CN114733490B - Cupric chloride ionic liquid modified molecular sieve, preparation method and application - Google Patents
Cupric chloride ionic liquid modified molecular sieve, preparation method and application Download PDFInfo
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- CN114733490B CN114733490B CN202210505223.8A CN202210505223A CN114733490B CN 114733490 B CN114733490 B CN 114733490B CN 202210505223 A CN202210505223 A CN 202210505223A CN 114733490 B CN114733490 B CN 114733490B
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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
- B01J20/02—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
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- 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
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- 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
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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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
- B01J20/3204—Inorganic carriers, supports or substrates
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a chlorocuprate ionic liquid modified molecular sieve, a preparation method and application thereof, and belongs to the field of gas adsorption separation. According to the preparation method, exchange and loading are completed at normal temperature by using the chlorcuprate ionic liquid impregnation mode, the modification process condition is mild, the original molecular sieve frame structure is maintained and improved, the molecular sieve stability and service life are improved, the advantages of the ionic liquid and the molecular sieve are also exerted, the performance of the secondarily synthesized molecular sieve is stable, and the specific surface area is large. The chlorocuprate ionic liquid modified molecular sieve disclosed by the invention combines the advantages of cuprous metal ions, ionic liquid and molecular sieve materials, can be used for adsorbing and drying CO gas in a mixed atmosphere environment, has pertinency to the adsorption of the CO gas, and is easy to regenerate.
Description
Technical Field
The invention belongs to the field of gas adsorption separation, and in particular relates to a chlorocuprate ionic liquid modified molecular sieve, a preparation method and application.
Background
Compared with the liquid adsorbent, the molecular sieve solid adsorbent has the advantages that the adsorbent cannot be mixed into the separated gas, and the problem of solvent loss is avoided. The adsorption quantity of the molecular sieve raw powder to CO gas is low, and the adsorption capacity of the molecular sieve raw powder to CO gas needs to be improved by a directional modification method. The ionic liquid has the advantages of stability, non-volatility and reproducibility, and some ionic liquids have good selective adsorption effect on acid gas, but the higher viscosity limits the application of the ionic liquid as an absorbent in vapor-liquid separation. The cuprous ions have a good outer-layer electronic structure, and adsorb CO molecules through sigma-pi synergistic effect.
Through searching, no research or patent for adsorbing CO gas by using the chlorocuprate ionic liquid modified molecular sieve exists at present. Most of the molecular sieves are cuprous chloride modified molecular sieves or ionic liquid modified molecular sieves for adsorbing CO gas. When the prior pure cuprous ions are used for modifying the molecular sieve, the cuprous ions are not easy to load on the internal framework of the molecular sieve, and the loaded molecular sieve is easy to damage the framework of the molecular sieve in the post-treatment process of drying and roasting, so that the stability of the adsorbent is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a chlorocuprate ionic liquid modified molecular sieve, a preparation method and application.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the chlorocuprate ionic liquid modified molecular sieve comprises the following steps:
(1) Soaking the molecular sieve in dilute hydrochloric acid for pretreatment, and then washing and drying;
(2) Adding the pretreated molecular sieve into chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid, adding dichloromethane as a dispersing agent, uniformly mixing, standing at room temperature for reaction until a precipitate appears, and separating the reaction liquid to obtain the precipitate;
(3) Washing and drying the precipitate, and then placing the precipitate in a vacuum furnace for roasting for 8 hours at 200-300 ℃ to obtain the chloridized 1-butyl-3-methylimidazole cuprate ionic liquid modified molecular sieve.
Further, the molecular sieve in the step (1) is one of a 5A molecular sieve and a 13X, Y type low silica alumina ratio molecular sieve.
Further, in the step (2), the mass ratio of the chloridized 1-butyl-3-methylimidazole copper chloride ionic liquid to the molecular sieve is (0.3-0.7): 1.
further, the synthesis method of the chloridized 1-butyl-3-methylimidazole cupric chloride ionic liquid in the step (2) comprises the following steps:
slowly dripping concentrated hydrochloric acid to dissolve CuCl until the CuCl is completely dissolved to generate chlorocupronic acid;
adding chlorinated 1-butyl-3-methylimidazole crystals into the chlorocupronic acid, adding deionized water until the solid is completely dissolved, reacting for 5 hours under the protection of nitrogen atmosphere and magnetic stirring of a water bath kettle at 40 ℃, standing for 12 hours at normal temperature, layering the solution, and leaving the ionic liquid at the lower layer through a separating funnel to obtain the chlorinated 1-butyl-3-methylimidazole chlorocuprate ionic liquid.
Further, the addition mass of the 1-butyl-3-methylimidazole chloride crystal is 1/2 of the mass of CuCl.
Further, the chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid in the step (2) is replaced by trimethylamine chlorocuprate, triethylamine chlorocuprate, tripropylamine chlorocuprate, 1-methylimidazole chlorocuprate, 1-ethylimidazole bromocuprate, 1-hexyl-3-methylimidazole chlorocuprate and/or N, N-dimethylaniline chlorocuprate.
