CN107500307B - A kind of preparation method and applications of zeolite molecular sieve - Google Patents

A kind of preparation method and applications of zeolite molecular sieve Download PDF

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CN107500307B
CN107500307B CN201710943405.2A CN201710943405A CN107500307B CN 107500307 B CN107500307 B CN 107500307B CN 201710943405 A CN201710943405 A CN 201710943405A CN 107500307 B CN107500307 B CN 107500307B
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molecular sieve
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zeolite molecular
solution
separation
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CN107500307A (en
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杨江峰
刘佳奇
尚华
杨成荫
李晋平
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Taiyuan University of Technology
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • 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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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/22—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • 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
    • 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
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The invention belongs to technical field of separation materials, and in particular to a kind of preparation method of zeolite molecular sieve.It more specifically, is a kind of couple of CH4And CO2Gas separation material with " molecule door " effect, the separation material can be widely applied to CO in natural gas2Separation and recycling.The preparation method is that carrying out silica alumina ratio adjusting, used material molar ratio is SiO2/Al2O3=4.0-4.26 obtains ZK-5 molecular sieve；Molecular sieve is added to potassium salt soln, heating stirring carries out ion exchange, and is continuously added into distilled water during heating to keep the total amount of solution constant；After ion exchange, continues washing filtering with deionized water, be dried to obtain K-ZK-5 zeolite molecular sieve.Change and K due to silica alumina ratio+Introducing so that the molecular sieve shows " molecule door " effect, i.e. the lesser CO of adsorption dynamics adsorption kinetics diameter2, to CH4And N2It is extremely low etc. biggish gas molecule adsorbance.

Description

A kind of preparation method and applications of zeolite molecular sieve
Technical field
The invention belongs to technical field of separation materials, and in particular to a kind of preparation method of zeolite molecular sieve.More specifically It says, is a kind of couple of CH4And CO2Gas separation material with " molecule door " effect, the separation material can be widely applied to natural gas Middle CO2Separation and recycling.
Background technique
Natural gas is one kind with CH4High-quality, efficient, clean low-carbon energy based on gas, can be divided into conventional gas And Unconventional gas.Currently, conventional gas has been widely used for the every field of production, life, and its demand day Benefit increases.Furthermore sub- quality natural gas reserves (including sour natural gas reserves) are distributed quite extensive, rich reserves.Sub- quality day Right gas reserves are defined as containing the CO for being greater than 2%2, 4% N2With the hydrogen sulfide (H of 4 ppm2S gas field).Half according to estimates Above natural gas resource contains the CO greater than 2%2, this is just to the exploitation (packet of sub- quality, unconventional and remote gas reserves Include by LNG produce exploitation) gas treatment propose new challenge.CO2、H2S and other sour gas must be from natural gases Middle removing, because in presence of water, these impurity can form the acid of corrosion pipeline and other equipment.Although the present invention is not Pay close attention to H2The removal of S, but it is also very necessary that these toxic sour gas are removed from natural gas.
Natural gas removes CO2Technique, mainly include following several method:
1. solution absorption techniques: utilizing CO2It reacts to each other in absorption tower with absorbent, makes CO2It is absorbed into chemistry In solvent, heat resolve goes out in Analytic Tower later, to be separated and be recycled.The processing disadvantages packet of conventional amine processing method It includes: (1) big energy needed for amine regeneration；(2) the relatively low CO of amine2Load capacity needs high solvent cycle rate and big The high pressure absorber of diameter；(3) corrosivity amine aqueous solution easily causes high equipment corrosion rate；(4) amine is easy to degrade and be formed with Machine acid.
2. cryogenic separation technology: cryogenic separation technology is to utilize the difference of each gas component boiling point in natural gas _ raw material gas, Each component in gas is required to condense out according to technique by cryogenic refrigeration, then will be separated one by one using the way of distillation. Although CO2Cryogenic separation as highly selective processing CO2Natural gas there are good potentiality, but the decarbonization process also has one A little disadvantages, if process equipment is at high cost, energy consumption is high.
