the high solid content, and the printing ink can be applied to 3D printing. And the space among the molecular sieve powder particles is fully filled with the organic binder, so that a stable supporting effect is achieved, and the printed integral molecular sieve block can be prevented from being deformed.

Description

Technical Field

[0001] The present invention relates to the field of preparation of molecular sieve adsorbents, and particularly relates to a 3D printing ink, a monolithic adsorbent, and a preparation method and application thereof. Background Art

[0002] Molecular sieves are a class of crystalline aluminosilicates. Due to their unique pore structure and internal electric field distribution, they can act as molecular sieves and are widely used as adsorbents in the fields of gas purification and separation.

[0003] Generally, the synthesized molecular sieve crystals are in powder form, and the particle size is generally in the range of 0.1 - 10 μm. When used as an adsorbent, it needs to be processed into millimeter-sized granular, spherical or strip-shaped forms, etc. However, these traditional configuration adsorbents generally have disadvantages such as large bed pressure drop, poor mass transfer and heat transfer effects, and easy particle wear during use. Processing into a monolithic adsorbent can effectively reduce the pressure drop, improve the mass transfer and heat transfer performance, and avoid particle wear between particles.

[0004] Different from the traditional forming methods of monolithic adsorbents, 3D printing technology is a bottom-up manufacturing method. By automatically controlling the "layer-by-layer stacking" of the printing ink, the structure of the printed object can be designed, so as to meet the customized requirements of materials for different application scenarios. At present, there are already some precedents of 3D printing monolithic molecular sieve adsorbents / catalysts. For example, adding expensive photoinitiators to the printing ink for photocuring treatment, and subsequent secondary hydrothermal crystallization treatment is required. The process is complex, and the secondary hydrothermal treatment easily leads to a decrease in the strength of the monolithic catalyst; a large amount of water is added during the preparation of the 3D printing ink, and the low solid content of the printing ink makes the printed monolithic molecular sieve block prone to deformation. Summary of the Invention

[0005] The present invention provides a 3D printing ink, a monolithic adsorbent, and a preparation method and application thereof. When using the 3D printing ink of the present invention to prepare a monolithic adsorbent, the process is simple, the strength is high, and it is not easy to deform.

[0006] The present invention provides a 3D printing ink, which includes the following components in terms of mass fraction:

[0007]

[0008] The 3D printing ink does not contain water;

[0009] The binder is a solid organic binder.

[0010] Preferably, the structure of the molecular sieve includes FAU, MFI, BEA, MCM-41, MCM-48 and One or more of SBA-15;

[0011] The molar ratio of silicon oxide to aluminum oxide in the molecular sieve is 5 - 550.

[0012] Preferably, the solid organic binder includes acrylic resin and / or epoxy resin;

[0013] The acrylic resin includes glycidyl methacrylate; the epoxy resin includes bisphenol A epoxy resin and / or novolac epoxy resin.

[0014] Preferably, the organic auxiliary includes organosilicon substances.

[0015] Preferably, the organosilicon substances include one or more of methylchlorosilane, methyl ethoxysilane, methyl silicone oil, and methylphenyl silicone oil.

[0016] The present invention also provides a preparation method of an integral adsorbent, comprising the following steps:

[0017] Heat the 3D printing ink described in the above technical solution to melt the solid organic binder therein, and then perform 3D printing according to the design to obtain a green body;

[0018] Roast the green body to obtain the integral adsorbent.

[0019] Preferably, the needle temperature used for 3D printing is the melting temperature of the solid organic binder, the needle diameter is 0.8 - 3 mm, and the needle inlet pressure is 0.5 - 1.5 MPa;

[0020] The printing speed of the 3D printing is 1 - 5 mm / s;

[0021] After the 3D printing, it further includes: performing low-temperature shaping on the obtained green embryo to obtain the green body;

[0022] The temperature of the low-temperature shaping is 0 - 15 °C, and the time is 1 - 2 h.

[0023] Preferably, the roasting temperature is 350 - 420 °C, the heat preservation time is 3 - 6 h, and the heating rate to the roasting temperature is 5 - 15 °C / min;

[0024] The roasting is carried out in an oxygen-free protective atmosphere.

