KR20170034637A - Absorbents for removing acid gases and preparing method thereof - Google Patents
Absorbents for removing acid gases and preparing method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
Abstract
Description
The present invention relates to an adsorbent for removing an acidic gas and a method for producing the same.
Generally, the natural gas mined from the natural gas field is composed mainly of methane (CH 4 ), and hydrocarbons such as ethane (C 2 H 6 ), propane (C 3 H 8 ) and butane (C 4 H 10 ) Examples of the impurities include an acid gas component such as carbon dioxide (CO 2 ) and hydrogen sulfide (H 2 S), nitrogen (N 2 ), helium (He), water (H 2 O) and mercury .
Natural gas can be compressed or liquefied during transport or storage, and carbon dioxide and water can be involved in condensation or hydrate formation, causing clogging of the pipe, or forming carbonic acid through the reaction, Together they can cause corrosion problems.
The impurities contained in the natural gas need to be removed through a pretreatment process before the natural gas is sent to the liquefaction process, and the acid gas removal process included in the natural gas is carried out using physical, chemical and physicochemical absorption liquids, And is being removed to a gas level of liquefied natural gas at less than 50 ppm of carbon dioxide and less than 4 ppm of hydrogen sulfide.
International Patent Publication No. 1992-020431 (published on Mar. 03, 1995) discloses an acid gas removing process using an absorption liquid, in which a known mixture of amine for removing acidic gases is used to change the amine selectivity to carbon dioxide and hydrogen sulfide And International Publication No. 2013-138437 (published on Sep. 19, 2013) discloses an amine absorption liquid which selectively removes only hydrogen sulfide in an acidic gas. In addition, International Publication No. 2013-188367 (published Dec. 19, 2013) discloses amines having various structures capable of minimizing amine loss and an acid gas removing process using the same.
Such a chemical absorption process must use a large amount of heavy absorbent, the space occupied by the absorption tower and the regeneration tower is large, a large amount of energy is used for regeneration of the amine absorbent, and when applied to floating structures such as marine environment, There is a problem that the absorption efficiency is lowered due to the flow of the gas.
In order to solve the problem of the acid gas removal process using the absorption liquid, an adsorption acid gas removal process which is not affected by the marine environment is proposed without using the amine liquid absorption liquid. Commercial CO 2 adsorbents include zeolite 4A, 5A, activated alumina, and activated carbon. However, adsorbed amounts of CH 4 and C 2 - and C 3 - are high, so they are applied to acid gas contained in natural gas at high pressure. Due to the loss of CH 4 and C 2 -, C 3 -, application is limited.
Metal Oragnic Framework (MOF) adsorbent, which has a high surface area and a porous adsorbent, has been proposed, but MOF also has a high adsorption amount of hydrocarbons, which makes it difficult to minimize the loss.
The present invention relates to an adsorbent for removing acidic gases having high selectivity for acid gas in a mixed gas and excellent stability against moisture, and a method for producing the same.
The problems to be solved by the present invention are not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.
One aspect of the present invention includes a porous metal organic framework (MOF) carrying an amine compound, wherein the amine compound is supported in an amount of 10 to 60 parts by weight per 100 parts by weight of the porous metal organic structure And an adsorbent for removing an acidic gas.
According to one embodiment of the present invention, the amine compound can penetrate the pores of the porous metal organic structure by capillary force.
According to one embodiment of the present invention, the amine compound can bind to the external and internal pores of the porous metal organic structure.
According to one embodiment of the present invention, the metal organic structure is MIL-101 (MIL = Materials of Institut Lavoisier), and the metal (M) in the MIL-101 is Fe, Al, Cr, Ti, V, and the like.
According to one embodiment of the present invention, the amine compound is selected from the group consisting of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEOA), diisopropanolamine, tetraethylene pentaamine (TEPA), triethylenetetraamine (TETA), pentaethylenehexamine, ethylenediamine (ED), diethylenetriamine (DETA), piperazine (PZ), polyethyleneimine, melamine, 3,5- , 2,4-triazole, adenine, 2-amino-1,4-benzenedicarboxylic acid, diisopropylamine, 3-amino-tetrazole, dodecylamine, tris- (2-aminoethyl) , And N, N'-dimethylethylenediamine.
