CN111039303B - Application of modified M-SAPO-RHO type zeolite molecular sieve as ethylene selective adsorbent - Google Patents
Application of modified M-SAPO-RHO type zeolite molecular sieve as ethylene selective adsorbent Download PDFInfo
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- 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 128
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 125
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000010457 zeolite Substances 0.000 title claims abstract description 113
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 110
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000005977 Ethylene Substances 0.000 title claims abstract description 47
- 239000003463 adsorbent Substances 0.000 title claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 34
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 150000001768 cations Chemical class 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000005342 ion exchange Methods 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 230000003213 activating effect Effects 0.000 claims description 13
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 38
- 239000000203 mixture Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 43
- 238000012360 testing method Methods 0.000 description 35
- 239000000243 solution Substances 0.000 description 33
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 30
- 238000001035 drying Methods 0.000 description 21
- 239000011343 solid material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000003795 desorption Methods 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene, ethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000045365 Microporus <basidiomycete fungus> Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Engineering & Computer Science (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides application of a modified M-SAPO-RHO type zeolite molecular sieve as an ethylene selective adsorbent, belonging to the technical field of ethylene separation. The invention provides a modified M-SAPO-RHO type zeolite molecular sieve as an ethylene selective adsorbent, wherein M comprises Li + And/or Na + (ii) a M/(Si + Al + P) = 0.01-0.17 in the modified M-SAPO-RHO type zeolite molecular sieve. The adsorption separation effect of the modified M-SAPO-RHO type zeolite molecular sieve utilized by the invention can be changed according to the change of M in the modified M-SAPO-RHO + The species and content of the ions achieve different separation effects. The modified M-SAPO-RHO type zeolite molecular sieve utilized by the invention has high crystallinity, good composition stability and good selective adsorption performance to ethylene, can realize fine control on selective adsorption capacity of ethylene and high-efficiency separation of ethylene/ethane, and improves the concentration of ethylene in mixed gas.
Description
Technical Field
The invention relates to the technical field of ethylene separation, in particular to application of a modified M-SAPO-RHO type zeolite molecular sieve as an ethylene selective adsorbent.
Background
Petrochemical industry is one of the pillar industries for promoting the economic development of the world, and at present, about 75 percent of petrochemical products are produced by ethylene, mainly comprising polyethylene, ethylene oxide, dichloroethane, styrene and the like, so that the ethylene is a leading product of the petrochemical industry and is commonly called as a 'mother of the petrochemical industry'.
At present, many studies are made at home and abroad on the recovery of organic gases containing ethylene and the like, wherein the ethylene separation method mainly comprises technologies such as a cryogenic separation method, an absorption separation method, an adsorption separation method, a membrane separation method and the like. Among them, the adsorption separation has high selectivity, simple process and low cost, and is favored by the researchers. The key of the ethylene adsorption separation is the selection of the adsorbent. At present, adsorbents for ethylene/ethane adsorption separation mainly include Metal Organic Frameworks (MOFs), carbon materials, transition metal composite materials (Cu/Ag-aluminum, resins, zeolites, carbonates and zeolites), cation-containing molecular sieves, titanium silicalite molecular sieves (cationic zeolites and titanosilicates), and the like, but have the disadvantages of high preparation cost, poor stability, poor selectivity, and the like, and limit the difficulty in applying the above materials to ethylene/ethane separation.
Disclosure of Invention
In view of the above, the present invention aims to provide the use of a modified zeolite molecular sieve of the M-SAPO-RHO type as an ethylene selective adsorbent. The modified M-SAPO-RHO type zeolite molecular sieve utilized by the invention can realize the high-efficiency separation of ethylene/ethane.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides application of a modified M-SAPO-RHO type zeolite molecular sieve as an ethylene selective adsorbent, which is characterized in that M comprises Li + And/or Na + (ii) a The modified M-SAPO-RHO type zeolite molecular sieve has the mol ratio of M/(Si + Al + P) = 0.01-0.17.
Preferably, the modified M-SAPO-RHO type zeolite molecular sieve is used as an ethylene selective adsorbent in an ethylene/ethane mixed system.