[0025] The present invention also provides an integral adsorbent prepared by the preparation method described in the above technical solution. The integral adsorbent has a compressive strength of 200 - 300 N / cm and a warpage degree of 0.1 - 0.3%.

[0026] The present invention also provides an application of the integral adsorbent described in the above technical solution in carbon monoxide separation and purification.

[0027] The 3D printing ink of the present invention does not use natural clay or inorganic binders such as silicon oxide and aluminum oxide. Only a solid organic binder is used. When preparing the monolithic adsorbent, the solid organic binder can be heated to the molten state for printing preparation. Different from the existing 3D printing ink preparation process that requires adding a large amount of water, it fully ensures that the 3D printing ink has a high solid content. The molecular sieve powder particles are fully filled with the organic binder, playing a stable supporting role, and can prevent the printed monolithic molecular sieve block from deforming Moreover, the molten organic binder in the printing process effectively avoids the oxidation of cuprous chloride to cupric chloride. Avoid affecting the loading effect of cuprous chloride and the CO adsorption performance of the monolithic adsorbent; by adjusting the dosage of each component, the distribution of cuprous chloride in the pores of the monolithic adsorbent is optimized, without blocking the pore structure of the molecular sieve and optimizing the loading amount of the molecular sieve, thereby improving the adsorption capacity and separation ability of the adsorbent for carbon monoxide.

[0028] Furthermore, the 3D printing ink of the present invention uses organosilicon substances as organic additives, which ensures the extrudability of the printing process, makes the printing process smoother, and the surface of the printed adsorbent block is also smoother.

[0029] Furthermore, the present invention immediately performs low-temperature shaping on the green body, which is beneficial to solving the deformation problem that the middle position of the green body is prone to depression during placement.

[0030] Furthermore, the present invention calcines the green body in an anaerobic protective atmosphere, which can transform the organic binder into a carbon material with developed pores. After calcination, it still fills between the molecular sieve particles, playing a supporting and strengthening role, contributing to obtaining a high-strength monolithic adsorbent. Different from adding inorganic binders that are prone to block the pores of the molecular sieve in the printing ink, the carbon material itself has a developed pore structure, providing a channel for gas diffusion, which is beneficial to improving the gas adsorption / desorption rate of the monolithic adsorbent.

[0031] Furthermore, the present invention calcines at an anaerobic and relatively low temperature, which can make cuprous chloride better dispersed on the surface of the carrier, avoiding the high-temperature gasification of cuprous chloride caused by high-temperature calcination in the traditional printing method.

[0032] The present invention has simple operation and cheap and easily available raw materials, which is conducive to industrial mass production. It is applicable to the processing and manufacturing of various molecular sieve adsorbent blocks, and has high research and commercial application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a digital photo of the 3D printed monolithic adsorbent block obtained in Example 1 of the present invention;

[0034] Figure 2 It is a scanning electron microscope photo of the 3D printed monolithic adsorbent block obtained in Example 1 of the present invention at different magnifications;

[0035] Figure 3 XRD pattern of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention;

[0036] Figure 4 N₂ adsorption - desorption isotherm of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention;

[0037] Figure 5 Adsorption isotherm diagrams of CO, CH₄, N₂, and H₂ of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention. Detailed implementation manners

[0038] The present invention provides a 3D printing ink, which comprises the following components by mass fraction:

[0039]

[0040]

[0041] The 3D printing ink does not contain water;

[0042] The binder is a solid organic binder.

[0043] By mass fraction, the 3D printing ink provided by the present invention comprises 40 - 75% of molecular sieve. In specific embodiments of the present invention, the mass fraction of the molecular sieve can be 40%, 45%, 50%, 55%, 60% or 70%; the structure of the molecular sieve preferably comprises one or more of FAU, MFI, BEA, MCM - 41, MCM - 48 and SBA - 15; the particle size of the molecular sieve is preferably 2 - 6 μm; the molar ratio of silicon oxide to aluminum oxide in the molecular sieve is preferably 5 - 550. In specific embodiments of the present invention, the molar ratio of silicon oxide to aluminum oxide in the molecular sieve can be 5, 10, 30, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, 500 or 550. The present invention adjusts the molar ratio of silicon oxide to aluminum oxide in the molecular sieve, so that the electric field in the molecular sieve has good selective separation ability for CO.