According to one embodiment of the invention, the acid gas is carbon dioxide (CO 2), hydrogen sulfide (H 2 S), sulfur dioxide (SO 2), and nitrogen dioxide can include at least one selected from the group consisting of (NO 2) .
According to one embodiment of the present invention, the adsorbent for removing acidic gases is at least 4 times higher than the porous metal organic structure on which the amine compound is not supported at a temperature of 25 ° C to 75 ° C and a carbon dioxide partial pressure of more than 0 and 20 kPa or less And may have an acid gas adsorption amount.
According to an embodiment of the present invention, the adsorbent for removing an acidic gas may have a carbon dioxide selectivity to methane of at least 40 by the following formula 1 at a temperature of 25 ° C to 75 ° C.
[Formula 1]
(Where q is the gas adsorption amount and p is the gas partial pressure).
Another aspect of the present invention relates to a method for preparing an amine compound, comprising: preparing an amine solution comprising an amine compound and an organic solvent; Immersing the porous metal organic structure in the amine solution so that the amine solution penetrates into the pores of the metal organic structure by capillary force to bind the porous metal organic structure to the pores of the metal organic structure; And washing the porous metal organic structure carrying the amine compound with an organic solvent to remove a residual amine compound not bound to the porous metal organic structure; And a method for producing an adsorbent for removing an acidic gas.
According to an embodiment of the present invention, the organic solvent may include at least one selected from the group consisting of toluene, benzene, xylene, pentane, nonane, decane, ether, dichloromethane and chlorobenzene.
According to one embodiment of the present invention, the amine compound of the amine solution to the organic solvent may be contained in a ratio of 1: 0.2 to 1: 4 (weight ratio).
According to an embodiment of the present invention, there is provided a method for preparing a porous metal organic structure, comprising the steps of: before the step of washing the residual amine compound, Drying step; And a second drying step of the amine compound-supported porous metal organic structure carried out in an inert gas atmosphere and at a temperature of 70 ° C to 100 ° C for 2 to 10 hours after the cleaning step of the residual amine compound; As shown in FIG.
According to an embodiment of the present invention, the adsorbent for removing acidic gases may be any one of the adsorbents for removing acidic gases according to the present invention.
According to an embodiment of the present invention, the penetration of the amine solution into the pores of the metal organic structure may be the penetration into the pore inlet and the pores.
The present invention can provide an adsorbent for removing acidic gases having high selectivity for acidic gas and excellent stability against moisture in the step of removing a large amount of acidic gas contained in the gas.
The adsorbent of the present invention can also be applied to a liquefied natural gas process to reduce the loss of hydrocarbons such as methane, ethane and the like and to provide a process for providing high purity natural gas with less than 50 ppm carbon dioxide, less than 4 ppm hydrogen sulfide, Can be applied.
Further, the adsorbent of the present invention can be applied not only to low pressure but also to adsorption / separation of acid gas at a high pressure of 6000 kPa or more.
FIG. 1 is a flow chart of a method for producing an adsorbent for removing an acidic gas according to an embodiment of the present invention.
2 is a cross-sectional view of a method for producing an adsorbent for removing an acidic gas according to an embodiment of the present invention.
3 is a flowchart illustrating an acid gas removal method according to an embodiment of the present invention.
4 is a graph (a) of the carbon dioxide isotherm adsorption equilibrium curve and a graph (b) of the methane isotherm adsorption equilibrium curve of the adsorbent for removing acid gases prepared in Examples and Comparative Examples of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear. Also, terminologies used herein are terms used to properly represent preferred embodiments of the present invention, which may vary depending on the user, intent of the operator, or custom in the field to which the present invention belongs. Therefore, the definitions of these terms should be based on the contents throughout this specification. Like reference symbols in the drawings denote like elements.
The present invention relates to an adsorbent for removing an acidic gas, and more particularly, to an adsorbent for removing an acidic gas, which removes a large amount of acidic gas contained in a gas and is excellent in stability against moisture.
According to an embodiment of the present invention, the adsorbent for removing acid gases may include a metal-organic framework (MOF) carrying an amine compound. The adsorbent for removing an acid gas is improved in adsorption and selectivity to an acid gas and can provide an improved acid gas isothermal adsorption equilibrium amount from a low pressure to a high pressure.
