CN114558546B - Cu (I)/molecular sieve adsorbent and preparation method and application thereof - Google Patents
Cu (I)/molecular sieve adsorbent and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 82
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003463 adsorbent Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 150000001879 copper Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 25
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 25
- 229940045803 cuprous chloride Drugs 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 abstract description 9
- 239000012298 atmosphere Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 32
- 230000000694 effects Effects 0.000 description 15
- 238000000926 separation method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000003068 static effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- 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
- B01J20/3007—Moulding, shaping or extruding
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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
- B01J20/3021—Milling, crushing or grinding
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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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a Cu (I)/molecular sieve adsorbent, and a preparation method and application thereof, wherein the preparation method comprises the following steps: selecting a molecular sieve, and drying the molecular sieve; adding the molecular sieve into an alcohol solvent, and stirring at room temperature until the molecular sieve is uniformly mixed; slowly adding monovalent copper salt powder, and stirring at room temperature to obtain a mixture; and filtering, drying, forming and grinding the mixture to obtain the Cu (I)/molecular sieve adsorbent. The whole preparation process is safe and simple, does not need to be synthesized in harsh environments such as dry inert atmosphere or vacuum, is environment-friendly and saves energy consumption. The Cu (I)/molecular sieve adsorbent provided by the invention is modified by introducing copper ions through a one-step method, so that the adsorption quantity of carbon monoxide of the molecular sieve can be improved, and the adsorption quantity of the CO reaches 4.1mmol/g under the conditions of the temperature of 25 ℃ and the pressure of 1000 mbar.
Description
Technical Field
The invention relates to the fields of adsorbent technology and adsorption materials, in particular to a Cu (I)/molecular sieve adsorbent, and a preparation method and application thereof.
Background
Hydrogen is an important clean and renewable energy source, and its efficient use remains a major difficulty. Methanol hydrogen production is considered to be one of the most promising hydrogen production technologies for hydrogen fuel cells, but the hydrogen produced by the method often contains carbon monoxide impurity gas, and trace CO can poison catalysts in the fuel cells, so that the normal operation of the cells is affected, particularly the hydrogen fuel cells taking platinum as a catalyst, and the content of CO must be as low as 0.2ppmv, so that the methanol reforming hydrogen production must be purified. The adsorption separation method is a method for realizing high-efficiency separation by utilizing the adsorption enrichment and desorption of an adsorption bed layer by utilizing the adsorption capability and selectivity difference of an adsorbent on different gas components. Depending on the mode of desorption regeneration, it can be classified into Temperature Swing Adsorption (TSA) and Pressure Swing Adsorption (PSA). The temperature swing adsorption realizes regeneration separation according to the adsorption capacity difference of the adsorbents at different temperatures, and the pressure swing adsorption realizes regeneration separation according to the adsorption capacity difference of the adsorbents at different pressures. Obviously, the heating-cooling process by varying the temperature is extremely energy-consuming, and compared with the PSA process, the regeneration rate is faster, the energy consumption is low, the equipment is simple and the degree of automation is high, and the large-scale industrial production is easy. Currently, there are various types of adsorbents such as porous carbon, porous organic polymers, metal organic frameworks, etc., which are being widely studied and have remarkable performance effects. Therefore, adsorption separation technology is expected to replace cryogenic separation technology in the near future.
Patent CN1103816a discloses a preparation method of zeolite adsorbent for high selectivity adsorption of carbon monoxide, which adopts ion exchange and impregnation method to load copper ion on NaY zeolite, but the zeolite is mixed with halloysite clay and pore-expanding agent, extruded and formed first, then treated with aqueous solution of NaOH containing SiO 2 to prepare composite carrier, then ion exchanged into Cu (ii) -Y zeolite by Cu 2+, finally reduced by CO or H 2 to prepare finished product, the process is complex and the cost is high. Patent CN112705180a discloses a method for preparing an adsorbent for CO pressure swing adsorption, which uses organic amine to perform gas-solid phase treatment on a modified carrier, then mixes with a copper source and forms the mixture to prepare an adsorbent precursor, so that the problems of low mechanical strength and low CO adsorption efficiency of a conventional adsorbent are solved, but the carrier is still required to be modified by an aluminum source and phosphoric acid, and the dispersity of copper ions is low.
