CN104492405B - Core-shell type molecular sieve microsphere and preparation method and application thereof - Google Patents
Core-shell type molecular sieve microsphere and preparation method and application thereof Download PDFInfo
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- CN104492405B CN104492405B CN201410738437.5A CN201410738437A CN104492405B CN 104492405 B CN104492405 B CN 104492405B CN 201410738437 A CN201410738437 A CN 201410738437A CN 104492405 B CN104492405 B CN 104492405B
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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
- 239000004005 microsphere Substances 0.000 title claims abstract description 71
- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 27
- 238000003786 synthesis reaction Methods 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 9
- -1 salt ion Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 22
- 238000003756 stirring Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- 239000011324 bead Substances 0.000 description 9
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011805 ball Substances 0.000 description 4
- 239000001175 calcium sulphate Substances 0.000 description 4
- 235000011132 calcium sulphate Nutrition 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- 229920001661 Chitosan Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004927 clay Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000004459 forage Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
-
- 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
- B01D2256/10—Nitrogen
-
- 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
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/102—Nitrogen
-
- 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
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
- B01D2257/7025—Methane
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- Y02C20/20—Capture or disposal of greenhouse gases of methane
-
- 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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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a core-shell type molecular sieve microsphere and a preparation method and application thereof, which are characterized in that a core-shell microsphere structure with an A type molecular sieve as a shell and A and X type molecular sieves as cores is adopted, NaA and NaX molecular sieve composite microspheres are prepared in one step, and then a layer of NaA type molecular sieve membrane grows on the surface of the NaA and NaX molecular sieve composite microspheres to form Na ion type core-shell type molecular sieve microspheres; and exchanging the K-type and Ca-type core-shell molecular sieve microspheres by using the K ion solution and the Ca ion solution. The core-shell type molecular sieve microsphere prepared by the invention does not contain a binder and has higher mechanical strength. The core-shell type molecular sieve microsphere prepared by the method is suitable for CO2/CH4、CO2/N2And CH4/N2The separation of the mixed gas and the preparation method are simple and easy for industrial production.
Description
Technical field
The present invention relates to a kind of core-shell type molecular sieve micro-sphere material and its production and use is and in particular to by this side
Method one step prepares the complex microsphere with naa and nax mixing crystal formation, prepares with a type molecular sieve after the synthesis of long film
For fine and close shell, a and x type molecular sieve is the core-shell type molecular sieve microsphere of core.It is primarily useful for the adsorbing separation of gas, increase
co2And ch4、n2The separation factor of bi-component gas.
Background technology
Greenhouse effect produced by CO2 emission is an alarming global environmental problem, most
co2How being produced by fossil-fueled of discharge, efficiently separate and trapping co from flue gas2For reduction greenhouse gases
Discharge is significant.In addition, co2It is also main foreign gas in natural gas and biogas, co2Presence can have a strong impact on
The unit energy content of natural gas and biogas, removes co therefore from natural gas and biogas2There is important practical significance.Low dense
Degree coal bed gas is then a kind of Unconventional forage, and main component is ch4And n2, wherein (ch4) it is less than 30%, lead to coal bed gas difficult
Directly to utilize, or traditional processing mode is directly vented, or low concentration burns, waste of resource also pollutes environment, with
When due to ch4And n2Molecule activity diameter close to and be difficult to separate, if can not solve cannot be good for the thickening problem of methane
Coal bed gas is developed and utilized.Therefore, a kind of environmental friendliness, stable performance, economic and practical co are developed2/ch4、co2/
n2、ch4/n2Adsorption and separation material is the study hotspot of gas absorption separation field.The isolation technics being directed to these gases are main
Including absorption, absorb, membrance separation and freeze and separate etc., wherein membrane separating method has that energy consumption is low, and the advantages of pollution-free, but film divides
From higher for equipment and material requirements.Ammonia and the easy etching apparatus of double Alkali absorption method and regeneration difficulty greatly, reclaim difficult,
Its application is very limited.Solid absorbent is simple to operate, corrosion-free to equipment when using, be relatively easy to regeneration, performance
Stable, save energy, has therefore expedited the emergence of the research boom of solid adsorption material.