According to one embodiment of the present invention, the porous metal organic structure has a high surface area and porosity, so it can provide a wide acid gas adsorption site on the supported amine compound. In addition, it has high thermal and chemical stability as well as good resistance to moisture, and can improve the stability of an adsorbent carrying an amine compound upon removal of acid gas from natural gas or the like.
In the MIL-101, the metal (M) is at least one selected from the group consisting of Fe, Al, Cr, Ti, Sc, and V as MIL-101 (MIL = Materials of Institut Lavoisier) (M = Fe, Al, Cr, Ti, Sc) or MIL-101 (M = Cr).
According to one embodiment of the present invention, the amine compound is supported on the porous metal organic structure to improve the degree of adsorption and selectivity to the acid gas, thereby improving the amount of adsorption of low acid gas on the porous metal organic structure at low pressure , The amount of adsorption of hydrocarbons such as methane and the like can be lowered when the acid gas is removed from natural gas or the like.
In one embodiment of the present invention, the amine compound may be bound by penetration into pores of the porous metal organic structure, for example, external pores and / or internal pores with capillary force.
In one embodiment of the present invention, the amine compound is an amine group-containing compound having an adsorptivity to an acid gas, and may be a primary amine, a secondary amine, a tertiary amine or an alkanolamine, an alkylalkanolamine, an aromatic amine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEOA), diisopropanolamine, tetraethylene pentaamine (TEPA), and the like. , Triethylene tetramine (TETA), pentaethylene hexamine, ethylenediamine (ED), diethylenetriamine (DETA), piperazine (PZ), polyethyleneimine, melamine, 3,5- Amino-tetrazole, dodecylamine, tris- (2-aminoethyl) -amine, and N, N-diisopropylamine, N'-dimethylethylenediamine, and the like.
In one embodiment of the present invention, the amine compound is used in an amount of 10 to 60 parts by weight per 100 parts by weight of the porous metal organic structure; Or 25 to 60 parts by weight. The amine compounds, when loaded to less than 10 parts by weight, but may increase the amount of acid gas absorption as compared to the porous metal-organic structure that is not supported at the low pressure of less than 10 kPa, CH 4 and C 2 -, C 3 - adsorption on The selectivity of the acid gas may be lowered, and if it exceeds 60 parts by weight, the pores may be blocked and the acidic gas adsorption amount may be lowered.
According to an embodiment of the present invention, the adsorbent for removing an acidic gas may be used for adsorbing and separating an acidic gas in a gas containing a natural gas, a biogas, etc. containing an acidic gas, (CO 2 ), hydrogen sulfide (H 2 S), sulfur dioxide (SO 2 ), and nitrogen dioxide (NO 2 ), preferably carbon dioxide (CO 2 ).
According to one embodiment of the present invention, the adsorbent for removing acidic gases is selected from the group consisting of 25 占 폚 to 75 占 폚; 25 DEG C to 50 DEG C; Or 25 캜; And an acid gas partial pressure of greater than 0 kPa and less than or equal to 120 kPa, which may have a higher acid adsorption amount than the porous metal organic structure, while having a lower adsorption amount to hydrocarbons. The hydrocarbons may be methane-based hydrocarbons, for example, methane (CH 4 ), ethane (C 2 H 6 ), propane (C 3 H 8 ), butane (C 4 H 10 ), and the like. As an example of the present invention, the adsorbent for removing acid gases may provide an adsorption amount of carbon dioxide of at least 4 times higher than the porous metal organic structure at a partial pressure of carbon dioxide of more than 0 and less than 20 kPa at 25 캜 to 75 캜, ; Greater than 20 kPa and less than 120 kPa; Greater than 20 kPa and less than 100 kPa; Greater than 20 kPa and less than 90 kPa; Greater than 20 kPa and less than 80 kPa; It is possible to provide a carbon dioxide adsorption amount of 1.5 times or more.
According to one embodiment of the present invention, at a temperature of from 25 캜 to 75 캜; 25 DEG C to 50 DEG C; Or an acid gas partial pressure of greater than 0 and less than or equal to 120 kPa at 25 < 0 >C; A hydrocarbon partial pressure greater than 0 and less than or equal to 6000 kPa; The acid gas selectivity for hydrocarbons is at least 40; 50 or more; 100 or more; 400 or more; 500 or more; 600 or more; 40 to 600; 40 to 500; 100 to 500; Or 400 to 500; And may preferably be 400 or more. The carbon dioxide selectivity can be calculated by the following equation (1). In one embodiment of the present invention, the hydrocarbons are methane, the acid gas is carbon dioxide, the partial pressure of methane is 6000 kPa, and the partial pressure of carbon dioxide is 120 kPa.