[0044] By mass fraction, the 3D printing ink provided by the present invention comprises 15 - 40% of cuprous chloride. In specific embodiments of the present invention, the mass fraction of the cuprous chloride can be 20%, 25%, 30%, 35% or 40%.

[0045] In terms of mass fraction, the 3D printing ink provided by the present invention includes a binder. The binder is a solid organic binder at 10-40%. In specific embodiments of the present invention, the mass fraction of the binder can be 15%, 20%, 25%, 30%, 35% or 40%; the solid organic binder is preferably in powder form; the solid organic binder preferably includes acrylic resin and / or epoxy resin; the acrylic resin preferably includes glycidyl methacrylate; the epoxy resin preferably includes bisphenol A epoxy resin and / or novolac epoxy resin. The carbon material formed by the solid organic binder selected in the present invention can improve the internal electric field distribution of the molecular sieve, and the formed carbon material has suitable functional groups and pore pairs, which can further improve the CO / N2 separation coefficient and CO / CH4 separation coefficient of the monolithic adsorbent.

[0046] In terms of mass fraction, the 3D printing ink provided by the present invention includes an organic auxiliary agent at 1-7%. In specific embodiments of the present invention, the mass fraction of the organic auxiliary agent can be 1%, 2%, 3%, 4%, 5% or 6%; the organic auxiliary agent preferably includes an organosilicon substance; the organosilicon substance preferably includes one or more of methylchlorosilane, methylethoxysilane, methyl silicone oil and methylphenyl silicone oil. Using organosilicon substances as organic auxiliary agents ensures the extrudability of the printing process, makes the printing process smoother, and the surface of the printed adsorbent block is also smoother.

[0047] The present invention also provides a method for preparing a monolithic adsorbent, comprising the following steps:

[0048] Heat the 3D printing ink described in the above technical solution until the solid organic binder therein melts, and then perform 3D printing to obtain a green body;

[0049] Roast the green body to obtain the monolithic adsorbent.

[0050] In the present invention, the organic binder of the 3D printing ink described in the above technical solution is melted and then 3D printed according to the design to obtain a green body.

[0051] In the present invention, the temperature of the needle used for 3D printing is preferably the melting temperature of the solid organic binder, the diameter of the needle is preferably 0.8-3 mm, and the inlet air pressure of the needle is preferably 0.5-1.5 MPa. In specific embodiments of the present invention, the diameter of the needle can be 0.8 mm, 1.2 mm, 1.6 mm, 2 mm, 2.4 mm, 2.8 mm or 3 mm, and the inlet air pressure of the needle can be 0.5 MPa, 0.8 MPa, 1.2 MPa or 1.5 MPa.

[0052] In the present invention, the printing speed of the 3D printing is preferably 1 to 5 mm / s. In a specific embodiment, the printing speed of the 3D printing can be 1 mm / s, 2 mm / s, 3 mm / s, 4 mm / s or 5 mm / s.

[0053] In the present invention, the temperature of the 3D printing is preferably 160 to 230 °C. In a specific embodiment of the present invention, the temperature of the 3D printing can be 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C or 230 °C, and the temperature is the temperature of the material in the needle.

[0054] After the 3D printing, the present invention preferably further includes: performing low-temperature shaping on the obtained initial embryo to obtain the embryo body. Immediately performing low-temperature shaping on the initial embryo is beneficial to solving the deformation problem that the middle position of the embryo body is prone to depression during placement.

[0055] In the present invention, the temperature of the low-temperature shaping is preferably 0 to 15 °C, and the time is preferably 1 to 2 h. In a specific embodiment of the present invention, the temperature of the low-temperature shaping can be 0 °C, 4 °C, 8 °C, 12 °C or 15 °C; the time can be 1 h, 1.2 h, 1.6 h or 2 h.

[0056] After obtaining the embryo body, the present invention calcines the embryo body to obtain the monolithic adsorbent.