3.CO2Selective film technology: CO2Selective film technology is in large-scale separation CO2Aspect is applied in gas industry With CO is captured in combustion product gases2Aspect is increasing.The business membrane technology used in gas industry mainly passes through solution- The non-porous polymer film of flooding mechanism separation component.Gas molecule is transmitted by solution diffusion mechanism, is passed through first by film By gas molecules sorb into film, then occurred by the diffusion of membrane material or infiltration.Therefore, pass through the group of natural gas feed Point solubility and the difference of migratory behaviour realize the separation of gas component.But membrane separation process there is also its inevitably Disadvantage, such as CH4Lose it is more, seldom arrive high-purity C H4, and film cost is more expensive and vulnerable to pollution.
4. adsorption separation technology: using adsorbent to CO in mixed gas2And CH4Adsorption come realize gas separate Technology.Similar with solution absorption process, adsorption separation technology needs to adsorb for gas separation and regeneration stage.Adsorbent is again Raw or desorption can pass through the suction using (thermal conversion adsorbs, TSA) and different pressures (pressure-variable adsorption, PSA) at different temperatures The difference of attached capacity is realized.The method that constantly research passed through adsorbing separation in recent years separates CO from natural gas2, thus conduct The potential alternative of solution absorption techniques.And in isolated absorbing process common adsorbent have carbon material (active carbon and Carbon molecular sieve), molecular sieve, the materials such as silica solution and metal organic framework (MOFs).Compare this few class adsorbent discovery: carbon Material does not have uniform pore structure, and MOFs stability of material is weaker, in comparison molecular sieve have uniform pore structure and Pore size, thermostabilization is good, and can modulation specific surface area and pore volume, therefore to the adsorbent of molecular sieve study and answer It is more.
Summary of the invention
In view of the foregoing, in order to solve CO in natural gas2Purification and recycling, the present invention provides a kind of zeolite molecules The preparation method and applications of sieve.
It with ZK-5 is that basis framework material (draped over one's shoulders by US4994249 patent that gas separation material proposed by the present invention, which is a kind of, It is prepared by the method for dew), the method by regulating and controlling silica alumina ratio and ion exchange, due to introducing more K in the duct of ZK-5+, Generate " molecule door " effect.The relatively large molecule of molecular dynamics diameter such as CH4And N2Adsorbance be substantially reduced, and aperture Diameter molecule CO2Adsorbance variation less, to obtain relatively high CO2/CH4Adsorptive selectivity.
Wherein " molecule door " effect refer specifically to the ion balance in the duct of certain molecular sieves can due to and guest molecule It interacts and leads to of short duration and reversible offset, the offset of ion balance can permit large-sized guest molecule access aperture Road.For different guest molecules, there is apparent differences for this phenomenon.Utilize " molecule door " effect that can make certain visitors Body molecule enters duct, and repels other guest molecules, and then obtains high Selective adsorption.It can be found in Jin Shang et al. Discriminative Separation of Gases by a " Molecular Trapdoor " Mechanism delivered In Chabazite Zeolites and Determination of Composition Range for " Molecular Trapdoor" Effect in Chabazite Zeolite.The present invention is achieved by the following technical solutions: a kind of zeolite The preparation method of molecular sieve, includes the following steps:
1) ZK-5 is prepared
Silica alumina ratio adjusting is carried out, used material molar ratio is SiO2/Al2O3=4.0-4.26 obtains different silica alumina ratios ZK-5 molecular sieve；
2) ion exchange
Molecular sieve is added to potassium salt soln, heating stirring carries out ion exchange, and is continuously added into during heating Distilled water is constant to keep the total amount of solution；After ion exchange, continues washing filtering with deionized water, be dried to obtain K-ZK-5 Zeolite molecular sieve.
It is method, i.e. this hair disclosed by US4994249 patent that the step 1), which prepares the technique of ZK-5, in the present invention The technique of ZK-5 is prepared used by bright except being adjusted to the silica alumina ratio of raw material, other are complete with method disclosed by the patent It is exactly the same.Also, using the ZK-5 molecular sieve that different silica alumina ratios are prepared after silica alumina ratio of the present invention, corresponding silicon Aluminium ratio is between 3.21-3.30, and corresponding K+With Cs+Molar ratio be about 0.66-0.69.But use is of the present invention Step 2 can significantly improve K+In ion balance (K+And Cs+) in content, K+Content can be up to 90% or more.