Preferably, the method for applying comprises the following steps: activating the modified M-SAPO-RHO type zeolite molecular sieve, and placing the activated molecular sieve in a mixed system containing ethylene to selectively adsorb the ethylene.
Preferably, the activation treatment is performed under vacuum conditions; the temperature of the activation treatment is 200-350 ℃, and the time is 4-10 h.
Preferably, the temperature of the selective adsorption is 298K, and the pressure is 0-1 bar.
Preferably, the preparation method of the modified M-SAPO-RHO type zeolite molecular sieve comprises the following steps:
mixing a silicon source, an aluminum source, phosphoric acid, a template agent, cetyl trimethyl ammonium bromide, SAPO-RHO seed crystals and water to obtain initial reaction gel; the template agent is diethylamine;
crystallizing the initial reaction gel to obtain an SAPO-RHO type zeolite molecular sieve, wherein the SAPO-RHO type molecular sieve contains a template agent;
directly mixing the SAPO-RHO type zeolite molecular sieve with a cation solution under the condition of not removing a template agent, and roasting after ion exchange to obtain a modified M-SAPO-RHO type zeolite molecular sieve; the cation in the cation solution comprises Li + And/or Na + (ii) a The concentration of the cation solution is 0.5-1.0 mol/L.
Preferably, the silicon source comprises one or more of silica sol, sodium silicate, a solid silicon source and white carbon black;
the aluminum source comprises one or more of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum sulfate, sodium aluminate, pseudo-boehmite, aluminum isopropoxide and gibbsite.
Preferably, the silicon source, the aluminum source and the phosphoric acid are respectively SiO 2 、Al 2 O 3 And P 2 O 5 The counting is carried out by the following steps of,
the molar ratio of the silicon source, the aluminum source, the phosphoric acid, the diethylamine, the hexadecyl trimethyl ammonium bromide and the water is (0.2-1) to 1, (0.8-1.2) to (1.0-2.4) to (0.03-0.2) to (40-200);
the mass ratio of the silicon source to the SAPO-RHO crystal seed is 1 (0.05-0.2).
Preferably, the crystallization temperature is 180-220 ℃ and the time is 24-48 h.
Preferably, the temperature of the ion exchange reaction is 40-80 ℃, and the time is 4-8 h;
the invention providesUse of a modified zeolite molecular sieve of the type M-SAPO-RHO, said M comprising Li, as an ethylene selective adsorbent + And/or Na + (ii) a The content of M is M/(Si + Al + P) = 0-0.17. The modified M-SAPO-RHO type zeolite molecular sieve utilized by the invention has the characteristics of stable structure, adjustable cation species and content and the like. The M-SAPO-RHO type zeolite molecular sieve obtained by the modification method can ensure the crystallinity of the original molecular sieve to a higher degree, has the characteristics of good composition stability, stable structure, good selective adsorption performance on ethylene and the like, can realize fine control on the selective adsorption capacity of ethylene, and further can realize high-efficiency separation of ethylene/ethane.
Drawings
FIG. 1 is an XRD pattern of SAPO-RHO and Li-SAPO-RHO prepared in example 1 and modified Na-SAPO-RHO type zeolite molecular sieve prepared in example 3;
FIG. 2 is SEM image of SAPO-RHO and Li-SAPO-RHO prepared in example 1 and modified Na-SAPO-RHO type zeolite molecular sieve prepared in example 3;
FIG. 3 is a graph of SAPO-RHO and Li-SAPO-RHO of example 1, modified Na-SAPO-RHO type zeolite molecular sieve pair C of example 3 2 H 4 And C 2 H 6 Adsorption isotherm diagram of (c).
Detailed Description
The invention provides application of a modified M-SAPO-RHO type zeolite molecular sieve as an ethylene selective adsorbent, wherein M comprises Li + And/or Na + (ii) a The modified M-SAPO-RHO type zeolite molecular sieve has the M/(Si + Al + P) molar ratio = 0.01-0.17.
In the invention, the molar ratio of M/(Si + Al + P) in the modified M-SAPO-RHO type zeolite molecular sieve is preferably 0.05-0.17, and more preferably 0.08-0.12.
In the present invention, the modified M-SAPO-RHO type zeolite molecular sieve is preferably used as an ethylene selective adsorbent in an ethylene/ethane mixed system.