[0057] In the present invention, the temperature of the calcination is preferably 350 to 420 °C, and the holding time is preferably 3 to 6 h. In a specific embodiment of the present invention, the temperature of the calcination can be 350 °C, 370 °C, 390 °C, 400 °C or 420 °C; the time can be 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h or 6 h. The present invention uses an anaerobic and relatively low-temperature calcination, which can better disperse cuprous chloride on the surface of the carrier, avoiding the high-temperature gasification of cuprous chloride caused by high-temperature calcination in the traditional printing method.

[0058] In the present invention, the heating rate for heating to the calcination temperature is preferably 5 to 15 °C / min. In a specific embodiment of the present invention, the heating rate can be 5 °C / min, 7 °C / min, 9 °C / min, 11 °C / min, 13 °C / min or 15 °C / min. The present invention improves the CO / N2 separation coefficient and CO / CH4 separation coefficient of the molecular the pore structure of the molecular sieve and prepares a carbon material with suitable porosity, which further improves the monolithic adsorbent by controlling the heating rate and calcination conditions; in addition, it also reduces the stress between the carbon material and the molecular sieve, thereby reducing the warpage degree of the monolithic adsorbent.

[0059] In the present invention, the calcination is preferably carried out in an oxygen-free protective atmosphere. In the present invention, the gas in the protective atmosphere preferably includes one or more of nitrogen, argon, and helium.

[0060] In the present invention, an oxygen-free protective atmosphere is used for calcining the embryo body, which can convert the organic binder into a carbon material with well-developed pores. After calcination, it still fills between the molecular sieve particles, playing a role in supporting and strengthening, and contributing to obtaining a high-strength monolithic adsorbent. Different from adding an inorganic binder that is likely to block the molecular sieve pores in the printing ink, the carbon material itself has a well-developed pore structure, providing a channel for gas diffusion and being beneficial to improving the gas adsorption / desorption rate of the monolithic adsorbent.

[0061] The present invention also provides a monolithic adsorbent prepared by the preparation method described in the above technical solution. The compressive strength of the monolithic adsorbent is 200 - 400 N / cm, and the warpage degree is 0.1 - 0.3%; the specific surface area of the monolithic adsorbent is preferably 200 - 600 m 2 / g, and the porosity is preferably 50 - 80%.

[0062] The present invention also provides the application of the monolithic adsorbent described in the above technical solution in carbon monoxide separation and purification.

[0063] The following is a detailed description of the 3D printing ink, monolithic adsorbent, and their preparation methods and applications provided by the present invention in conjunction with examples, but they should not be construed as limiting the protection scope of the present invention.

[0064] Example 1

[0065] 20 g of NaY molecular sieve powder with a particle size of 2.3 μm (belonging to the FAU topological structure, with a molar ratio of silica to alumina of 5.25), 10 g of cuprous chloride, 10 g of bisphenol A epoxy resin powder, and 1 g of methyl silicone oil were mixed and manually ground evenly with an agate mortar to obtain a mixed powder, which was heated to 200 °C to a molten state to prepare 3D printing ink;

[0066] The molten 3D printing ink was transferred to a 3D printing needle, and the needle was heated to 200 °C. During the printing process, the temperature of the printing needle was always maintained at 200 °C, and the diameter of the printing needle was 1.2 mm;

[0067] Using Auto CAD software to construct a product model, designing the printing block size (a cuboid, with both length and width of 2 cm and height of 0.8 cm). During printing, the diameter of the rod was 1.1 mm, the filling density was 50%, the layer spacing was 0.5 mm, the fixed printing speed was 2 mm / s, the printing pressure was set at 1 MPa, and 3D printing was carried out for molding. The printing environment temperature was 5 °C, and it was maintained for 1 h after printing to fully shape it to obtain a 3D printed initial embryo;

[0068] The 3D printed green body after low-temperature shaping is placed in a muffle furnace for programmed heating roasting. The roasting atmosphere is nitrogen protection, the heating rate is 5 °C / min, the roasting temperature is 350 °C, and the holding time after the temperature reaches is After 6 h, a 3D printed monolithic adsorbent is obtained.