As the further improvement of technical solution of the present invention, the concentration of potassium salt soln is 0.5M-2M, needed for every gram molecule sieve Solution be 30-50mL.
As the further improvement of technical solution of the present invention, in step 2, the heating temperature is 343-363K, exchange time Number is 3 times -6 times, and the time of each heating stirring is 4-12 hours.
As the further improvement of technical solution of the present invention, the potassium salt soln is KCl solution, KNO3Solution or K2SO4It is molten Liquid.
Invention further provides a kind of any of the above-described K-ZK-5 that the preparation method of zeolite molecular sieve is prepared boilings Stone molecular sieve is as CO2Adsorbent is in CO2Separation and recycling in application.
The present invention also provides a kind of any of the above-described K-ZK-5 zeolites that the preparation method of zeolite molecular sieve is prepared point Son sieve is as CO2Adsorbent CO in removing natural gas2Application.
The present invention is with ZK-5 molecular sieve for basic framework material, the method by adjusting silica alumina ratio and ion exchange, system It is standby gone out the K-ZK-5 of specific silica alumina ratio.Change and K due to silica alumina ratio+Introducing so that the molecular sieve shows " molecule Door " effect, the i.e. lesser CO of adsorption dynamics adsorption kinetics diameter2, to CH4And N2It is extremely low etc. biggish gas molecule adsorbance therefore pre- Sentence to CO2/CH4Gaseous mixture CO with higher2Selectivity.The separation material can be adapted for CO in natural gas2Purification and return It receives, there is critically important practical value.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.
Fig. 1 is the XRD diffraction pattern for the K-ZK-5 that Examples 1 and 2 are prepared.As can be seen from the figure the position of diffraction maximum It coincide with ZK-5 of the relative intensity and in patent document, this proves that using embodiment preparation be ZK-5 molecular sieve.
A, b are respectively the EDS map of Examples 1 and 2 in Fig. 2.Energy spectrum analysis shows in K-ZK-5 mainly containing Si, Al, K tri- Kind element and a small amount of Cs, wherein being about 9/1 by the molar ratio for calculating discovery K and Cs.
Fig. 3 is the CH of Examples 1 and 24、CO2、N2Adsorption isotherm at 298K.From the figure we can see that implementing Example 1 and 2 pair CO2Adsorbance with higher, and to CH4And N2Adsorbance it is lower, or even as the raising adsorbance of pressure is small In N2, show " molecule door " effect.
Fig. 4 is by Langmuir-Freundlich isotherm model to the CO of sample2、CH4Pure gas component gas is inhaled Attached thermoisopleth is fitted, and fitting parameter calculates material to CO according to perfect solution adsorption theory (IAST)2/CH4Mixed gas Adsorptive selectivity figure.As seen from the figure, there is excellent CO using embodiment 1 prepared by the method for the present invention2/CH4Absorption selection Property, the CO in 298K, 100kPa2/CH4Adsorptive selectivity reach 283.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work Other embodiment belongs to the range that the present invention is protected.
Generally, zeolite molecular sieve K-ZK-5 of the invention described method can be prepared through the invention.Under The reaction scheme and embodiment in face are for being further illustrated the contents of the present invention.
The professional of fields will be appreciated that preparation method described in the invention can be used to suitably prepare perhaps Other zeolite molecular sieves K-ZK-5 mostly of the invention.For example, the technological parameter of the preparation method of those non-illustrations according to the present invention, Or the reaction condition of embodiment is made into some conventional modifications.