In the present invention, the method of application preferably comprises the steps of: activating the modified M-SAPO-RHO type zeolite molecular sieve, and placing the activated molecular sieve in a mixed system containing ethylene to selectively adsorb the ethylene.
In the present invention, the activation treatment is preferably performed under vacuum conditions. In the present invention, the degree of vacuum is not particularly limited, and a degree of vacuum known in the art may be used. In the present invention, the temperature of the activation treatment is preferably 200 to 350 ℃, more preferably 220 to 320 ℃, and most preferably 250 to 300 ℃; the time for the activation treatment is preferably 4 to 10 hours, more preferably 5 to 8 hours, and most preferably 5 to 6 hours. In the invention, the purpose of the activation treatment is to remove physical water in the molecular sieve, if the molecular sieve is not subjected to the activation treatment, the water and gas have competitive adsorption, so that the adsorption effect of ethylene gas is influenced, and the activated modified M-SAPO-RHO type zeolite molecular sieve has better selective adsorption performance on ethylene.
The invention preferably reduces the temperature of the activated modified M-SAPO-RHO type zeolite molecular sieve to room temperature, and then places the molecular sieve in a mixed system containing ethylene to selectively adsorb ethylene.
In the present invention, the ethylene-containing mixed system preferably includes an ethylene/ethane mixed system, propylene/propane, and methane.
In the present invention, the temperature of the selective adsorption is preferably 273 to 298K, more preferably 298K; the pressure for the selective adsorption is preferably 0 to 1bar, more preferably 1bar.
In the invention, the preparation method of the modified M-SAPO-RHO type zeolite molecular sieve preferably comprises the following steps:
mixing a silicon source, an aluminum source, phosphoric acid, a template agent, cetyl trimethyl ammonium bromide, SAPO-RHO seed crystals and water to obtain initial reaction gel; the template agent is diethylamine;
crystallizing the initial reaction gel to obtain an SAPO-RHO type zeolite molecular sieve, wherein the SAPO-RHO type molecular sieve contains a template agent;
under the condition of not removing a template agent, directly mixing the SAPO-RHO type zeolite molecular sieve with a cation solution, carrying out ion exchange reaction, and then roasting to obtain a modified M-SAPO-RHO type zeolite molecular sieve; the cation in the cation solution comprises Li + And/or Na + (ii) a The concentration of the cation solution is 0.5-1.0 mol/L.
In the present invention, unless otherwise specified, all the raw material components are commercially available products well known to those skilled in the art.
Mixing a silicon source, an aluminum source, phosphoric acid, a template agent, hexadecyl trimethyl bromide, SAPO-RHO crystal seeds subjected to high-temperature roasting and template agent removal and water to obtain initial reaction gel; the template agent is diethylamine.
In the present invention, the silicon source preferably includes one or more of silica sol, sodium silicate, solid silicon source and white carbon black, and more preferably includes silica sol or white carbon black. In the present invention, the silica content in the silica sol is preferably 30 to 40wt%, more preferably 40wt%.
In the present invention, the aluminum source preferably comprises one or more of aluminum hydroxide, alumina, aluminum chloride, aluminum sulfate, sodium aluminate, pseudoboehmite, aluminum isopropoxide and gibbsite.
In the invention, the silicon source, the aluminum source and the phosphoric acid are respectively used as SiO 2 、Al 2 O 3 And P 2 O 5 The molar ratio of the silicon source, the aluminum source, the phosphoric acid, the diethylamine, the hexadecyltrimethylammonium bromide and the water is preferably (0.2-1): 1 (0.8-1): 1.0-2.4): 0.03-0.2): 40-200),: more preferably (0.3-0.8): 1 (0.85-0.95): 1.5-2.0) (0.05-0.15): 50-180),: most preferably (0.4-0.6): 1 (0.85-0.9): 1.8-2.0) (0.05-0.10): 80-150.
In the present invention, the SAPO-RHO seeds are preferably synthesized according to the method described in the literature "x.su et Al./microporus and Mesoporous Materials 144 (2011) 113-119" and have a silicon content of Si/(Si + Al + P) molar ratio =0.135. In the invention, the SAPO-RHO crystal seed is preferably obtained by removing the template agent through high-temperature roasting, namely the SAPO-RHO crystal seed does not contain the template agent.