Further, the chloridized 1-butyl-3-methylimidazole chlorcuprate ionic liquid in the step (2) is replaced by chloridized cuprate ionic liquid taking amine, pyridine, pyrimidine or thiophene as a core.
The chlorocuprate ionic liquid modified molecular sieve is prepared by the preparation method.
The application of the chlorocuprate ionic liquid modified molecular sieve is used as an adsorbent for separating, eliminating, enriching and purifying CO gas.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the chlorocuprate ionic liquid modified molecular sieve, exchange and loading are completed at normal temperature in a chlorocuprate ionic liquid impregnation mode, the modification process condition is mild, the original molecular sieve frame structure is maintained and improved, the stability and service life of the molecular sieve are improved, the advantages of the ionic liquid and the molecular sieve are exerted, the performance of the secondarily synthesized molecular sieve is stable, and the specific surface area is large.
The chlorocuprate ionic liquid modified molecular sieve disclosed by the invention combines the advantages of cuprous metal ions, ionic liquid and molecular sieve materials, and can be used for adsorbing and drying CO gas in a mixed atmosphere environment.
The application of the chlorocuprate ionic liquid modified molecular sieve has pertinence to CO gas adsorption and is easy to regenerate. After molecular sieve adsorption is finished, CO gas can be resolved by heating or reducing pressure (or vacuumizing) to complete regeneration.
Drawings
Fig. 1 is an SEM image of example 1, in which fig. 1 (a) is an SEM image of the surface of the 5A molecular sieve before modification, fig. 1 (b) is an SEM image of the interior of the 5A molecular sieve before modification, fig. 1 (c) is an SEM image of the surface after modification, and fig. 1 (d) is an SEM image of the interior of the molecular sieve after modification.
Fig. 2 is a schematic structural diagram of the adsorption performance test apparatus of example 1.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the attached drawing figures:
example 1
(1) Synthesis of chlorinated 1-butyl-3-methylimidazole chlorocuprate
20g of CuCl white powder is weighed and added into a three-necked flask, and concentrated hydrochloric acid is slowly added dropwise until the CuCl is completely dissolved to generate the cupric chloride acid. Then adding 10g of 1-butyl-3-methylimidazole chloride crystal, adding 80mL of deionized water until the 1-butyl-3-methylimidazole chloride crystal is completely dissolved, reacting for 5h under the protection of nitrogen atmosphere in a water bath kettle under magnetic stirring, standing for 12h at normal temperature, layering the solution, leaving an ionic liquid phase through a separating funnel, and drying the ionic liquid for 12h under the condition of vacuum at 60 ℃ to obtain the 1-butyl-3-methylimidazole chloride cuprate ionic liquid.
(2) Molecular sieve pretreatment
10g of 5A molecular sieve is weighed, 1mol/L hydrochloric acid with the volume being 10 times that of the molecular sieve is added, the mixture is stirred by a glass rod and then soaked for 12 hours, filtered and then washed to be neutral by distilled water, and then the mixture is put into a drying box and dried for 24 hours at 80 ℃.
(3) Modification of chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid
Putting the pretreated molecular sieve into a conical flask, adding the prepared chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid according to the mass ratio of the ionic liquid to the molecular sieve of 0.7, adding 60g of methylene dichloride, putting a volumetric flask on an oscillator, oscillating for 10h at 320 times/frequency division rate, standing for 12h until the solution is separated from particles, carrying out suction filtration to recover a solid part, and washing with distilled water.
The filtered residue was placed in a vacuum oven for 24h at an oven temperature of 63 ℃.
Roasting and activating: and (3) placing the dried molecular sieve into a vacuum furnace, and roasting for 8 hours at 300 ℃ to obtain the chloridized 1-butyl-3-methylimidazole cupric chloride ionic liquid modified molecular sieve.
Referring to fig. 1, fig. 1 is an SEM image of example 1, in which fig. 1 (a) is an SEM image of the surface of the 5A molecular sieve before modification, fig. 1 (b) is an SEM image of the interior of the 5A molecular sieve before modification, fig. 1 (c) is an SEM image of the surface after modification, and fig. 1 (d) is an SEM image of the interior of the molecular sieve after modification, and it is understood from the comparison of the figures that the cupric chloride ionic liquid is loaded on the surface and the interior of the molecular sieve and takes a sphere or ellipsoid shape. The modified molecular sieve has larger internal pore size, increased adsorption sites and increased specific surface area, and is more beneficial to the diffusion and mass transfer of CO molecules.
Referring to fig. 2, fig. 2 is a schematic structural diagram of an adsorption performance testing device in embodiment 1, wherein an inlet of a testing chamber is connected with high-purity nitrogen and carbon monoxide, an outlet pipeline of the testing chamber is connected with a testing instrument and a tail gas absorbing chamber in two ways, and the testing chamber is also connected with a vacuum pump, a pressure gauge and a thermometer. Through the test of the adsorption performance testing device, the adsorption performance and the desorption performance of the chlorcuprate ionic liquid modified molecular sieve of the chloridized 1-butyl-3-methylimidazole cuprate ionic liquid of the embodiment 1 are shown in the table 1 and the table 2, and as can be seen from the table 1 and the table 2, the chloridized cuprate ionic liquid modified molecular sieve improves the adsorption site number of the original molecular sieve, and the CO gas adsorption capacity is increased to a certain extent. When 50 ℃ (323K) or less, the adsorption amount increases with the increase of the temperature; at above 50 ℃, the adsorption amount gradually decreases until no adsorption or complete desorption is achieved.