The professional technicians of fields it should also be recognized that: the individual preparation method systems proved in the embodiment of the present invention The characteristics of had for obtained zeolite molecular sieve K-ZK-5 (the characteristics of Fig. 1 to 4 is shown), other those non-examples of the invention The zeolite molecular sieve K-ZK-5 that the preparation method of card is prepared similarly has, equally to CO2Adsorbance with higher, and To CH4And N2Adsorbance it is lower, or even with pressure raising adsorbance be less than N2, show " molecule door " effect.Non- example The zeolite molecular sieve K-ZK-5 that the preparation method of card is prepared will not separate and recycle CO to them2In effect obviously have Detrimental effect.
Technical solution of the present invention is described in detail with reference to the accompanying drawing.
Embodiment 1
A kind of preparation method of zeolite molecular sieve, includes the following steps:
1-1) by 40mL distilled water, the mixture heating of 14g potassium hydroxide and 8g aluminium hydroxide becomes limpid until solution Transparent (amount for remaining distilled water is 40mL), room temperature is cooling to can be obtained potassium metaaluminate solution for use.
Potassium metaaluminate solution is mixed with CsOH solution 1-2), is subsequently added into silica solution, stirring 10 minutes to be mixed Uniform shape is presented in object solution, and the molar ratio of raw material is 2.4K2O:0.06Cs2O:4.0SiO2: Al2O3:36H2O。
1-3) in the autoclave for the polytetrafluoroethyllining lining that mixture is then transferred to 23mL, reacted 4 days under 423K, After the completion of crystallization, is washed, filtered with distillation, obtaining white powder after drying under 373K.Obtained sample by XRD characterization into Row determination obtains ZK-5.Measuring its silica alumina ratio by elemental analysis is 3.21.
2) 5 g molecular sieves are added to the solution of 200mL 1M KCl, heating stirring 12h carries out ion friendship at 353K It changes, and is continuously added into distilled water during heating to keep the total amount of solution constant；After four exchanges, deionization is used Water continues washing filtering, and for 24 hours, obtained product is K-ZK-5-1 to sample for drying at 373K.
Embodiment 2
A kind of preparation method of zeolite molecular sieve, includes the following steps:
1-1) by 40mL distilled water, the mixture heating of 14g potassium hydroxide and 8g aluminium hydroxide becomes limpid until solution Transparent (amount for remaining distilled water is 40mL), room temperature is cooling to can be obtained potassium metaaluminate solution for use.
Potassium metaaluminate solution is mixed with CsOH solution 1-2), is subsequently added into silica solution, stirring 10 minutes to be mixed Uniform shape is presented in object solution, and the molar ratio of raw material is 2.4K2O:0.06Cs2O:4.26SiO2: Al2O3:36H2O。
1-3) in the autoclave for the polytetrafluoroethyllining lining that mixture is then transferred to 23mL, reacted 4 days under 423K, After the completion of crystallization, is washed, filtered with distillation, obtaining white powder after drying under 373K.Obtained sample by XRD characterization into Row determination obtains ZK-5.Measuring its silica alumina ratio by elemental analysis is 3.30.
2) 5 g molecular sieves are added to the solution of 250 mL 1M KCl, the heating stirring 12h at 353K.Carry out ion Exchange, and it is continuously added into distilled water during heating to keep the total amount of solution constant；After exchanging three times, spend from Sub- water continues washing filtering, and for 24 hours, obtained product is K-ZK-5-2 to sample for drying at 373K.
Table 1 is the specific surface area of Examples 1 and 2.The specific surface area of embodiment 1-2 is fitted adsorption curve meter by DR It obtains, it can be seen that all material all has higher specific surface area.
The comparison of 1 specific surface area of table
Embodiment Embodiment 1 Embodiment 2
Specific surface area (m2/ g) 303.24 326.93
Embodiment 3
A kind of preparation method of zeolite molecular sieve, includes the following steps:
1-1) by 40mL distilled water, the mixture heating of 14g potassium hydroxide and 8g aluminium hydroxide becomes limpid until solution Transparent (amount for remaining distilled water is 40mL), room temperature is cooling to can be obtained potassium metaaluminate solution for use.