In the invention, the silicon source is used as SiO 2 The mass ratio of the silicon source to the SAPO-RHO seed crystal is preferably 1 (0.02-0.2), more preferably 1 (0.05-0.15), and most preferably 1 (0.1-0).15)。
In the present invention, the mixing of the silicon source, the aluminum source, the phosphoric acid, the template, the cetyltrimethylammonium bromide, the SAPO-RHO seed crystal and the water preferably comprises the following steps:
carrying out first mixing on water, an aluminum source and phosphoric acid to obtain a first mixed system;
carrying out second mixing on the first mixed system, a silicon source and a template agent to obtain a second mixed system;
thirdly mixing the second mixed system and hexadecyl trimethyl ammonium bromide to obtain initial gel;
and fourthly, mixing the initial gel and the SAPO-RHO crystal seeds to obtain the initial reaction gel.
The time for the first mixing is not specially limited, and the raw materials can be uniformly mixed. In the present invention, the time of the second mixing is preferably 2h; the time of the third mixing is preferably 3h; the time for the fourth mixing is preferably 10 to 20min. In the present invention, the mixing is preferably performed by stirring, and the stirring speed in the present invention is not particularly limited, and a stirring speed known in the art may be used.
After the initial reaction gel is obtained, crystallizing the initial reaction gel to obtain the SAPO-RHO type zeolite molecular sieve, wherein the SAPO-RHO type molecular sieve contains a template agent.
In the present invention, the crystallization is preferably static crystallization or dynamic crystallization. The equipment adopted by the static crystallization is not particularly limited, and the static crystallization equipment known in the field can be adopted; in the embodiment of the present invention, the static crystallization is preferably performed in a high pressure reaction vessel.
The equipment adopted by the dynamic crystallization is not particularly limited, and the dynamic crystallization equipment well known in the field can be adopted; in the embodiment of the present invention, the dynamic crystallization is preferably performed in a rotary oven; the rotation speed of the rotary oven is not particularly limited in the present invention, and any rotation speed known in the art may be used.
In the present invention, the temperature of the static crystallization and the dynamic crystallization is independently preferably 180 to 220 ℃, more preferably 190 to 210 ℃, and most preferably 190 to 200 ℃; the time for the dynamic crystallization and the static crystallization is independently preferably 24 to 48 hours, more preferably 27 to 42 hours, and most preferably 30 to 36 hours.
After crystallization, the invention preferably performs solid-liquid separation on the system obtained after crystallization, and dries the obtained solid material to obtain the SAPO-RHO type zeolite molecular sieve which contains the template agent. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode well known in the field, such as suction filtration or centrifugal separation, can be adopted. The drying method is not particularly limited in the invention, and the technical scheme of drying which is well known to the technicians in the field can be adopted; in the embodiment of the present invention, the drying manner is preferably drying; in the invention, the drying temperature is preferably 80-120 ℃, and more preferably 100 ℃; the drying time is preferably 12h.
In the present invention, the average crystal grain size of the SAPO-RHO type zeolite molecular sieve is preferably 0.5 to 3 μm, and more preferably 0.5 to 2 μm; the crystal morphology structure is 12-face body type.
The SAPO-RHO type zeolite molecular sieve prepared by the invention has high crystallinity, good composition stability, adjustable silicon-aluminum ratio and good repeatability.
After the SAPO-RHO type zeolite molecular sieve is obtained, the invention takes the SAPO-RHO type zeolite molecular sieve containing the organic template agent as a precursor of ion exchange to be directly mixed with a required cation solution under the condition of not removing the template agent, and the modified M-SAPO-RHO type zeolite molecular sieve is obtained by roasting after the ion exchange reaction; the cation in the cation solution comprises Li + And Na + One or more of the above; the concentration of the cation solution is 0.5-1.0 mol/L.
In the present invention, the cations in the cation solution are preferably derived from a soluble lithium salt and/or a soluble sodium salt. In the present invention, the soluble lithium salt preferably includes lithium chloride and/or lithium nitrate; the soluble sodium salt preferably comprises sodium chloride and/or sodium nitrate.