In summary, although some preparation methods of adsorbents for adsorbing carbon monoxide have been reported in the prior art, the preparation process is complex and the cost is high, and how to find a simple and quick preparation method of the adsorbent is realized at the same time: a. the adsorbent has high pore volume, high specific surface area and high adsorption capacity; b. the selectivity to carbon monoxide is high, and the separation effect is obvious in a hydrogen-carbon monoxide separation system; c. the copper ion has higher dispersity, which is the technical problem to be solved at present.
Disclosure of Invention
Aiming at the problems of low adsorption capacity, low adsorption rate, low adsorption selectivity and complex adsorbent preparation existing in the existing CO attachment, the preparation method has the advantages of simple steps, easy realization, large adsorption capacity, high selectivity and the like.
First, the invention provides a preparation method of a Cu (I)/molecular sieve adsorbent, which comprises the following steps:
Selecting a molecular sieve, and drying the molecular sieve;
Adding the molecular sieve into an alcohol solvent, and stirring at room temperature until the molecular sieve is uniformly mixed;
Slowly adding monovalent copper salt powder, and stirring at room temperature to obtain a mixture;
and filtering, drying, tabletting, forming and grinding the mixture to obtain the Cu (I)/molecular sieve adsorbent.
Preferably, the molecular sieve is one or more of a 5A molecular sieve, a ZSM-5 molecular sieve, a 13X molecular sieve, or a NaY molecular sieve.
Preferably, the monovalent copper salt is one or more of cuprous chloride or cuprous sulfate.
Preferably, the alcohol solvent is one or more of ethanol, methanol, propanol or butanol.
Preferably, the molar ratio of the molecular sieve, the monovalent copper salt and the alcohol solvent is (0.8-1.2): 0.1-0.4): 20-50.
Preferably, the temperature of the molecular sieve is 80-120 ℃ and the drying time is 8-16 h.
Preferably, the temperature of the drying is 80-120 ℃, and the drying time is 8-16 h.
Preferably, the pressure of the tabletting molding is 1.0-2.5 MPa, and the grinding mesh number of the grinding is 20-80 meshes.
Further, the invention also provides a Cu (I)/molecular sieve adsorbent, which is prepared by the preparation method of the Cu (I)/molecular sieve adsorbent.
The invention also provides an application of the Cu (I)/molecular sieve adsorbent in carbon monoxide adsorption.
The beneficial effects are that:
1) According to the invention, different molecular sieves are used as carriers, cuprous chloride is used as a copper source, the copper (I)/molecular sieve adsorbent is directly prepared by mixing the copper (I)/molecular sieve adsorbent in an ethanol solution through a one-step method, the dispersity of monovalent copper ions can be remarkably improved by using an alcohol solvent, monovalent Cu + is effectively protected in the preparation process by providing liquid-phase reduction conditions in the preparation process, and contact air is prevented from being oxidized into Cu 2+, so that the monovalent copper ions are more uniformly loaded on the surface and pore channels of the molecular sieve; the existing adsorbent preparation methods are mostly ion exchange methods, copper ions cannot be uniformly loaded in molecular sieve pore channels, and Cu loading cannot be controlled.
2) Compared with the common dipping method and the double-solvent method for adsorbing carbon monoxide, the method provided by the application has the advantages of providing pi complexation effect by uniformly loading monovalent copper ions on the surface and in the pore canal, greatly improving the adsorption quantity, and having high activity, high stability and high reproducibility. Meanwhile, compared with the prior art that monovalent copper salt is loaded on a molecular sieve, the monovalent copper salt is generally ground firstly and then heated in inert gas at high temperature, the preparation process of the application does not need inert gas protection and does not need harsh conditions such as high temperature, high pressure and the like, so that the method is safe, simple and convenient, environment-friendly and energy-saving. In addition, the method can lead the surface and pore canal of the molecular sieve to load more uniform monovalent copper ions, and through carrying out monovalent copper modification on the molecular sieve, the CO and monovalent copper form pi complex bonds, and the pi complex bonds are stronger than Van der Waals force, so that the prepared molecular sieve adsorbent improves the selectivity on CO on one hand, solves the problem of unobvious separation effect in a hydrogen-carbon monoxide separation system, and improves the adsorption quantity on CO on the other hand. Therefore, the molecular sieve adsorbent prepared by the method can keep excellent adsorption performance and selectivity at room temperature, has good regeneration performance, and is suitable for the process of adsorbing and separating carbon monoxide.