Zeolitic material, because having the advantages of well-regulated nano-pore structure and good heat stability, can be used for the suction of gas
Echo separation field.As caa zeolite molecular sieve is added to enough ccl by patent (cn 102350303a)4In solvent, stirring
Under the conditions of time of infusion；Remove ccl4Solvent, adds kcl solution, carries out rapid filtration under suction, sucking filtration does not stop to stir after stirring simultaneously
Mix and add water flushing；Finally prepared kcaa zeolite molecular sieve is placed in 50 DEG C of baking ovens and is dried, and is subsequently put in vacuum drying oven and lives
Change a period of time.Obtain kcaa zeolite molecular sieve for co2Adsorbance be 4mmol/g, for co2/n2Selectivity is up to 129.
A type molecular sieve after specific process ion exchange is for co2/n2Selectivity ratios higher, preparation method is simple, but for
co2Adsorbance be not very high, and the zeolitic material after this synthesis is powder, unfavorable with industrial practical application.Except entering
Row ion-exchanged, can also reach the effect of the adsorption seperation of gas of molecular sieve by methods such as acid treatments, such as patent (cn
102219235a) na type molecular sieve be impregnated in the h of 3m2so4In solution, uniform stirring, standing 1h filters, drying at room temperature 24h,
It is dried under the conditions of 100 DEG C, after roasting, obtain a/h-na.The a/h-na molecular sieve of the method preparation, preparation process is simple, for
ch4/n2Separation factor reach 2.66, can be used for pressure-variable adsorption and separate, but selectivity needs to be improved further.Document
Sodium aluminate solution is added drop-wise to sodium hydroxide, hydrogen by (chemical engineering journal, 2013,230,380 388)
In potassium oxide and Ludox mixed solution, it is used tetramethyl oxyammonia to prepare t type molecular sieve as structure directing agent,
Under the conditions of 288k, 100kpa, to co2、ch4、n2Adsorbance be respectively 4.81mmol/g, 0.99mmol/g and 1.72mmol/g.
To co2/ch4、co2/n2、ch4/n2Gas selectivity be 4.9,2.8 and 1.7 respectively.The t type molecular sieve of the method preparation is brilliant
Grain is little, to co2、ch4And n2Adsorbance all higher, but selectivity or relatively low.
The patent of research zeolitic solid adsorbent and document great majority are based on dusty material at this stage.Dusty material exists
Occur in commercial Application that powder dress agent dust is big, the problems such as difficult separation and recycling, discharge carry serious secretly.Zeolite formed product is solution
The certainly key of zeolite powder industrial problems, common method is to add binding agent, and extrusion shapes.As patent (cn
1103816a) use nay zeolite and clay class Kaolin, expanding agent mixing extrusion molding, drying, roasting, alkali process are obtained
The nay zeolite of soap-free emulsion polymeization dosage form is the Zeolite support of main body.But the use of binding agent can reduce consolidating of zeolite in formed body to be contained
Amount, and binding agent does not have molecular sieve property, can block the duct of molecular sieve, and then affect molecular sieve catalytic performance and select to inhale
Attached ability.The preparation method of Adhesive-free Molecular Sieve formed body has also been widely studied, and such as patent (cn 103508463a) will
Sodium silicate aqueous solution and peptizer solution mixing system, for colloidal sol, are prepared into hydrogel bead by forming oil column, through washing, always
Change, be dried, silica dioxide gel bead is made in roasting, adding sodium metaaluminate and directed agents, after crystallization, be dried to obtain binder free
Spherical faujasite granule.Patent (cn 101348261) is with least in kieselguhr, white carbon, Ludox or waterglass
Planting is silicon source, with least one of the oxide of aluminum, aluminium salt or aluminate as aluminium source raw material, adds the desired amount of seeding director
Carry out kneading extruded moulding, process through hydrothermal crystallizing and obtain binder free zsm-11 moulded zeolite.Although said method is prepared
Binder free zeolitic material, but complex steps, process is complicated, increases life cycle of the product, improves preparation cost.