In the present invention, the SAPO-RHO type zeolite molecular sieve and the cationic solution are preferably mixed by stirring, and the stirring speed in the present invention is not particularly limited, and may be any stirring speed known in the art. In the present invention, the ratio of the mass of the SAPO-RHO type zeolite molecular sieve to the volume of the cation solution in the cation solution (i.e., solid-to-liquid ratio S/L) is preferably 1g: (20 to 100) mL, more preferably 1g: (50-100) mL.
In the invention, the temperature of the ion exchange reaction is 20-80 ℃, and more preferably 40-60 ℃; the time is preferably 4 to 8 hours, more preferably 4 to 6 hours. In the present invention, during the ion exchange reaction, li + And/or Na + Ion exchange is carried out on the SAPO-RHO type zeolite molecular sieve, and the cation composition and content of the SAPO-RHO type zeolite molecular sieve are changed, so that the selective adsorption capacity of the modified M-SAPO-RHO on ethylene is greatly improved.
After the ion exchange reaction, the invention roasts the obtained ion exchange product to obtain the modified M-SAPO-RHO type zeolite molecular sieve. In the present invention, it is preferable that before the calcination, the solid-liquid separation is performed on the system obtained after the ion exchange reaction, and the obtained solid material is washed with water and dried. In the present invention, the number of times of the water washing is preferably 3 times, and the purpose of the water washing is to remove impurities remaining on the surface of the sample. The solid-liquid separation mode is not particularly limited in the invention, and a solid-liquid separation mode known in the field, such as suction filtration or centrifugation, can be adopted. In the present invention, the drying temperature is preferably 80 to 120 ℃, more preferably 100 ℃, and the time is preferably 12 hours.
In the invention, the roasting temperature is preferably 550-800 ℃, and more preferably 550-700 ℃; the time is preferably 3 to 8 hours, more preferably 3 to 6 hours. In the present invention, the atmosphere for the calcination is preferably an air atmosphere. In the present invention, the purpose of the calcination is to remove the organic template from the sample.
The modified M-SAPO-RHO type zeolite molecular sieve prepared by the invention can ensure that the shape of the crystallinity of the molecular sieve is not damaged in the ion exchange process to a great extent, and the cation composition and the content of the M-SAPO-RHO type molecular sieve after ion exchange are changed by changing the type and the concentration of the alkali metal cation salt solution, thereby further improving the selective adsorption of the modified M-SAPO-RHO type zeolite molecular sieve to ethylene and realizing the high-efficiency separation of ethylene/ethane.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Under the condition of stirring at room temperature, adding 2.3g of phosphoric acid and 1.4g of pseudo-boehmite into 7mL of water, stirring to uniformly mix the materials, adding 0.9g of silica sol and 0.15g of hexadecyl trimethyl ammonium bromide, stirring for 2 hours until the materials are uniformly mixed, then slowly adding 1.75g of diethylamine, stirring for 3 hours to obtain initial gel, then adding 0.036g of SAPO-RHO crystal seeds, and stirring for 15 minutes to obtain final uniform initial reaction gel; transferring the gel into a high-pressure reaction kettle, crystallizing for 48 hours at the temperature of 200 ℃, then performing suction filtration or centrifugal separation, and drying the obtained solid material for 12 hours at the temperature of 100 ℃ to obtain the SAPO-RHO type zeolite molecular sieve; the relative crystallinity of the SAPO-RHO type zeolite molecular sieve is 100 percent;
the XRD pattern of the SAPO-RHO type zeolite molecular sieve is shown in figure 1, and as can be seen from figure 1, the synthesized product of the invention is the SAPO-RHO type zeolite molecular sieve with good crystallinity; the SEM image of the SAPO-RHO type zeolite molecular sieve is shown in FIG. 2, and as can be seen from FIG. 2, the obtained product under the synthesis conditions is pure phase, and no other heterogeneous phase is generated.