[Formula 1]
(Where q is the gas adsorption amount, p is the gas partial pressure, a is the acid gas, and i is the hydrocarbon)
The present invention relates to a method for producing an adsorbent for removing an acidic gas, and the above production method relates to a method for impregnating an amine compound into a porous metal organic structure.
1, the method for preparing an adsorbent for removing an acidic gas according to an embodiment of the present invention comprises the steps of preparing an amine solution (S1 ); Carrying step S2; A first drying step (S3); Cleaning step S4; And a second drying step (S5).
Step (S1) of preparing the amine solution is a step of preparing an amine solution by mixing an amine compound and an organic solvent. The amine compound is as mentioned above. The organic solvent may be any organic solvent which dissolves the amine compound and does not inhibit the capillary force upon deposition. In one embodiment of the present invention, the organic solvent is at least one selected from the group consisting of toluene, benzene, xylene, , Decane, ether, dichloromethane, and chlorobenzene, preferably toluene.
In one embodiment of the present invention, the amine compound and the organic solvent are used in a weight ratio of 1: 0.2 to 1: 4; 1: 0.2 to 1: 3 (weight ratio); 1: 0.2 to 1: 1.5 (weight ratio); 1: 0.3 to 1: 1.0 (weight ratio); 1: 0.3 to 1: 0.8 (weight ratio); 1: 0.3 to 1: 0.7 (weight ratio); 1: 0.5 to 1: 1.0 (weight ratio); 1: 0.5 to 1: 0.8 (weight ratio); Or 1: 0.5 to 1: 0.7 (weight ratio); When the organic solvent is less than 0.2 in the mixing ratio, it may be difficult to sufficiently dissolve the amine compound, or it may be difficult to uniformly support the amine compound, and when the organic solvent is more than 4 The penetration ability of the amine compound into the porous organometal structure may be lowered and the content of the amine compound penetrating into the pores of the porous organometal structure may be decreased to reduce the capillary force due to the diffusion of the amine compound, It may be difficult to obtain an effect of improving selectivity and adsorption power.
The supporting step S2 is a step of bringing the amine solution prepared in step S1 into contact with the porous metal organic structure to impregnate and support the amine solution in the pores of the porous metal organic structure.
2 is a cross-sectional view of a method for producing an adsorbent for removing an acidic gas according to an embodiment of the present invention. In step S2 of FIG. 2, , Immersing the porous metal organic structure in an amine solution, the amine solution is imbibed by the capillary force in the pores of the porous metal organic structure, for example, in the pore openings, inside the pores, or both, Organic structure. In step S2, the amine solution prepared in step S1 is applied to quickly penetrate the amine solution into the pores by the capillary force to enable the high concentration of the amine compound to be supported in the pores. When the acid gas is removed, It is possible to increase the contact amount or the contact area.
In one example of the present invention, step S2 may be performed at room temperature or at a temperature of 25 to 50 DEG C, preferably at room temperature. When the temperature exceeds 50 캜, a part of the first amine compound previously bound to the metal in the porous metal organic structure interferes with the penetration of the amine compound into the pore, and penetrates into the pores of the porous organometallic structure due to such interference The content of the amine compound is lowered and it may be difficult to obtain the effect of improving the acid gas selectivity and the adsorption power.
In an embodiment of the present invention, the step (S2) may be performed in an inert gas atmosphere to prevent contact with active oxygen or the like during the loading, and the inert gas may be nitrogen, argon, hydrogen or the like, .
In an example of the present invention, step (S2) can be carried out by stirring the porous metal organic structure and the amine solution to uniformly carry the amine compound into the porous metal organic structure. The stirring may be carried out using a conventional stirrer, and a stirring rate of 25 to 2000 rpm; Preferably 500 to 1500 rpm.
The first drying step (S3) is a step of removing the organic solvent from the porous metal organic structure after step (S2). Step S3 may remove the organic solution infiltrated into the pores and the organic solvent on the surface of the porous metal organic structure to further strengthen the bond between the amine compound and the metal organic structure in the pores.