Therefore, develop a kind of preparation process simply, the complicated high adsorption capacity exchanging and processing, high selectivity need not be carried out
Adhesive-free Molecular Sieve micro-sphere material has very great practical significance and using value.
Content of the invention
The invention aims to improve prior art prepare binder free zeolitic material and its gas separate apply
The deficiency of aspect, and develop a kind of core-shell type molecular sieve microsphere of binder free；It is a further object of the present invention to provide it is above-mentioned
The preparation method of core-shell type molecular sieve microsphere, further object of the present invention is to provide above-mentioned core-shell type molecular sieve microsphere in co2、
n2And ch4Application in bi-component gas adsorbing separation.
The technical scheme is that a kind of core-shell type molecular sieve microsphere it is characterised in that using a type molecular sieve as shell, a
It is the core-shell particles structure of core with x type molecular sieve；In its center, the quality of x type molecular sieve accounts for the 50%-90% of nuclear mass；Nucleocapsid
The particle size range of microsphere is 0.5-3.0mm, and shell thickness is 1-12 μm；Core-shell type molecular sieve microsphere is na ion-type, ca ion
Type or k ion-type.
Present invention also offers the preparation method of above-mentioned core-shell type molecular sieve microsphere: prepare naa and nax molecule one step ahead
Sieve complex microsphere, then on naa and nax molecular sieve complex microsphere surface, one layer of naa type molecular screen membrane of growth forms na ion
Type core-shell type molecular sieve microsphere；Or form the hud typed of K-type and ca type again after k solion and ca solion exchange
Molecular sieve microsphere.Its concrete preparation process is as follows:
1), by shitosan, acetic acid and Ludox according to shitosan: hac:sio2: h2The mol ratio of o is (0.0003-
0.0009): (0.3-0.5): (1.35-2.7): (50-100) is configured to silicon solution；Again by sodium hydroxide, sodium aluminate and water according to
na2O:al2o3: h2The mol ratio of o is (2.0-6.0): (1.0-3.0): (30-60) is configured to aluminum solutions；The silicon solution that will prepare
It is added drop-wise in aluminum solutions, form spherical little particle, dipping, then hydro-thermal reaction, the spheroidal particle obtaining, through washing, dry
To shitosan/naa/nax composite, roasting removes naa the and nax molecular sieve microsphere that shitosan obtains binder free；
2), according to sodium aluminate, sodium silicate and water mol ratio be (0.5-2.0): (0.3-1.2): (60-200) prepares long film
Synthetic solvent, long film Synthesis liquid after aging, by step 1) be obtained naa and nax molecular sieve microsphere be added to aging after
In long film synthetic solvent；After heating the synthesis of long film, by product be washed to neutrality and be dried to obtain naa be shell, naa and
Nax is the na ion-type core-shell type molecular sieve microsphere of core；Or add in na ion-type core-shell type molecular sieve microsphere and contain k
The aqueous solution of ion or ca ion carries out ion exchange, obtain after washing and drying k ion-type core-shell type molecular sieve microsphere or ca from
Subtype core-shell type molecular sieve microsphere.
Preferred steps 1) in silicon solution be added drop-wise to the mass ratio (0.8-0.95) of silicon solution and aluminum solutions in aluminum solutions: 1.Excellent
Select step 1) described in dip time be 6-24h；Described hydrothermal temperature is 60 DEG C -110 DEG C, and the hydro-thermal reaction time is
3-12h；Described washing is to be washed till ph for 7-9 using deionized water；Described baking temperature is 60 DEG C -80 DEG C, drying time
For 4-8h；Described sintering temperature is 550 DEG C -600 DEG C, and roasting time is 1-2h.