3) The adsorbent selects 5A, ZSM-5, 13X and NaY molecular sieves with more proper pore diameters as a matrix, and the pore diameter is 1.33-2.5 times of the kinetic diameter of carbon monoxide, so that the adsorbent has a better adsorption effect and is convenient to operate.
Drawings
The following is a brief description of what is expressed in the drawings of the specification:
FIG. 1 is a flow chart of a method for preparing a Cu (I)/molecular sieve adsorbent according to the present disclosure;
FIG. 2 is a graph showing isothermal adsorption of carbon monoxide by Cu (I)/molecular sieve adsorbents prepared in examples 1-5 according to the present application;
FIG. 3 is a graph showing isothermal adsorption of carbon monoxide by Cu (I)/molecular sieve adsorbents prepared in example 3 and comparative examples 1-5 according to the present application;
FIG. 4 is a graph showing isothermal adsorption of carbon monoxide by Cu (I)/molecular sieve adsorbents prepared in example 1 and comparative examples 6-10 according to the present application;
FIG. 5 is a graph showing isothermal adsorption of carbon monoxide by the molecular sieve adsorbents according to comparative examples 11 to 14.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the application provides a Cu (I)/molecular sieve adsorbent and a preparation method thereof, as shown in figure 1, and the method comprises the following steps:
s1: selecting a molecular sieve, and drying the molecular sieve;
s2: adding the molecular sieve into an alcohol solvent, and stirring at room temperature until the molecular sieve is uniformly mixed;
S3: slowly adding monovalent copper salt powder, and stirring at room temperature to obtain a mixture;
s4: and filtering, drying, tabletting, forming and grinding the mixture to obtain the Cu (I)/molecular sieve adsorbent.
Example 1
Drying 1g of 5A molecular sieve, uniformly mixing with 30mL of ethanol, stirring at room temperature for 10min, slowly adding 0.1g of cuprous sulfate into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and forming after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/5A adsorbent.
Example 2
Drying 1g of 5A molecular sieve, uniformly mixing with 30mL of ethanol, stirring at room temperature for 10min, slowly adding 0.2g of cuprous chloride into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and forming after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/5A adsorbent.
Example 3
Drying 1g of 5A molecular sieve, uniformly mixing with 30mL of ethanol, stirring at room temperature for 10min, slowly adding 0.3g of cuprous chloride into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and forming after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/5A adsorbent.
Example 4
Drying 1g of 13X molecular sieve, uniformly mixing with 30mL of ethanol, stirring at room temperature for 10min, slowly adding 0.4g of cuprous chloride into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and molding after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/13X adsorbent.
Example 5
Drying 1g of NaY molecular sieve, uniformly mixing with 30mL of ethanol, stirring at room temperature for 10min, slowly adding 0.5g of cuprous chloride into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and molding after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/NaY adsorbent.
Carbon monoxide adsorption tests were performed on an IGA intelligent gravimetric analyzer using the adsorbents prepared in examples 1-5 for adsorption. The purity of carbon monoxide in the gas is 99.9%, the activity test experimental condition of the adsorbent is that the static adsorption test is carried out on the adsorbent filled with Cu (I)/molecular sieve on an IGA intelligent gravimetric analyzer under the conditions that the temperature is 25 ℃ and the pressure is 0-1000mbar, the quality change in a sample tube is detected, and the static adsorption quantity is obtained, and the test result is shown in figure 2. It can be seen that the adsorbents prepared by the scheme of the application have ideal adsorption effect on CO, wherein the maximum adsorption amount can reach 4.12mmol/g (25 ℃ C., 1000 mbar).