In one embodiment of the present invention, the porous metal organic structure carrying the amine compound after step (S2) has an inert gas atmosphere and a temperature of 70 to 100 DEG C; Preferably from 80 DEG C to 90 DEG C for 2 to 10 hours; The solvent may be removed for preferably 3 to 6 hours. The inert gas is as mentioned above.
The cleaning step S4 is a step of cleaning the amine compound not participating in the loading after step S3. In an embodiment of the present invention, after the step S3, the porous metal organic structure carrying the amine compound is put into an organic solvent and washed with an organic solvent while stirring to remove the residual amine compound not bound to the porous metal organic structure .
In one example of the present invention, the organic solvent may be an organic solvent as proposed in the present invention, and the stirring may be carried out using a conventional stirrer or spray, for 0.5 to 3 hours; Preferably from 0.5 to 1.5 hours, from 25 to 2000 rpm; Preferably 500 to 1500 rpm; Lt; / RTI >
The second drying step (S5) is a step of removing the organic solvent from the porous metal organic structure carrying the washed amine compound after step S4. In one embodiment of the present invention, after the step S4, the porous metal organic structure carrying the amine compound is filtered and separated from the organic solvent, and an inert gas atmosphere and a temperature of 70 to 100 DEG C; Preferably at a temperature of from 70 DEG C to 90 DEG C for from 2 to 10 hours; The solvent may be removed for preferably 4 to 8 hours. The inert gas is as mentioned above.
The present invention relates to a method for removing an acidic gas in a mixed gas containing an acidic gas, wherein the acidic gas removing method comprises the steps of adsorbing an acidic gas while minimizing loss of hydrocarbon gas using the adsorbent for removing an acidic gas according to the present invention It is possible to remove the acid gas from the gas partial pressure of high pressure as well as low pressure.
According to an embodiment of the present invention, the method for producing an acidic gas will be described with reference to Fig. 3 is a flowchart illustrating an acidic gas removal method according to an embodiment of the present invention. In FIG. 3, the acidic gas removal method includes: preparing an adsorbent Sa1; A contact step Sa2 of the adsorbent with the mixed gas and a regeneration step Sa3 of the adsorbent.
The step (Sa1) of preparing the adsorbent is a step of preparing an adsorbent for removing an acidic gas in a form suitable for the adsorbing and separating apparatus. As an example of the present invention, it can be prepared in the form of a dispersion of the adsorbent for removing an acidic gas, a powder, a molded article, and the like. The adsorbent for removing an acidic gas may be an adsorbent prepared using the acidic gas production method according to the present invention. The dispersion may be prepared by mixing the adsorbent of the present invention with water, an organic solvent, If necessary, more suitable additives can be added. The adsorbent may be included in an amount of 100 to 150 parts by weight based on 100 parts by weight of the dispersion (or the solvent). The powder is powder alone; Or a binder containing at least one of cement such as gypsum and hydrated cement, clay such as bentonite, ataflugite, kaolin, and ceramics such as alumina, silica, zirconia, titania and the like, Lt; / RTI > The adsorbent may be included in the binder in an amount of 1 to 20 parts by weight based on 100 parts by weight of the binder.
The step (Sa2) of contacting the adsorbent with the mixed gas is carried out in such a manner that the prepared adsorbent for removing an acidic gas is attached to an adsorption separation apparatus for removing an acidic gas and a mixed gas requiring removal of an acidic gas is flowed into the apparatus, Is brought into contact with an adsorbent, and an acidic gas is adsorbed and removed in the mixed gas. The device may be a temperature swing adsorption (TSA) device, a pressure swing adsorption (PSA) device, a vacuum swing adsorption (VSA) device, a temperature-vacuum swing adsorption, TVSA) and Pressure & Temperature swing adsorption (PTSA) devices. Of the mixed gas, and the like, natural gas, bio gas containing acid gas, the acid gas is carbon dioxide (CO 2), hydrogen sulfide (H 2 S), sulfur dioxide (SO 2), and nitrogen dioxide (NO 2) And may include at least one kind of carbon dioxide, preferably carbon dioxide.
The regeneration step (Sa3) of the adsorbent is a step of regenerating the adsorbent by removing the acidic gas from the adsorbent adsorbing the acidic gas after step Sa2, and the regeneration step may be performed at a temperature of 70 to 200 ° C .
The present invention is not limited thereto but may be embodied in other specific forms without departing from the spirit or scope of the present invention as set forth in the following claims, The present invention can be variously modified and changed.
