CN110124731A - A kind of in-situ synthetic method of metal SAPO-34 molecular sieve and application - Google Patents
A kind of in-situ synthetic method of metal SAPO-34 molecular sieve and application Download PDFInfo
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- CN110124731A CN110124731A CN201910427785.3A CN201910427785A CN110124731A CN 110124731 A CN110124731 A CN 110124731A CN 201910427785 A CN201910427785 A CN 201910427785A CN 110124731 A CN110124731 A CN 110124731A
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- molecular sieve
- crystallization
- sapo
- metal
- meapso
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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 62
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 61
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 30
- 230000008025 crystallization Effects 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000003483 aging Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 235000011007 phosphoric acid Nutrition 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910001593 boehmite Inorganic materials 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008279 sol Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 235000012211 aluminium silicate Nutrition 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 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 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002253 acid Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000012452 mother liquor Substances 0.000 abstract 1
- 230000011218 segmentation Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910001631 strontium chloride Inorganic materials 0.000 description 3
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of in-situ synthetic method of metal SAPO-34 molecular sieve and applications.Synthetic method is the following steps are included: silicon source, phosphorus source, silicon source, water, metal salt solution and organic amine template are mixed, and is sufficiently stirred；Complete gel will be stirred after mixing and is fitted into crystallization in hydrothermal synthesis kettle, after crystallization is complete, separate solid crystallization product and mother liquor, and washed, dry, roasting obtains MeAPSO-34 molecular sieve catalyst.The present invention uses a step in-situ synthesis, and segmentation crystallization prepares metal SAPO-34 molecular sieve, thus the acid site property of effectively modulation SAPO-34 molecular sieve.The catalyst is applied to methanol to olefins reaction and is able to extend catalyst life, and improves yield of light olefins, especially increases the yield of ethylene.
Description
Technical field
The invention belongs to technical field of molecular sieve, and in particular to a kind of in-situ synthetic method of metal SAPO-34 molecular sieve
And its application in oxygenatedchemicals olefine reaction.
Technical background
1984, U.S. combinating carbide company (UCC) develops silicoaluminophosphate Series Molecules sieve, and (SAPO-n, n were represented
Structure model), wherein SAPO-34 is most of interest by people.The cellular structure and acidity of SAPO-34 determines that it is urged a variety of
Change the potential using value in reaction.In fact, SAPO-34 molecular sieve is due to good selectivity of light olefin and excellent
Thermal stability and hydrothermal stability etc., be successfully applied in methanol-to-olefins (MTO) industrial production equipment, for development
Non-oil resource produces the products such as ethylene, propylene, and alleviation petroleum resources are in short supply, realizes that the clean and effective of coal utilizes, has weight
The strategic importance wanted.
It is since quick carbon distribution is made by the main problem that the catalyst of active component faces at present of SAPO-34 molecular sieve
At catalyst life it is short, and selectivity of light olefin is to be improved.MTO reaction belongs to acid catalyzed reaction, framework of molecular sieve
The intensity and number of middle acid centre directly affect the selectivity of low-carbon alkene, and suitable acid amount and strong/weak acid ratio are conducive to
The generation of low-carbon alkene.Change at present there are mainly two types of acid site intensity sum number purpose modes, in SAPO-34 framework of molecular sieve
The middle coordination environment and relative amount for introducing metal ion or changing framework of molecular sieve silicon.The wherein introducing meeting of metal ion
Cause the variation of acidic zeolite and aperture size.Aperture, which becomes smaller, can limit the diffusion of macromolecular, be conducive to small molecule low-carbon alkene
The raising of hydrocarbon-selective, and acid site intensity it is modulated after can form the acid site of moderate strength, be also beneficial to low-carbon alkene
It generates.
Patent CN1704390 is modified SAPO-34 by using metallic element Zn to obtain ZnAPSO-34 molecular sieve,
The molecular sieve is used in methanol to olefins reaction, the selectivity of low-carbon alkene is improved.But modified point is not expressly mentioned in text
The preparation method of son sieve.
Patent CN1754624A is prepared for a kind of metal-modified SAPO-34 molecular sieve using infusion process.This method process compared with
Complexity, and the stability of catalyst is affected.
Patent CN104244679A prepares spherical heteroatom using hydrothermal crystallization method by the addition of chelating agent
NiAPSO-34 molecular sieve, but the molecular sieve is low compared with the crystallinity of classic cube SAPO-34 molecular sieve, and global molecular sieve is straight
About 8~12 μm of diameter, partial size is bigger than normal.