Comparative example 1
Drying 1g of 5A molecular sieve, uniformly mixing with 30mL of water, stirring at room temperature for 10min, slowly adding 0.1g of cuprous chloride into the mixture, stirring at room temperature for 3h, filtering the obtained mixture, drying at 75 ℃ for 12h, tabletting and molding after treatment, wherein the pressure is 1.5MPa, and the grinding mesh number is 60, thus obtaining the Cu (I)/5A adsorbent.
Comparative examples 2 to 5
Cu (I)/5A adsorbents were prepared and adsorption test was performed according to each of the steps and conditions of comparative example 1. The conditions of the modification are shown in Table 1, except that the addition amount of cuprous chloride is changed.
Carbon monoxide adsorption tests were performed on an IGA intelligent gravimetric analyzer using the adsorbents prepared in comparative examples 1-5 for adsorption. The purity of carbon monoxide in the gas is 99.9%, the activity test experimental condition of the adsorbent is that the static adsorption test is carried out on the IGA intelligent gravimetric analyzer by the adsorbent filled with Cu (I)/molecular sieve under the conditions of the temperature of 25 ℃ and the pressure range of 0-1000mbar, the static adsorption quantity is obtained by detecting the mass change in the sample tube, the test result is shown in figure 3, and compared with the test result of the embodiment 3, the adsorption effect of the prepared adsorbent CO is not ideal as compared with the scheme provided by the application when water is used for replacing alcohol solvent in the preparation process.
Comparative example 6
1G of 5A molecular sieve is dried, mixed and ground with 0.1g of cuprous chloride at room temperature, the obtained mixture is filtered, and the mixture is heated for 12 hours in an inert gas atmosphere at 400 ℃ to obtain the Cu (I)/5A adsorbent.
Comparative examples 7 to 10
Cu (I)/5A adsorbents were prepared and adsorption tested according to the respective procedures and conditions of example 11. The conditions of the modification are shown in Table 1, except that the addition amount of cuprous chloride is changed.
Carbon monoxide adsorption tests were performed on an IGA intelligent gravimetric analyzer using the adsorbents prepared in comparative examples 6-10. The purity of carbon monoxide in the gas is 99.9%, the activity test experimental condition of the adsorbent is that under the conditions that the temperature is 25 ℃ and the pressure range is 0-1000mbar, the static adsorption test is carried out on the adsorbent filled with Cu (I)/molecular sieve on an IGA intelligent gravimetric analyzer, the quality change in a sample tube is detected, the static adsorption quantity is obtained, the test result is shown in figure 4, and compared with the test result of the embodiment 1, when the solvent is not used in the preparation process, the molecular sieve and a copper source are directly ground and mixed, and the adsorption effect of the prepared adsorbent CO is not ideal as compared with the scheme provided by the application.
Comparative example 11
The adsorbent was synthesized by impregnation, and 1g of 5A molecular sieve was uniformly mixed with 30mL of water, stirred at room temperature for 10min, 0.3g of copper chloride was slowly added thereto, stirred at room temperature for 3h, the resulting mixture was filtered, and reduced at 200℃under vacuum for 12h. Tabletting and molding after treatment to obtain the Cu (I)/5A adsorbent.
Comparative example 12
The adsorbent was synthesized by impregnation, and 1g of 5A molecular sieve was uniformly mixed with 30 parts of ethanol, stirred at room temperature for 10 minutes, 0.3g of copper sulfate was slowly added thereto, stirred at room temperature for 3 hours, the resulting mixture was filtered, and reduced at 200℃under vacuum for 12 hours. Tabletting and molding after treatment to obtain the Cu (I)/5A adsorbent.