[0069] Figure 1 This is the digital photo of the 3D printed monolithic adsorbent block obtained in Example 1 of the present invention;

[0070] Figure 2 This is the scanning electron microscope photos of the 3D printed monolithic adsorbent block obtained in Example 1 of the present invention at different magnifications;

[0071] Figure 3 This is the XRD pattern of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention.

[0072] Example 2

[0073] 20 g of ZSM-5 molecular sieve powder with a particle size of 4.3 μm (belonging to the MFI topological structure, with a molar ratio of silica to alumina of 520), 4.5 g of cuprous chloride, 3 g of phenolic epoxy resin powder, and 0.5 g of methyl silicone oil are mixed and manually ground evenly with an agate mortar to obtain a mixed powder, and then heated to 180 °C to the molten state to prepare 3D printing ink;

[0074] The molten 3D printing ink is transferred to a 3D printing needle, and the needle is heated to 160 °C. During the printing process, the temperature of the printing needle is always maintained at 160 °C, and the diameter of the printing needle is 1.3 mm;

[0075] Use Auto CAD software to construct a product model, design the printing block size (cylinder, diameter 2 cm, height 2 cm). When printing, the rod diameter is 1.2 mm, the filling density is 46%, the layer spacing is 0.9 mm, the fixed printing speed is 1.5 mm / s, the printing pressure is set at 0.52 MPa, perform 3D printing and forming, the printing environment temperature is 15 °C, and it is still maintained for 2 h after printing to make it fully shaped to obtain a 3D printed green body;

[0076] The 3D printed green body after low-temperature shaping is placed in a muffle furnace for programmed heating roasting. The roasting atmosphere is nitrogen protection, the heating rate is 15 °C / min, the roasting temperature is 420 °C, and the holding time is 3 h after the temperature reaches to obtain the 3D printed monolithic adsorbent.

[0077] Example 3

[0078] Mix 20 g of Beta zeolite powder with a particle size of 5.7 μm (belonging to the BEA topological structure, with a molar ratio of silica to alumina of 26), 8 g of cuprous chloride, 8 g of glycidyl methacrylate powder, and 2 g of methylchlorosilane, and manually grind them evenly with an agate mortar to obtain a mixed powder. Then heat it to 230 °C until it reaches a molten state to prepare 3D printing ink;

[0079] Transfer the molten 3D printing ink to a 3D printing needle, and heat the needle to 230 °C. During the printing process, the temperature of the printing needle is always maintained at 230 °C, and the diameter of the printing needle is 3.0 mm;

[0080] Use Auto CAD software to construct a product model, design the printing block size (cube, with length, width, and height all being 3 cm). During printing, the diameter of the rod is 2.8 mm, the filling density is 55%, the layer spacing is 2.4 mm, the fixed printing speed is 4.5 mm / s, and the printing pressure is set at 1.5 MPa. Carry out 3D printing and forming. The printing environment temperature is 0 °C, and it is maintained for 2 h after printing to allow it to fully shape and obtain a 3D printed embryo;

[0081] Place the 3D printed green body after low-temperature shaping in a muffle furnace for programmed temperature rise roasting, and the roasting gas Under the protection of argon atmosphere, the heating rate is 10 °C / min, the calcination temperature is 420 °C, and after the temperature rises, keep it for 3 h to obtain the 3D printed monolithic adsorbent.

[0082] Example 4

[0083] Mix 20 g of MCM-41 zeolite powder with a particle size of 3.8 μm (with a molar ratio of silica to alumina of 60), 15 g of cuprous chloride, 8 g of phenolic epoxy resin powder, and 3 g of methyl ethoxysilane, and manually grind them evenly with an agate mortar to obtain a mixed powder. Then heat it to 210 °C until it reaches a molten state to prepare 3D printing ink;

[0084] Transfer the molten 3D printing ink to a 3D printing needle, and heat the needle to 210 °C. During the printing process, the temperature of the printing needle is always maintained at 210 °C, and the diameter of the printing needle is 0.8 mm;

[0085] Use Auto CAD software to construct a product model, design the printing block size (cuboid, with length and width both being 3 cm and height being 2 cm). During printing, the diameter of the rod is 0.75 mm, the filling density is 45%, the layer spacing is 0.65 mm, the fixed printing speed is 1 mm / s, and the printing pressure is set at 0.75 MPa. Carry out 3D printing and forming. The printing environment temperature is 10 °C, and it is maintained for 1 h after printing to allow it to fully shape and obtain a 3D printed embryo;

[0086] The 3D printed green body after low-temperature shaping is placed in a muffle furnace for programmed heating roasting. The roasting atmosphere is helium protection, the heating rate is 5 °C / min, the roasting temperature is 420 °C, and after the temperature rises, the holding time is 3 h to obtain the 3D printed monolithic adsorbent.