Preferred steps 2) in the aging temperature of long film Synthesis liquid be 50-70 DEG C, ageing time be 0.5-1.0h.Preferred steps
2) in, naa/nax molecular sieve microsphere and the mass ratio of long film Synthesis liquid are 1:(10-20).Preferred steps 2) in heating long film synthesis
Temperature be 80 DEG C -100 DEG C, the time be 4-48h；Long film synthesis number of times is 1-3 time；Described washing is to make to be washed with deionized water
It is 7-9 to ph.Preferred steps 2) in k salt ion solution or ca salt ion solution concentration be 0.1-0.3mol/l；Ion exchange
During core-shell type molecular sieve with the mass ratio of k salt ion solution or ca salt ion solution as 1:(30-60)；During ion exchange
Between be 6-24h.
Present invention also offers above-mentioned core-shell type molecular sieve microsphere is in co2、ch4And n2In bi-component gas adsorbing separation
Application.
Beneficial effect:
The core-shell type molecular sieve microsphere that the present invention prepares has compared with high selection absorbability and higher adsorbance, prepares
Method is simple, to co2/ch4、co2/n2、ch4/n2The more general adsorbent of separation factor of mixed gas will height.This is hud typed simultaneously
Molecular sieve microsphere has high mechanical properties, heat stability and corrosion resistance.The present invention is gone out using organic biomass one-step synthesis
Naa/nax complex microsphere, forms with a type molecular sieve as shell after carrying out long film, a and x type molecular sieve is the hud typed molecule of core
Sieve, can preferably play the adsorption selectivity of material using this special nucleocapsid structure.Additionally, this material produces week
Phase is short, low cost and can repeat recycle, therefore can carry out use of large-scale production.
Brief description
Fig. 1 is the electron microscope of sample q1, and wherein (a) represents that sample q1 microsphere, (b) represent sample q1 microsphere surface, (c) table
Sample product q1 core；
Fig. 2 is the electron microscope of sample q2, and wherein (a) represents that sample q2 bead interface, (b) represent sample q2 microsphere surface；
Fig. 3 is the electron microscope of sample q3, and wherein (a) represents that sample q3 bead interface, (b) represent sample q3 microsphere surface；
Fig. 4 is the electron microscope of sample q4, and wherein (a) represents that sample q4 bead interface, (b) represent sample q4 microsphere surface；
Fig. 5 is the electron microscope of sample q5, and wherein (a) represents that sample q5 bead interface, (b) represent sample q5 microsphere surface；
Fig. 6 is the electron microscope of sample q6, and wherein (a) represents that sample q6 bead interface, (b) represent sample q6 microsphere surface；
Fig. 7 is the xrd figure of sample q1 sample q1；
Fig. 8 is the xrd figure of sample q2；
Fig. 9 schemes for sample q3xrd；
Figure 10 is the xrd figure of sample q4；
Figure 11 schemes for sample q5xrd；
Figure 12 is the xrd figure of sample q6；
Figure 13 is sample q9 to co2/ch4Breakthrough curve；
Figure 14 is sample q9 to c02/n2Breakthrough curve.