The molecular sieve of the chlorcuprate ionic liquid has the characteristics of large CO gas adsorption capacity, high selectivity, high adsorption efficiency, convenient separation and the like, and the raw materials in the preparation process of the molecular sieve are low in price, do not use noble metal catalysts, are environment-friendly and safe, and belong to the secondary green synthesis of the molecular sieve. The chlorocuprate ionic liquid molecular sieve can be used as an adsorbent and can be used in the fields of CO gas separation, elimination, enrichment and purification. In addition, by using the method for preparing the modified molecular sieve, more special metal element ionic liquids can be solidly loaded on porous materials such as membrane materials, MOF materials, active carbon and the like, the gas adsorption separation effect can have the characteristics of metal ions, ionic liquids and porous carrier materials, and large-scale industrial application is realized through temperature swing adsorption, pressure swing adsorption or membrane separation methods.
TABLE 1 adsorption capacities of modified molecular sieves at different pressures
| Air source pressure, mpa | 0.1 | 0.5 | 0.7 | 1 | 1.2 | 1.5 | 2 |
| 298K, static adsorption capacity, ml/g | 30 | 50 | 60 | 90 | 100 | 110 | 113 |
Table 2 desorption capacities of modified molecular sieves at different pressures
Example 2
Replacing the molecular sieve in the step (2) of the example 1 with a 13X type low silica alumina ratio molecular sieve;
the mass ratio of the ionic liquid to the molecular sieve in the step (3) is 0.3, and roasting and activating in the step (3): the temperature was 200℃and the other conditions were the same as in example 1.
Example 3
Replacing the molecular sieve in the step (2) of the example 1 with a Y-type low silica alumina ratio molecular sieve;
the mass ratio of the ionic liquid to the molecular sieve in the step (3) is 0.5, and the roasting and activating in the step (3): the temperature was 250℃and the other conditions were the same as in example 1.
The chloride 1-butyl-3-methylimidazole chlorocuprate ionic liquid in the step (3) of the embodiment 1 can be replaced by proton type cuprous salt ionic liquids such as trimethylamine chlorocuprate, triethylamine chlorocuprate, tripropylamine chlorocuprate and the like, aprotic type cupric salt ionic liquids such as 1-methylimidazole chlorocuprate, 1-ethylimidazole bromocuprate, 1-hexyl-3-methylimidazole chlorocuprate, N-dimethylaniline chlorocuprate and the like, and also more types of chlorocuprate ionic liquids such as amines, pyridine, pyrimidine, thiophene and the like as cores, and the corresponding chlorocuprate ionic liquids are loaded on molecular sieves with low silicon aluminum ratio such as NaA, 13X, Y types and the like, so that the chlorocuprate ionic liquid modified molecular sieve for adsorbing CO gas can be prepared.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (1)
1. The application of the chlorocuprate ionic liquid modified molecular sieve is characterized in that the chlorocuprate ionic liquid modified molecular sieve is used as an adsorbent for separating, eliminating, enriching or purifying CO gas, and the preparation method of the chlorocuprate ionic liquid modified molecular sieve comprises the following steps:
(1) Soaking the molecular sieve in dilute hydrochloric acid for pretreatment;
the molecular sieve in the step (1) is a 5A molecular sieve;
(2) Adding the pretreated molecular sieve into chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid, adding dichloromethane as a dispersing agent, uniformly mixing, standing at room temperature for reaction until a precipitate appears, and separating the reaction liquid to obtain the precipitate;
(3) Washing and drying the precipitate, and then placing the precipitate in a vacuum furnace for roasting for 8 hours at 200-300 ℃ to obtain a chloridized 1-butyl-3-methylimidazole cuprate ionic liquid modified molecular sieve;
in the step (2), the mass ratio of the chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid to the molecular sieve is (0.3-0.7): 1, a step of;
the synthesis method of the chloridized 1-butyl-3-methylimidazole chlorocuprate ionic liquid in the step (2) comprises the following steps:
dropwise adding concentrated hydrochloric acid into CuCl to dissolve the CuCl, and continuously dropwise adding the concentrated hydrochloric acid until the CuCl is completely dissolved to generate chlorocupronic acid;
adding chlorinated 1-butyl-3-methylimidazole crystals into the chlorocupronic acid, adding deionized water until the solid is completely dissolved, reacting for 5 hours under the protection of nitrogen atmosphere and magnetic stirring of a water bath kettle at 40 ℃, standing for 12 hours at normal temperature, layering the solution, and leaving the ionic liquid at the lower layer through a separating funnel to obtain chlorinated 1-butyl-3-methylimidazole chlorocuprate ionic liquid;
the addition mass of the chloridized 1-butyl-3-methylimidazole crystal is 1/2 of the mass of CuCl.
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