Comparative example 13
Synthesizing the adsorbent by a double-solvent method, uniformly mixing 1g of 5A molecular sieve with 200mL of n-hexane, firstly carrying out ultrasonic treatment at room temperature for 30min, then stirring at room temperature for 10min, slowly adding 18mL of aqueous solution containing 0.3g of copper chloride into the stirred solution, stirring at room temperature for 4h, carrying out vacuum reduction at 200 ℃ for 12h, carrying out treatment, and tabletting and forming to obtain the Cu (I)/5A adsorbent.
Comparative example 14
Synthesizing the adsorbent by a double-solvent method, uniformly mixing 1g of 5A molecular sieve with 200mL of n-hexane, firstly carrying out ultrasonic treatment at room temperature for 30min, then stirring at room temperature for 10min, slowly adding 18mL of aqueous solution containing 0.3g of copper sulfate into the stirred solution, stirring at room temperature for 4h, carrying out vacuum reduction at 200 ℃ for 12h, carrying out treatment, and tabletting and forming to obtain the Cu (I)/5A adsorbent.
Carbon monoxide adsorption tests were performed on an IGA intelligent gravimetric analyzer using the adsorbents prepared in comparative examples 11-14 for adsorption. The purity of carbon monoxide in the gas is 99.9%, the activity test experimental condition of the adsorbent is that the static adsorption test is carried out on the adsorbent filled with Cu (I)/molecular sieve on an IGA intelligent gravimetric analyzer under the conditions that the temperature is 25 ℃ and the pressure is 0-1000mbar, the quality change in a sample tube is detected, the static adsorption quantity is obtained, the test result is shown in figure 5, and the adsorption effect of the adsorbent prepared by the traditional impregnation method or the double-solvent method is still not ideal as compared with the scheme provided by the application.
The carbon monoxide adsorption test results for each example and comparative example are shown in Table 1 at a temperature of 25℃and a pressure of 1000 mbar.
TABLE 1 Each example, comparative example component addition amount and adsorption test result
Numbering device | Molecular sieve | Copper source | Molecular sieve copper source (wt: wt) | CO adsorption quantity (mmol/g) |
Example 1 | 5A | Cuprous sulfate | 1:0.1 | 2.89 |
Example 2 | 5A | Cuprous chloride | 1:0.2 | 3.84 |
Example 3 | 5A | Cuprous chloride | 1:0.3 | 4.12 |
Example 4 | 13X | Cuprous chloride | 1:0.4 | 3.25 |
Example 5 | NaY | Cuprous chloride | 1:0.5 | 3.21 |
Comparative example 1 | 5A | Cuprous chloride | 1:0.1 | 1.48 |
Comparative example 2 | 5A | Cuprous chloride | 1:0.2 | 1.64 |
Comparative example 3 | 5A | Cuprous chloride | 1:0.3 | 1.85 |
Comparative example 4 | 5A | Cuprous chloride | 1:0.4 | 1.77 |
Comparative example 5 | 5A | Cuprous chloride | 1:0.5 | 1.09 |
Comparative example 6 | 5A | Cuprous chloride | 1:0.1 | 2.35 |
Comparative example 7 | 5A | Cuprous chloride | 1:0.2 | 2.49 |
Comparative example 8 | 5A | Cuprous chloride | 1:0.3 | 2.64 |
Comparative example 9 | 5A | Cuprous chloride | 1:0.4 | 2.63 |
Comparative example 10 | 5A | Cuprous chloride | 1:0.5 | 2.52 |
Comparative example 11 | 5A | Copper chloride | 1:0.3 | 1.29 |
Comparative example 12 | 5A | Copper sulfate | 1:0.3 | 1.37 |
Comparative example 13 | 5A | Copper chloride | 1:0.3 | 1.53 |
Comparative example 14 | 5A | Copper sulfate | 1:0.3 | 1.69 |
As can be seen from the comparison results of the examples and the comparative examples, the technical scheme provided by the invention well solves the problems of low adsorption capacity, low adsorption rate, poor adsorption selectivity and the like, and achieves better technical effects.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. A method for preparing a Cu (I)/molecular sieve adsorbent, which is characterized by comprising the following steps:
Selecting a molecular sieve, and drying the molecular sieve, wherein the molecular sieve is a 5A molecular sieve;
Adding the molecular sieve into an alcohol solvent, and stirring at room temperature until the molecular sieve is uniformly mixed;
Slowly adding monovalent copper salt powder, and stirring at room temperature to obtain a mixture;
And filtering, drying, tabletting, forming and grinding the mixture to obtain the Cu (I)/molecular sieve adsorbent, wherein the drying temperature is 60-120 ℃, and the drying time is 8-16 h.