Specific embodiment
Embodiment 1:
The Ludox of 8.3g 30% is added in 28.57g deionized water, then is added thereto to the shitosan of 1.0g,
Under conditions of stirring in above-mentioned solution dropwise Deca 1.6g 36% acetic acid, after stirring, form sticky shitosan two
Silica solution, the mol ratio of this silicon solution is 0.0004cs:0.3hac:1.4sio2:54h2o.5.68g sodium hydroxide is added
To in 83.8g deionized water, after fully dissolving, add 2.24g sodium aluminate, stir to clarify, form aluminum solutions, this aluminum solutions
Mol ratio be 3na2o:2al2o3:34h2o.Silicon solution is added drop-wise in aluminum solutions for 0.9:1 with mass ratio, is formed scattered
Gelled pill.After completion of dropping, ball and aluminum solutions are impregnated 8h at ambient temperature, then by ball together with aluminum solutions 70
Hydro-thermal 12h in DEG C baking oven, the microsphere obtaining fully washs and 7h is dried under the conditions of 60 DEG C to ph=7, obtains final product naa/nax/ shell
Polysaccharide complex microsphere.Naa/nax/ chitosan compound microsphere is put into Muffle furnace, roasting 2h, programming rate under the conditions of 550 DEG C
For 2 DEG C/min, obtain naa the and nax complex microsphere of binder free, bead size is 0.5-3.0mm, is designated as sample q1, sample
The electron microscope of q1 is as shown in figure 1, can be seen that from figure the surface of naa and nax complex microsphere is substantially that naa type cube is brilliant
Grain, is substantially nax and naa type zeolite crystal at core, and wherein x type molecular sieve quality fraction is 60%.The xrd of q1 schemes such as
It can be seen that a type and the characteristic peak of x type simultaneously shown in Fig. 7, and peak intensity is essentially identical.Will be molten for 7.8g nine water sodium silicate
Solution forms solution a1 in 19.9g deionized water, and 3.0g sodium aluminate is dissolved in formation solution a2 in 11.0g deionized water, molten
After solution finishes, a1 is poured slowly in a2 solution, under the conditions of 50 DEG C, stirs aging 1h, sodium aluminate in this long film synthetic solvent:
Sodium silicate: water mol ratio is 1.4:1:64.Long film synthetic solvent is added in sample q1 with mass ratio 20:1, then by sample
Q1 is placed in 100 DEG C of baking ovens lower crystallization 5h together with long film synthetic solvent, and the microsphere deionized water obtaining fully is washed to ph
For 8,5h is dried under the conditions of 80 DEG C and obtains hud typed molecular sieve microsphere, be designated as sample q2, the interface of sample q2 and surface
Electron microscope as shown in Fig. 2 as can be seen from the figure interface exist 1.0 μ m-thick shell, surface is to show intergrowth
State.The xrd of sample q2 schemes as shown in figure 8, all a type and x type characteristic peak, will height before the longer film process of intensity.
Embodiment 2:
The Ludox of 10.9g 30% is added in 35.3g deionized water, then is added thereto to the shitosan of 2.0g,
Under conditions of stirring in above-mentioned solution dropwise Deca 1.82g 36% acetic acid, after stirring, obtain silicon solution mole
Than for 0.0008cs:0.5hac:2.5sio2:90h2o.6.05g sodium hydroxide is added in 40.8g deionized water, treats fully
After dissolving, add 18.6g sodium aluminate, stir to clarify, form aluminum solutions, the mol ratio of this aluminum solutions is 5na2o:3al2o3:
60h2o.Silicon solution is added drop-wise to formation gelled pill in aluminum solutions with mass ratio for 0.8:1.After completion of dropping, ball is molten with aluminum
Liquid impregnates 23h at ambient temperature, then together with aluminum solutions, ball is placed on hydro-thermal 4h in 100 DEG C of baking ovens, and obtain is micro-
Ball fully washs to ph=8.Microsphere is dried 4h under the conditions of 80 DEG C, obtains final product naa/nax/ chitosan compound microsphere.By naa/
Nax/ chitosan compound microsphere puts into Muffle furnace, roasting 1h under the conditions of 600 DEG C, and programming rate is 5 DEG C/min, obtains soap-free emulsion polymeization
Naa the and nax complex microsphere of agent, bead size is 1.5-3.0mm.Naa the and nax complex microsphere surface obtaining is mainly a type
Molecular sieve, core is naa and nax molecular sieve mixed crystal, and wherein x type molecular sieve quality fraction is 90%.By 1.18g nine water silicon
Sour sodium is dissolved in formation solution b1 in 20g deionized water, and 0.55g sodium aluminate is dissolved in formation solution b2 in 20g deionized water,
After dissolving finishes, b1 is poured slowly in b2 solution, under the conditions of 70 DEG C, stirs aging 0.5h, aluminic acid in this long film synthetic solvent
Sodium: sodium silicate: water mol ratio is 0.6:0.37:199.Long film synthetic solvent is added in sample q1 with mass ratio 10:1, so
Afterwards sample q1 is placed in together with long film synthetic solvent in 85 DEG C of baking ovens lower crystallization 40h, the microsphere deionized water obtaining is abundant
Washing to ph is 9,5h is dried and obtains hud typed molecular sieve microsphere, be designated as sample q3, the Electronic Speculum of sample q3 under the conditions of 80 DEG C
As shown in figure 3, q3 surface microstructure is comparatively dense, microsphere intensity improves figure, but interface does not occur shell-like structure.Sample q3
Xrd scheme as shown in figure 9, a type and x type characteristic peak all occur.