Patent CN107986297A discloses a kind of preparation method of metal-modified mesoporous SAPO-34 molecular sieve.Pass through
The SAPO-34 molecular sieve with micropore canals and mesopore orbit is prepared in the addition of mesoporous template and micropore template agent.This point
Son sieve is for facilitating the raising of ethylene selectivity in methanol to olefins reaction.But the preparation method slightly complicated of molecular sieve,
And the crystallinity of metal modified molecular screen decreases.
In the preparation of metal-modified SAPO-34 molecular sieve described above, or it joined the substance with special role,
Or synthesis process is more complex or synthetic method has certain side effect to the performance of catalyst, there is limitation product actual production
The unfavorable factor of application, therefore seek one kind and be simple and efficient, be at low cost, and be able to ascend SAPO-34 points of catalyst performance
Son sieve and preparation method thereof has very big influence and value to the development of oxygenatedchemicals alkene technology.
Summary of the invention
The present invention overcomes deficiency in the prior art, problem to be solved be to provide a kind of synthetic method it is simple, can be real
It is Shi Xingqiang, at low cost, and the reactivity worth of catalyst can be significantly improved, the SAPO-34 molecule of catalyst stability is not reduced
The preparation method of sieve.The metal modified molecular screen is mainly used in preparing low-carbon olefin from oxygen-containing compounds reaction, low for improving
The selectivity of carbon olefin, especially ethylene selectivity have extremely important effect.
The present invention uses traditional hydrothermal synthesis method, using conventional mould agent, passes through preferred suitable metal-modified member
Plain fabricated in situ goes out MeAPSO-34 molecular sieve.Compared to unmodified molecular sieve, metal modified molecular screen reduces acid site
Intensity is conducive to low-carbon alkene so as to form the acid site for the moderate strength for being more suitable for oxygenatedchemicals olefine reaction
It generates.Meanwhile the introducing of metallic element, reduce orifice diameter, the more conducively diffusion of ethylene.And the side for passing through fabricated in situ
Metallic element is introduced into framework of molecular sieve by method, and the stability of catalyst will not be affected.
The present invention uses in-situ synthesis, and simple, efficient, without adding other auxiliary agents, multistage crystallization is also beneficial to be formed
Property is more stable, the more uniform SAPO-34 molecular sieve of grain size.The molecular sieve is anti-for oxygenatedchemicals alkene
It answers, in MTO reaction, there is higher selectivity of light olefin and higher ethylene selectivity, compared to unmodified
The total recovery of SAPO-34 molecular sieve, ethylene and propylene can be improved 4% or so, and 7% or so, while molecule can be improved in yield of ethene
Sieve life longer 30% or so.
The purpose of the present invention is by the following technical programs to solve.
MeAPSO-34 molecular sieve of the present invention, synthesis step are as follows.
A) silicon source, phosphorus source, silicon source, water, metal salt solution and organic amine template are mixed, and stirred evenly, obtained
The Primogel mixed liquor of MeAPSO-34 molecular sieve；
B) above-mentioned mixed liquor is fitted into hydrothermal synthesis kettle, carries out a Duan Laohua at 50~100 DEG C, ageing time 0~
12h；
C) 80~150 DEG C of progress, two sections of agings are continuously heating to after one section of aging, ageing time 0~12h, two sections
Aging temperature is at least 20 DEG C high compared with one section of aging temperature；
D) after two sections of agings, 160~220 DEG C are continuously heating to, carries out 10~80h of hydrothermal crystallizing；
E) it after crystallization, is centrifugated, washs, being dried to obtain solid product, and in air at 450~650 DEG C
Template contained in 3~10 hours removal original powders is roasted, MeAPSO-34 molecular sieve is obtained.
Step a) the silicon source is selected from silica solution, ethyl orthosilicate, active silica, sodium metasilicate, the height through overactivation
The mixing of one or more of ridge soil or gangue through overactivation；Source of aluminium be selected from boehmite, boehmite,
The mixing of one or more of Aluminum sol, aluminium oxide, aluminium hydroxide, aluminum soluble salt or aluminium isopropoxide；Phosphorus source is selected from
Orthophosphoric acid；The template is selected from diethylamine, triethylamine, morpholine, tetraethyl ammonium hydroxide, etamon chloride, tetrem bromide
Change the mixing of one or more of ammonium, diisopropylamine or di-n-propylamine.
Step a) the metal salt is selected from the transition metal such as alkaline-earth metal and nickel, cobalt, zinc, manganese, iron such as magnesium, calcium, barium, strontium
Nitrate, sulfate, acetate, one of chloro salt or a variety of mixing, wherein being preferably selected from strontium, nickel, cobalt, zinc, manganese
One of salt or a variety of mixing, the metal salt are soluble easily in water.
This metal-modified SAPO-34 molecular sieve, which is used as in catalysis oxygenatedchemicals olefine reaction, has height
Selectivity of light olefin, especially high ethylene selectivity.