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution at room temperature for 5h in a proportion of 50, filtering, washing the obtained solid material with deionized water, drying at 100 ℃ for 12h, and then roasting in a muffle furnace at 600 ℃ for 4h to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.067.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and the temperature of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 2
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve prepared in the example 1 and 0.5mol/L lithium chloride solution at room temperature for 5 hours at a ratio of 50, filtering, washing the obtained solid material with deionized water, drying at 100 ℃ for 12 hours, and then roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.07.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and 350 ℃, performing a single-component gas isothermal adsorption and desorption test after the sample is cooled to room temperature, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Comparative example 1
The SAPO-RHO type zeolite molecular sieve prepared in the example 1 is activated for 10 hours under the vacuum condition and the temperature of 350 ℃, and after the sample is cooled to the room temperature, a single-component gas isothermal adsorption and desorption test is carried out, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in the table 1.
Comparative example 2
According to the literature (Microporous and Mesoporous Materials 144 (2011) 113-119), by adding CTAB in the beginning of the reaction, according to DEA: al: P: si: H 2 The mol ratio of O is 1.0.
Activating the pure-phase SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and the temperature of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 3
According to the technical scheme, the method comprises the following steps that (1) according to the S/L =1 ratio of the mass of the SAPO-RHO type zeolite molecular sieve to the volume of a sodium chloride solution: the SAPO-RHO type zeolite molecular sieve prepared in the example 1 and 1mol/L sodium chloride solution are stirred and mixed for 5 hours at room temperature, then filtered, the obtained solid material is washed by deionized water and dried for 12 hours at 100 ℃, and then the solid material is placed in a muffle furnace and roasted for 4 hours at 600 ℃ to obtain the modified Na-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Na/(Si + Al + P) is =0.125.
The XRD pattern of the modified Na-SAPO-RHO type zeolite molecular sieve is shown in figure 1, and as can be seen from figure 1, the synthesized product of the invention is the modified Na-SAPO-RHO type zeolite molecular sieve, and has good crystallinity; the SEM image of the modified Na-SAPO-RHO type zeolite molecular sieve is shown in FIG. 2, and as can be seen from FIG. 2, the obtained product under the synthesis conditions is pure phase, and no other impurity phase is generated.
Activating the modified Na-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and the temperature of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 4
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to sodium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve prepared in example 1 and 0.5mol/L sodium chloride solution at room temperature for 5 hours at a ratio of 50, filtering, washing the obtained solid material with deionized water, drying at 100 ℃ for 12 hours, and then roasting in a muffle furnace at 600 ℃ for 4 hours to obtain the modified Na-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Na/(Si + Al + P) is =0.08.
Activating the modified Na-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and the temperature of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 5
Under the condition of stirring at room temperature, adding 2.3g of phosphoric acid and 2.04g of aluminum isopropoxide into 14mL of water, adding 0.36g of white carbon black and 0.2g of hexadecyl trimethyl ammonium bromide, stirring for 2 hours until the mixture is uniform, then slowly adding 1.75g of diethylamine, stirring for 3 hours to obtain initial gel, then adding 0.036g of SAPO-RHO seed crystal, and stirring for 15 minutes to obtain uniform sol; and transferring the sol into a high-pressure reaction kettle, crystallizing for 24 hours at the temperature of 200 ℃, filtering, and drying the obtained solid material for 12 hours at the temperature of 100 ℃ to obtain the SAPO-RHO type zeolite molecular sieve with the relative crystallinity of 100%.
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution at the room temperature for 5 hours at a ratio of 50, filtering, washing the obtained solid material with deionized water, drying at the temperature of 110 ℃ for 12 hours, and then roasting in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.09.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and the temperature of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 6
Under the condition of stirring at room temperature, adding 1.15 g of phosphoric acid and 0.7g of pseudo-boehmite into 7.2mL of water, stirring to mix uniformly, adding 0.45g of silica sol and 0.1g of hexadecyl trimethyl ammonium bromide, stirring for 2h until the mixture is mixed uniformly, then slowly adding 0.66g of diethylamine, stirring for 3h to obtain initial gel, then adding 0.018g of SAPO-RHO crystal seed, and stirring for 15min to obtain uniform sol; and transferring the sol into a high-pressure reaction kettle, crystallizing for 48 hours at the temperature of 200 ℃, filtering, and drying the obtained solid material for 12 hours at the temperature of 100 ℃ to obtain the SAPO-RHO type zeolite molecular sieve with the relative crystallinity of 99.5%.