Embodiment 3:
According to long film synthesis liquid and preparation method thereof in the same manner as in Example 1 and long film method, sample q2 with mass ratio is
The ratio of 1:20 is added in long film Synthesis liquid, and crystallization 5h under the conditions of 100 DEG C carries out two vice-minister's films.Hud typed point obtaining
Son sieve microsphere is designated as q4, and, as shown in figure 4, shell thickness is 3.8 μm, surface interaction growth fraction sample q2 will for the electron microscope of sample q4
Good.As shown in Figure 10, all a type and x type characteristic peak in the xrd figure of sample q3, and x type peak intensity is higher than the intensity of a.
Embodiment 4:
According to long film synthesis liquid and preparation method thereof in the same manner as in Example 1 and long film method, sample q4 with mass ratio is
The ratio of 1:20 is added in long film Synthesis liquid, and crystallization 5h under the conditions of 100 DEG C carries out three vice-minister's films.Hud typed point obtaining
Son sieve microsphere is designated as q5, as shown in figure 5, shell thickness is 10.7 μm, surface is in intergrowth to the electron microscope of sample q5, film layer base
Originally there is no defect.As shown in figure 11, all a type and the x type characteristic peak of higher-strength in the xrd figure of sample q5.
Embodiment 5:
According to long film synthesis liquid and preparation method thereof in the same manner as in Example 2 and long film method, sample q3 with mass ratio is
The ratio of 1:10 is added in long film Synthesis liquid, and crystallization 40h under the conditions of 85 DEG C carries out two vice-minister's films.Hud typed point obtaining
Son sieve microsphere is designated as q6, as shown in fig. 6, shell thickness is 3.2 μm, surface is in intergrowth to the electron microscope of sample q6.Sample q6
Xrd figure as shown in figure 12, a type and the x type characteristic peak of higher-strength all occur.
Embodiment 6:
Prepare the calcium chloride solution of 0.1mol/l, 1.11g calcium chloride solution is added in 100g deionized water.Then will
Calcium chloride solution is added in sample q5 with mass ratio 40:1, exchanges 10h under stirring condition.Remove calcium chloride solution, spend from
Wash after sub- water punching and 6h is dried under the conditions of 60 DEG C.Obtain the core-shell type molecular sieve after calcium ion-exchanged, be designated as q7.
Embodiment 7:
Prepare the Klorvess Liquid of 0.1mol/l, 7.45g Klorvess Liquid is added in 100g deionized water.By chlorination
Potassium solution is added in sample q5 and q6 with mass ratio for 50:1, exchanges 12h under stirring condition, removes Klorvess Liquid, spends
Ionized water is dried 4h after rinsing under the conditions of 80 DEG C, obtains the long membrane molecule sieve after potassium ion exchanges, is designated as q8 and q9 respectively.