Manufacturing example
PBS et al., Int. J. Energy Res. 37 (2013) 746-753. ≪ tb >< TABLE > To remove impurities, water, solvent, atmospheric gas (CO 2 , N 2 , etc.) contained in the synthesized MIL-101 (Cr), treat at 180 ° C under vacuum for 12-18 hours.
Example One
Toluene (0.5 g) and TEPA (Tetraethylenepentamine, 1.2 g) were prepared and then mixed to dissolve TEPA in toluene. The toluene solution in which TEPA was dissolved was placed in a sonicator to prepare a homogeneous mixture. MIL-101 (Cr) (1 g) was loaded into a toluene solution containing TEPA and impregnated in a nitrogen atmosphere at room temperature by a stirrer to prepare 19 wt% TEPA-supported MIL-101 (Cr). The TEPA-loaded MIL-101 (Cr) was dried at 70 ° C and nitrogen atmosphere for 6 hours, and TEPA-supported MIL-101 (Cr) was immersed in toluene (26 g) to remove non- After stirring for 8 hours, TEPA-supported MIL-101 (Cr) was isolated using a centrifuge. In order to remove toluene remaining on the TEPA-supported MIL-101 (Cr), 19 wt% TEPA-supported MIL-101 (Cr) was prepared by treating in an oven at 90 ° C for 3 hours or more.
Example 2
24 wt% TEPA-supported MIL-101 (Cr) was prepared in the same manner as in Example 1 except that TEPA (tetraethylenepentamine, 1.4 g) was used.
Example 3
29 wt% TEPA-supported MIL-101 (Cr) was prepared in the same manner as in Example 1 except that TEPA (Tetraethylenepentamine, 1.6 g) was used.
Experimental Example One
The N content was quantitatively analyzed using an automatic elemental analyzer (
Experimental Example 2
(Cr) and MIL-101 (Cr) prepared in Examples 1 to 3 using CO 2 (purity: 99.999%) at 0 to 120 kPa and BELSORP-mini The isothermal adsorption equilibrium of CO 2 in 101 (Cr) (Comparative Example 1) was measured and shown in FIG. 4 (a) and Table 1.
Experimental Example 3
(Cr) and MIL-101 (Cr) prepared in Examples 1 to 3, using CH 4 (purity: 99.999%) at 0 to 6000 kPa at 25 ° C and BELSORP- Cr) are shown in Figure 4 (b) and Table 1 to measure the equilibrium adsorption isotherm of the CH 4 (Comparative example 1).
Experimental Example 4
The gas mixed with CO 2 (purity: 99.999%) and CH 4 (purity: 99.999%) of 120 kPa and 25,000 ° C at a temperature of 25 ° C and BEL SAPOR-HP, BEL Japan, The CO 2 / CH 4 selectivity of the supported MIL-101 (Cr) and MIL-101 (Cr) (Comparative Example 1) was measured and is shown in Table 1.
CO 2 / CH 4 selectivity
(120 kPa)
(6000 kPa)
4 and Table 1, it can be seen that the acid gas adsorbents prepared in Examples 1 to 3 exhibited significantly higher carbon dioxide selectivity than MIL-101 (Cr). In Examples 1 to 3, the amount of carbon dioxide adsorption was increased as compared with that of MIL-101 (Cr) at 50 kPa or less, and the adsorption amount was increased at high pressure. In addition, Examples 1 and 2 show a lower amount of carbon dioxide adsorption than MIL-101 (Cr) at 120 kPa, but provide a lower adsorption amount of CH 4 than MIL-101 (Cr) It can be confirmed that the loss of the hydrogen hydrocarbon is reduced.
Claims (14)
The amine compound is supported in an amount of 10 to 60 parts by weight based on 100 parts by weight of the porous metal organic structure.
Adsorbent for removing acid gases.
Wherein the amine compound is permeable to the pores of the porous metal organic structure by capillary force.
Wherein the amine compound is bonded to the outer and inner pores of the porous metal organic structure.
The metal organic structure is MIL-101 (MIL = Materials of Institut Lavoisier)
Wherein the metal (M) in the MIL-101 comprises at least one selected from the group consisting of Fe, Al, Cr, Ti, Sc, and V.