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution at the room temperature for 5h according to the proportion of 100, filtering, washing the obtained solid material with deionized water, drying at the temperature of 100 ℃ for 12h, and then roasting in a muffle furnace at the temperature of 600 ℃ for 4h to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.085.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and 350 ℃, performing a single-component gas isothermal adsorption and desorption test after the sample is cooled to room temperature, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 7
Under the condition of stirring at room temperature, adding 0.95g of phosphoric acid and 1.02g of aluminum isopropoxide into 10mL of water, stirring to uniformly mix the phosphoric acid and the aluminum isopropoxide, adding 0.45g of silica sol and 0.15g of hexadecyl trimethyl ammonium bromide, stirring for 2 hours until the mixture is uniformly mixed, then slowly adding 0.87g of diethylamine, stirring for 3 hours to obtain initial gel, then adding 0.02g of SAPO-RHO crystal seeds, and stirring for 15 minutes to obtain uniform sol; transferring the sol into a high-pressure reaction kettle, crystallizing at 180 ℃ for 48h, filtering, drying the obtained solid material at 100 ℃ for 12h to obtain the SAPO-RHO type zeolite molecular sieve with the relative crystallinity of 100 percent
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution at the room temperature for 5 hours in a proportion of 100, filtering, washing the obtained solid material with deionized water, drying at the temperature of 100 ℃ for 12 hours, and then roasting in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain the Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.086.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition and 350 ℃, performing a single-component gas isothermal adsorption and desorption test after the sample is cooled to room temperature, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 8
Under the condition of stirring at room temperature, adding 0.92g of phosphoric acid and 0.7g of pseudo-boehmite into 3.6mL of water, stirring to mix uniformly, adding 0.15g of white carbon black and 0.18g of hexadecyl trimethyl ammonium bromide, stirring for 2h until the mixture is mixed uniformly, then slowly adding 0.87g of diethylamine, stirring for 3h to obtain initial gel, then adding 0.018g of SAPO-RHO crystal seed, and stirring for 15min to obtain uniform sol; and transferring the gel into a high-pressure reaction kettle, crystallizing for 48 hours at 180 ℃, then performing suction filtration or centrifugation for separation, and drying the obtained solid material for 12 hours at 100 ℃ to obtain the SAPO-RHO type zeolite molecular sieve with the relative crystallinity of 95.4%.
According to the weight ratio S/L =1 of SAPO-RHO type zeolite molecular sieve to lithium chloride solution: stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution at the room temperature for 5 hours in a proportion of 100, filtering, washing the obtained solid material with deionized water, drying at the temperature of 110 ℃ for 12 hours, and then roasting in a muffle furnace at the temperature of 600 ℃ for 4 hours to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the molar ratio of Li/(Si + Al + P) is =0.092.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
Example 9
Under the condition of stirring at room temperature, adding 2.3kg of phosphoric acid and 1.4kg of pseudo-boehmite into 7L of water, stirring to uniformly mix the materials, adding 0.9kg of silica sol and 0.1kg of hexadecyl trimethyl ammonium bromide, stirring for 2 hours until the materials are uniformly mixed, then slowly adding 1.75kg of diethylamine, stirring for 3 hours to obtain initial gel, then adding 0.036kg of SAPO-RHO crystal seeds, and stirring for 15 minutes to obtain uniform sol; and transferring the sol into a high-pressure reaction kettle, crystallizing for 48 hours at the temperature of 200 ℃, filtering, and drying the obtained solid material for 12 hours at the temperature of 100 ℃ to obtain the SAPO-RHO type zeolite molecular sieve with the relative crystallinity of 100%.
Stirring and mixing the SAPO-RHO type zeolite molecular sieve and 1mol/L lithium chloride solution for 5h at room temperature according to the proportion of the SAPO-RHO type zeolite molecular sieve to the lithium chloride solution with the volume ratio S/L =1 of 50, filtering, washing the obtained solid material with deionized water, drying for 12h at 100 ℃, and then roasting for 4h at 600 ℃ in a muffle furnace to obtain the modified Li-SAPO-RHO type zeolite molecular sieve, wherein the Li/(Si + Al + P) molar ratio =0.07.