Embodiment 8:
Prepare the calcium sulphate soln of 0.25mol/l, 2.5g calcium sulphate soln is added in 100g deionized water.Then will
Calcium sulphate soln is added in sample q5 with mass ratio 50:1, exchanges 20h under stirring condition.Remove calcium sulphate soln, spend from
Sub- water is dried 4h after rinsing under the conditions of 80 DEG C.Obtain the core-shell type molecular sieve after calcium ion-exchanged, be designated as q10.
Embodiment 9:
Prepare the potassium nitrate solution of 0.25mol/l, 2.5g potassium nitrate solution is added in 100g deionized water.Then will
Potassium nitrate solution is added in sample q6 with mass ratio 50:1, exchanges 20h under stirring condition.Remove potassium nitrate solution, spend from
Sub- water is dried 4h after rinsing under the conditions of 80 DEG C, obtains the core-shell type molecular sieve after potassium ion exchanges, is designated as q11.
co2/ch4Breakthrough curve on sample q9 core-shell type molecular sieve is shown in Figure 13, and experiment condition is: test before with 2 DEG C/
The heating rate of min is heated to 300 DEG C, is incubated 4h, the helium with flow velocity as 10ml/min for the period not sweep by blow off, removes adsorbent
Middle adsorbed impurity, then naturally cools to room temperature.Molecular sieve consumption=2.3g；Adsorptive pressure=101.3kpa, absorption temperature
Degree=298k；Adsorption tube entrance adds co2And ch4Flow velocity is respectively the gaseous mixture of 1.7ml/min and 2.3ml/min, using peace
The each gas concentration in Jie Lun (7820a) chromatography of gases on-line determination exit, time dependent according to measured gas concentration
Data draws breakthrough curve.co2/ch4Breakthrough curve is shown in initial 1500s, co2Adsorbed completely, ch4Substantially not by
Absorption.,After 1500s, exit co2Concentration is gradually increased, during about 2500s outlet co2 concentration suitable with air inlet it is meant that suction
Attached reach saturation.
Breakthrough curve on sample q9 core-shell type molecular sieve for the co2/n2 is shown in Figure 14, and experiment condition is: test before with 2 DEG C/
The heating rate of min is heated to 300 DEG C, is incubated 4h, the helium with flow velocity as 10ml/min for the period not sweep by blow off, removes adsorbent
Middle adsorbed impurity, then naturally cools to room temperature.Molecular sieve consumption=2.3g；Adsorptive pressure=101.3kpa, absorption temperature
Degree=298k；Adsorption tube entrance adds co2And n2Flow velocity is respectively the gaseous mixture of 1.5ml/min and 7.8ml/min, using peace
The each gas concentration in Jie Lun (7820a) chromatography of gases on-line determination exit, time dependent according to measured gas concentration
Data draws breakthrough curve.co2/n2Breakthrough curve is shown in initial 500s, co2Adsorbed completely, n2Do not adsorb.2000s
Afterwards, exit co2Concentration is gradually increased, and during about 2000s, outlet co2 concentration is suitable with air inlet reaches saturation it is meant that adsorbing.