[0087] Example 5

[0088] The only difference from Example 1 is that the molecular sieve is MCM-48 powder.

[0089] Example 6

[0090] The only difference from Example 1 is that the molecular sieve is SBA-15 powder.

[0091] Comparative Example 1

[0092] The only difference from Example 1 is that kaolin is used as the binder.

[0093] Comparative Example 2

[0094] The only difference from Example 2 is that silica sol is used as the binder.

[0095] Comparative Example 3

[0096] The only difference from Example 3 is that pseudo-boehmite is used as the binder.

[0097] The samples obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were tested for compressive strength, specific surface area, warpage, CO, N2, and CH4 adsorption capacity (25 °C, 1 bar), and the results are shown in Table 1.

[0098] Figure 4 It is the N2 adsorption-desorption diagram of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention;

[0099] Figure 5 The CO, CH4, N2, and H2 adsorption of the 3D printed monolithic adsorbent obtained in Example 1 of the present invention Attached isotherm diagram.

[0100] Table 1 Test results of compressive strength, specific surface area, and warpage of the samples obtained in Examples 1 to 6 and Comparative Examples 1 to 3

[0101]

[0102] As can be seen from Table 1, the products obtained by the present invention have higher compressive strength, larger specific surface area, lower warpage, higher CO adsorption capacity and selectivity.

[0103] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A 3D printing ink, characterized in that: In terms of mass fraction, it includes the following components: The 3D printing ink does not contain water; The adhesive is a solid organic adhesive.

2. The 3D printing ink according to claim 1, characterized in that: The structure of the molecular sieve includes one or more of FAU, MFI, BEA, MCM-41, MCM-48 and SBA-15; The molar ratio of silicon oxide to aluminum oxide in the molecular sieve is 5 to 550.

3. The 3D printing ink according to claim 1, characterized in that: The solid organic adhesive includes acrylic resin and / or epoxy resin; The acrylic resin includes glycidyl methacrylate; the epoxy resin includes bisphenol A epoxy resin and / or novolac epoxy resin.

4. The 3D printing ink according to claim 1, characterized in that: The organic auxiliary agent includes organic silicon substances.

5. The 3D printing ink according to claim 4, characterized in that: The organic silicon material includes one or more of methylchlorosilane, methylethoxysilane, methyl silicone oil and methylphenyl silicone oil.

6. A method for preparing a monolithic adsorbent, characterized in that: The following steps are involved: The 3D printing ink according to any one of claims 1 to 5 is heated until the solid organic binder therein is melted, and then 3D printing is performed according to the design to obtain an embryo; The embryo body is calcined to obtain the monolithic adsorbent.

7. The preparation method according to claim 6, characterized in that: The needle temperature used in the 3D printing is the melting temperature of the solid organic adhesive, the needle diameter is 0.8 to 3 mm, and the needle inlet pressure is 0.5 to 1.5 MPa; The printing speed of the 3D printing is 1 to 5 mm / s; After the 3D printing, the method further includes: subjecting the obtained primary embryo to low-temperature shaping to obtain the embryo body; The temperature of the low-temperature shaping is 0-15°C and the time is 1-2h.

8. The preparation method according to claim 6, characterized in that: The calcination temperature is 350-420°C, the holding time is 3-6h, and the heating rate to the calcination temperature is 5-15°C / min; The calcination is carried out in an oxygen-free protective atmosphere.

9. The monolithic adsorbent prepared by the preparation method according to any one of claims 6 to 8, characterized in that: The compressive strength of the integral adsorbent is 200-300 N / cm, and the warpage is 0.1-0.3%.

10. Use of the monolithic adsorbent according to claim 9 in separation and purification of carbon monoxide.

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