Activating the modified Li-SAPO-RHO type zeolite molecular sieve for 10 hours under the vacuum condition of 350 ℃, cooling the sample to room temperature, and then performing single-component gas isothermal adsorption and desorption test, wherein the test temperature is 298K, the test pressure is 1bar, and the separation results are shown in Table 1.
TABLE 1 separation Effect of modified M-SAPO-RHO type zeolite molecular sieves and SAPO-RHO type zeolite molecular sieves
As can be seen from Table 1, the selective adsorption performance of the modified M-SAPO-RHO type zeolite molecular sieve obtained by ion exchange modification is remarkably improved compared with that of the unmodified SAPO-RHO type zeolite molecular sieve.
SAPO-RHO and modified Li-SAPO-RHO as prepared in example 1 and Na-SAPO-RHO as prepared in example 3 were performed at a test temperature of 298K at test pressures of 0.2bar, 0.4bar, 0.6bar, 0.8bar and 1.0bar with respect to C 2 H 4 And C 2 H 6 The saturated adsorption capacity of (a) is shown in fig. 3 and table 2.
TABLE 2 results of saturated adsorption capacity (mmol/g) measurement
As can be seen from FIG. 3 and Table 2, the modified M-SAPO-RHO type zeolite molecular sieve pair C obtained by ion exchange modification of the unmodified SAPO-RHO type zeolite molecular sieve 2 H 4 The selective adsorption performance is obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. Use of a modified zeolite molecular sieve of the M-SAPO-RHO type as an ethylene selective adsorbent in an ethylene/ethane mixed system, characterized in that said M comprises Li + And/or Na + (ii) a The molar ratio of M/(Si + Al + P) in the modified M-SAPO-RHO type zeolite molecular sieve is =0.05 to 0.17; the activation treatment is carried out under vacuum condition; the temperature of the activation treatment is 200-350 ℃, and the time is 4-10 h.
2. The application according to claim 1, characterized in that the method of application comprises the following steps: activating the modified M-SAPO-RHO type zeolite molecular sieve, and placing the activated molecular sieve in a mixed system containing ethylene to selectively adsorb the ethylene.
3. The use according to claim 2, wherein the selective adsorption is carried out at a temperature of 298K and at a pressure of 0 to 1bar.
4. Use according to claim 1, characterized in that the preparation process of said modified zeolite molecular sieve of the M-SAPO-RHO type comprises the following steps:
mixing a silicon source, an aluminum source, phosphoric acid, a template agent, cetyl trimethyl ammonium bromide, SAPO-RHO seed crystals and water to obtain initial reaction gel; the template agent is diethylamine;
crystallizing the initial reaction gel to obtain a SAPO-RHO type zeolite molecular sieve, wherein the SAPO-RHO type zeolite molecular sieve contains a template agent;
directly mixing the SAPO-RHO type zeolite molecular sieve with a cation solution under the condition of not removing a template agent, and roasting after ion exchange to obtain a modified M-SAPO-RHO type zeolite molecular sieve; the cation in the cation solution comprises Na + And/or Li + (ii) a The concentration of the cation solution is 0.5 to 1.0mol/L.
5. The application of claim 4, wherein the silicon source comprises one or more of silica sol, sodium silicate and white carbon black;
the aluminum source comprises one or more of aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum sulfate, sodium aluminate, pseudo-boehmite, aluminum isopropoxide and gibbsite.
6. The use of claim 4 or 5, wherein the source of silicon, the source of aluminum, and the phosphoric acid are SiO, al, or a combination thereof 2 、Al 2 O 3 And P 2 O 5 The counting is carried out on the basis of the number of the counter,
the molar ratio of the silicon source, the aluminum source, the phosphoric acid, the diethylamine, the hexadecyl trimethyl ammonium bromide and the water is (0.2 to 1) to (0.8 to 1.2) to (1.0 to 2.4) to (0.03 to 0.2) to (40 to 200);
the mass ratio of the silicon source to the SAPO-RHO seed crystal is 1 (0.05 to 0.2).
7. The use as claimed in claim 4, wherein the crystallization is carried out at 180 to 220 ℃ for 24 to 48h.
8. The use according to claim 4, wherein the ion exchange reaction is carried out at a temperature of 40 to 80 ℃ for 4 to 8h;
the roasting temperature is 550 to 800 ℃, and the time is 3 to 8h.
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