Table 1 sample is to n2、ch4、co2The adsorbance of single-component gas
* condition: temperature is 298k, pressure is 100kpa
Claims (7)
1. a kind of method preparing core-shell type molecular sieve microsphere, its concrete preparation process is as follows:
1), by shitosan, acetic acid and Ludox according to shitosan: hac:sio2: h2The mol ratio of o is (0.0003-0.0009):
(0.3-0.5): (1.35-2.7): (50-100) is configured to silicon solution；Again by sodium hydroxide, sodium aluminate and water according to na2O:
al2o3: h2The mol ratio of o is (2.0-6.0): (1.0-3.0): (30-60) is configured to aluminum solutions；The silicon solution Deca that will prepare
To in aluminum solutions, form spherical little particle, dipping, then hydro-thermal reaction, the spheroidal particle obtaining, through washing, be dried to obtain shell
Polysaccharide/naa/nax composite, roasting removes naa the and nax molecular sieve microsphere that shitosan obtains binder free；
2) it is, (0.5-2.0): (0.3-1.2) according to sodium aluminate, sodium silicate and water mol ratio: (60-200) prepares the synthesis of long film
Solution, long film Synthesis liquid after aging, by step 1) be obtained naa and nax molecular sieve microsphere be added to aging after long film
In synthetic solvent；After heating the synthesis of long film, by product be washed to neutrality and be dried to obtain naa be shell, naa and nax be
The na ion-type core-shell type molecular sieve microsphere of core；Or add in na ion-type core-shell type molecular sieve and contain k ion or ca
The aqueous solution of ion carries out ion exchange, obtains k ion-type core-shell type molecular sieve microsphere or ca ion-type nucleocapsid after washing and drying
Type molecular sieve microsphere；Using a type molecular sieve as shell, a and x type molecular sieve is the nucleocapsid of core to obtained core-shell type molecular sieve microsphere
Micro-sphere structure；In its center, the quality of x type molecular sieve accounts for the 50%-90% of nuclear mass；The particle size range of core-shell particles is 0.5-
3.0mm, shell thickness is 1-12 μm；Core-shell type molecular sieve microsphere is na ion-type, ca ion-type or k ion-type.
2. in accordance with the method for claim 1 it is characterised in that step 1) in silicon solution be added drop-wise in aluminum solutions silicon solution with
The mass ratio (0.8-0.95) of aluminum solutions: 1.
3. method according to claim 1 is it is characterised in that step 1) described in dip time be 6-24h；Described
Hydrothermal temperature is 60 DEG C -110 DEG C, and the hydro-thermal reaction time is 3-12h；Described washing is to be washed till ph using deionized water to be
7-9；Described baking temperature is 60 DEG C -80 DEG C, and drying time is 4-8h；Described sintering temperature is 550 DEG C -600 DEG C, roasting
Time is 1-2h.
4. method according to claim 1 is it is characterised in that step 2) in the aging temperature of long film Synthesis liquid be 50-70
DEG C, ageing time is 0.5-1.0h.
5. in accordance with the method for claim 1 it is characterised in that step 2) in naa/nax molecular sieve microsphere and long film Synthesis liquid
Mass ratio be 1:(10-20).
6. in accordance with the method for claim 1 it is characterised in that step 2) in the temperature of heating long film synthesis be 80 DEG C -100
DEG C, the time is 4-48h；Long film synthesis number of times is 1-3 time；Described washing is to be washed till ph for 7-9 using deionized water.
7. in accordance with the method for claim 1 it is characterised in that step 2) in k salt ion solution or ca salt ion solution dense
Spend for 0.1-0.3mol/l；The quality of core-shell type molecular sieve and k salt ion solution or ca salt ion solution in ion exchange process
Than for 1:(30-60)；Ion-exchange time is 6-24h.
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| CN107185488B (en) * | 2017-05-27 | 2020-06-19 | 华东理工大学 | Core-shell type composite molecular sieve and application thereof in separating carbon dioxide |
| CN112973624A (en) * | 2021-03-23 | 2021-06-18 | 南京永成分子筛有限公司 | High-efficiency 4A molecular sieve |
| CN114405461B (en) * | 2021-12-17 | 2024-04-16 | 中海油天津化工研究设计院有限公司 | Preparation method of core-shell mixed-crystal coal-based Fischer-Tropsch synthesis oleo-alkane-alkene separation adsorbent |
| CN116474746A (en) * | 2022-01-15 | 2023-07-25 | 中国石油化工股份有限公司 | Multi-layer core-shell structure adsorbent and preparation method thereof |
| CN116078346B (en) * | 2022-12-23 | 2024-10-11 | 中科催化新技术(大连)股份有限公司 | Preparation method of X-type molecular sieve and A-type molecular sieve composite adsorbent |
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