The amine compound may be selected from monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), methyldiethanolamine (MDEOA), diisopropanolamine, tetraethylene pentaamine (TEPA), triethylenetetramine ), Pentaethylene hexaamine, ethylenediamine (ED), diethylenetriamine (DETA), piperazine (PZ), polyethyleneimine, melamine, 3,5-diamino-1,2,4-triazole, Amino-1,4-benzenedicarboxylic acid, diisopropylamine, 3-amino-tetrazole, dodecylamine, tris- (2-aminoethyl) -amine, and N, N'-dimethylethylenediamine Wherein the adsorbent contains at least one member selected from the group consisting of nitrogen and oxygen.
Wherein the acidic gas comprises at least one selected from the group consisting of carbon dioxide (CO 2 ), hydrogen sulfide (H 2 S), sulfur dioxide (SO 2 ), and nitrogen dioxide (NO 2 ).
Wherein the adsorbent for removing acid gases has an acid gas adsorption amount at least four times higher than that of the porous metal organic structure not supporting the amine compound at a temperature of 25 ° C to 75 ° C and a carbon dioxide partial pressure of more than 0 and 20 kPa or less. Adsorbent for removing acid gases.
Wherein the adsorbent for removing an acidic gas has a carbon dioxide selectivity to methane of at least 40 at a temperature of from 25 캜 to 75 캜 according to the following formula 1:
[Formula 1]
(Where q is the gas adsorption amount and p is the gas partial pressure).
Immersing the porous metal organic structure in the amine solution so that the amine solution penetrates into the pores of the metal organic structure by capillary force to bind the porous metal organic structure to the pores of the metal organic structure; And
A cleaning step of washing the porous metal organic structure carrying the amine compound with an organic solvent to remove a residual amine compound not bound to the porous metal organic structure;
Wherein the adsorbent for adsorbing an acidic gas is an adsorbent.
Wherein the organic solvent comprises at least one selected from the group consisting of toluene, benzene, xylene, pentane, nonane, decane, ether, dichloromethane and chlorobenzene.
Wherein the amine compound of the amine solution to the organic solvent is contained in an amount of 1: 0.2 to 1: 4 (weight ratio).
A first drying step of the amine compound-supported porous metal organic structure carried out in an inert gas atmosphere and at a temperature of from 70 DEG C to 100 DEG C for from 2 to 10 hours before the step of washing the residual amine compound; And
A second drying step of the amine compound-supported porous metal organic structure carried out in an inert gas atmosphere and at a temperature of 70 ° C to 100 ° C for 2 to 10 hours after the cleaning step of the residual amine compound;
Wherein the adsorbent for adsorbing an acidic gas comprises an adsorbent.
Wherein the acidic gas removing adsorbent is the acidic gas removing adsorbent according to any one of claims 1 to 8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108329486A (en) * | 2018-05-09 | 2018-07-27 | 北京化工大学 | A kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure |
| KR20180115494A (en) * | 2017-04-13 | 2018-10-23 | 국방과학연구소 | Surface modified metal organic franeworks for removal of toxic gases |
| CN111375273A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
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| CN115449086A (en) * | 2022-09-27 | 2022-12-09 | 中国石油大学(北京) | Amino modified MIL-101 (Cr) and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180115494A (en) * | 2017-04-13 | 2018-10-23 | 국방과학연구소 | Surface modified metal organic franeworks for removal of toxic gases |
| CN108329486A (en) * | 2018-05-09 | 2018-07-27 | 北京化工大学 | A kind of preparation method and application of the metal-organic framework materials of hybrid mesoporous structure |
| CN108329486B (en) * | 2018-05-09 | 2020-12-11 | 北京化工大学 | Preparation method and application of metal organic framework material with mesoporous hybrid structure |
| CN111375273A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
| CN111375271A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Method and device for treating flue gas containing sulfur dioxide |
| CN111375271B (en) * | 2018-12-31 | 2022-05-03 | 中国石油化工股份有限公司 | Method and device for treating flue gas containing sulfur dioxide |
| CN111375273B (en) * | 2018-12-31 | 2022-05-03 | 中国石油化工股份有限公司 | Treatment method and device for sulfur dioxide-containing waste gas |
| CN115449086A (en) * | 2022-09-27 | 2022-12-09 | 中国石油大学(北京) | Amino modified MIL-101 (Cr) and preparation method and application thereof |
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