Potassium metaaluminate solution is mixed with CsOH solution 1-2), is subsequently added into silica solution, stirring 10 minutes to be mixed Uniform shape is presented in object solution, and the molar ratio of raw material is 2.4K2O:0.06Cs2O:4.1SiO2: Al2O3:36H2O。
1-3) in the autoclave for the polytetrafluoroethyllining lining that mixture is then transferred to 23mL, reacted 4 days under 423K, After the completion of crystallization, is washed, filtered with distillation, obtaining white powder after drying under 373K.Obtained sample by XRD characterization into Row determination obtains ZK-5.Measuring its silica alumina ratio by elemental analysis is 3.24.
2) 5 g molecular sieves are added to the solution of 150 mL 0.5M KCl, the heating stirring 4h at 363K.Carry out ion Exchange, and it is continuously added into distilled water during heating to keep the total amount of solution constant；To six times exchange after, spend from Sub- water continues washing filtering, and for 24 hours, obtained product is K-ZK-5-3 to sample for drying at 373K.
Embodiment 4
A kind of preparation method of zeolite molecular sieve, includes the following steps:
1-1) by 40mL distilled water, the mixture heating of 14g potassium hydroxide and 8g aluminium hydroxide becomes limpid until solution Transparent (amount for remaining distilled water is 40mL), room temperature is cooling to can be obtained potassium metaaluminate solution for use.
Potassium metaaluminate solution is mixed with CsOH solution 1-2), is subsequently added into silica solution, stirring 10 minutes to be mixed Uniform shape is presented in object solution, and the molar ratio of raw material is 2.4K2O:0.06Cs2O:4.2SiO2: Al2O3:36H2O。
1-3) in the autoclave for the polytetrafluoroethyllining lining that mixture is then transferred to 23mL, reacted 4 days under 423K, After the completion of crystallization, is washed, filtered with distillation, obtaining white powder after drying under 373K.Obtained sample by XRD characterization into Row determination obtains ZK-5.Measuring its silica alumina ratio by elemental analysis is 3.27.
2) 5 g molecular sieves are added to the solution of 150 mL 2M KCl, the heating stirring 8h at 343K.Carry out ion friendship It changes, and is continuously added into distilled water during heating to keep the total amount of solution constant；After six exchanges, deionization is used Water continues washing filtering, and for 24 hours, obtained product is K-ZK-5-4 to sample for drying at 373K.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.

Claims (6)

1. a kind of preparation method of zeolite molecular sieve, which comprises the steps of:
1) ZK-5 is prepared
Silica alumina ratio adjusting is carried out, used material molar ratio is SiO2/Al2O3=4.0-4.26 obtains the ZK-5 of different silica alumina ratios Molecular sieve；
2) ion exchange
Molecular sieve is added to potassium salt soln, heating stirring carries out ion exchange, and is continuously added into distillation during heating Water is constant to keep the total amount of solution；After ion exchange, continues washing filtering with deionized water, be dried to obtain K-ZK-5 zeolite Molecular sieve.
2. a kind of preparation method of zeolite molecular sieve according to claim 1, which is characterized in that the concentration of potassium salt soln is 0.5M-2M, the required solution of every gram molecule sieve is 30-50mL.
3. a kind of preparation method of zeolite molecular sieve according to claim 1, which is characterized in that described to add in step 2 Hot temperature is 343-363K, and exchange times are 3 times -6 times, and the time of each heating stirring is 4-12 hours.
4. a kind of preparation method of zeolite molecular sieve according to claim 1, which is characterized in that the potassium salt soln is KCl solution, KNO3Solution or K2SO4Solution.
5. a kind of K-ZK-5 that the preparation method of zeolite molecular sieve is prepared described in Claims 1-4 any claim Zeolite molecular sieve is as CO2Adsorbent is in CO2Separation and recycling in application.
6. a kind of K-ZK-5 that the preparation method of zeolite molecular sieve is prepared described in Claims 1-4 any claim Zeolite molecular sieve is as CO2Adsorbent CO in removing natural gas2Application.
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CN113424717B (en) * 2021-07-15 2022-05-31 浙江大学 Method for promoting photosynthetic efficiency of facility horticultural crops by using zeolite molecular sieve
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