2. The method for preparing the Cu (I)/molecular sieve adsorbent according to claim 1, wherein the monovalent copper salt is one or more of cuprous chloride or cuprous sulfate.
3. The method for preparing a Cu (I)/molecular sieve adsorbent as recited in claim 1, wherein the alcoholic solvent is one or more of ethanol, methanol, propanol, or butanol.
4. The preparation method of the Cu (I)/molecular sieve adsorbent according to claim 1, wherein the mass ratio of the molecular sieve, the monovalent copper salt and the alcohol solvent is (0.8-1.2): 0.1-0.4): 20-50.
5. The method for preparing a Cu (I)/molecular sieve adsorbent according to claim 1, wherein the pressure of the tabletting is 1.0-2.5 mpa, and the grinding mesh number of the grinding is 20-80 mesh.
6. A Cu (I)/molecular sieve adsorbent prepared by the method of any of claims 1-5.
7. Use of a Cu (I)/molecular sieve adsorbent as defined in claim 6 for carbon monoxide adsorption.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101947430A (en) * | 2010-10-11 | 2011-01-19 | 孙玉坤 | Gas separation adsorbent for pressure swing adsorption process and preparation method and application thereof |
CN103553070A (en) * | 2013-10-30 | 2014-02-05 | 西南化工研究设计院有限公司 | 13X type molecular sieve for CO adsorption, as well as preparation method and applications of molecular sieve |
KR20170076502A (en) * | 2015-12-24 | 2017-07-04 | 주식회사 포스코 | Adsorbent for selective adsorption of carbon monoxide and method for preparation thereof |
CN110652960A (en) * | 2018-06-28 | 2020-01-07 | 中国科学院大连化学物理研究所 | Carbon monoxide adsorbent and preparation method and application thereof |
CN112755956A (en) * | 2020-12-29 | 2021-05-07 | 洛阳建龙微纳新材料股份有限公司 | High-selectivity carbon monoxide adsorbent and preparation method and application thereof |
CN112808230A (en) * | 2020-12-24 | 2021-05-18 | 大连理工大学 | Preparation method of Cu (I)/Y adsorbent and application thereof in dynamic removal of low-concentration CO |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101947430A (en) * | 2010-10-11 | 2011-01-19 | 孙玉坤 | Gas separation adsorbent for pressure swing adsorption process and preparation method and application thereof |
CN103553070A (en) * | 2013-10-30 | 2014-02-05 | 西南化工研究设计院有限公司 | 13X type molecular sieve for CO adsorption, as well as preparation method and applications of molecular sieve |
KR20170076502A (en) * | 2015-12-24 | 2017-07-04 | 주식회사 포스코 | Adsorbent for selective adsorption of carbon monoxide and method for preparation thereof |
CN110652960A (en) * | 2018-06-28 | 2020-01-07 | 中国科学院大连化学物理研究所 | Carbon monoxide adsorbent and preparation method and application thereof |
CN112808230A (en) * | 2020-12-24 | 2021-05-18 | 大连理工大学 | Preparation method of Cu (I)/Y adsorbent and application thereof in dynamic removal of low-concentration CO |
CN112755956A (en) * | 2020-12-29 | 2021-05-07 | 洛阳建龙微纳新材料股份有限公司 | High-selectivity carbon monoxide adsorbent and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
CuCl负载型吸附剂吸附CO的研究;李丽;《山西化工》(第1期);第34-36页 * |
分子筛负载CuCl制备CO吸附剂的研究;李丽;《山西化工》;第33卷(第6期);第16-18页 * |
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