Compared with prior art, the invention has the advantages that.
1. the synthesis of MeAPSO-34 molecular sieve of the invention uses hydrothermal synthesis method, it is easier to realize the industry of molecular sieve
Production.
2. the synthesis of MeAPSO-34 molecular sieve of the invention uses in-situ synthetic method, simple, efficient, and stability
It is good.
3. being dropped in synthesis material of the invention without adding other solvents other than water or the auxiliary agent with special role
Low cost of material, avoids the separating step of subsequent complexity.
4. MeAPSO-34 molecular sieve prepared by the present invention is applied in oxygenatedchemicals olefine reaction, the service life is more
Long, selectivity of light olefin and ethylene selectivity are higher.
Detailed description of the invention
Fig. 1 is the XRD spectra of the embodiment of the present invention 1~6 and the sintetics of comparative example 1 and 2.
Specific embodiment
The following examples will be further described the present invention, but not thereby limit the invention.
Embodiment 1
85.65g water and 1.82g nickel nitrate is first added under room temperature into beaker, stirs evenly and is completely dissolved, then according to
Secondary addition 12.14g boehmite, 19.22g phosphoric acid and 6.67g silica solution are sufficiently mixed stirring 1 hour, are eventually adding
32.04g triethylamine continues stirring 1 hour, obtains NiAPSO-34 molecular sieve initial gel mixture；Primogel is mixed
Object is fitted into stainless steel cauldron, then reaction kettle is put into homogeneous reactor, is warming up to 70 DEG C, constant temperature 5 hours；One section pre-
After crystallization, 120 DEG C are continuously heating to, constant temperature 5h；After two sections of pre- crystallization, 200 DEG C are continuously heating to, constant temperature 48h.
After crystallization, reaction kettle and chilling are taken out；Solid product is centrifuged, and is washed with deionized to neutrality, and dried
After night, NiAPSO-34 molecular screen primary powder is obtained；Original powder obtains NiAPSO-34 molecular sieve in roasting 4 hours through 600 DEG C and (is denoted as
C-1).The XRD spectra of C-1 is as shown in Figure 1.
Embodiment 2
16g water and 0.75g strontium chloride is first added under room temperature into beaker, is completely dissolved strontium chloride.Then to another burning
It is separately added into 40g water, 13.67g boehmite, 27g phosphoric acid and 28.7g silica solution in cup, after being sufficiently mixed stirring 1 hour
The aqueous solution of strontium chloride is added, stirs evenly, is eventually adding 17.54g diisopropylamine, continues stirring 1 hour, obtains SrAPSO-
34 molecular sieve initial gel mixtures；Initial gel mixture is fitted into stainless steel cauldron, then reaction kettle is put into homogeneously
In reactor, 110 DEG C are warming up to, constant temperature 7h；After pre- crystallization, 220 DEG C are continuously heating to, constant temperature 20h.After crystallization,
Take out reaction kettle and chilling；Solid product is centrifuged, and is washed with deionized to neutrality, and after being dried overnight, is obtained
SrAPSO-34 molecular screen primary powder；Original powder roasts 3 hours through 650 DEG C and obtains SrAPSO-34 molecular sieve (being denoted as C-2).C-2's
XRD spectra is as shown in Figure 1.
Embodiment 3
10g water and 0.1g cobaltous sulfate is first added under room temperature into beaker, is completely dissolved cobaltous sulfate.Then to another burning
70g water, 8.5g aluminium isopropoxide, 16.4g phosphoric acid, 14.8g ethyl orthosilicate and 24.8g triethylamine and 15.3g are separately added into cup
Morpholine is added the aqueous solution of cobaltous sulfate, continues stirring 1 hour, obtain CoAPSO-34 molecular sieve after being sufficiently mixed stirring 1 hour
Initial gel mixture；Initial gel mixture is fitted into stainless steel cauldron, then reaction kettle is put into homogeneous reactor
It is interior, it is warming up to 100 DEG C, constant temperature 4 hours；After one section of pre- crystallization, 150 DEG C are continuously heating to, constant temperature 8h；Two sections of pre- crystallization
After, 160 DEG C are continuously heating to, constant temperature 80h.After crystallization, reaction kettle and chilling are taken out；Solid product is through centrifugation point
From being washed with deionized to neutrality, and after being dried overnight, obtain CoAPSO-34 molecular screen primary powder；Original powder is roasted through 550 DEG C
It burns 6 hours and obtains CoAPSO-34 molecular sieve (being denoted as C-3).The XRD spectra of C-3 is as shown in Figure 1.
Embodiment 4
102g water, 18.2g boehmite, 2g silica solution, 23.7g phosphoric acid, 3.3g tetra- is successively added under room temperature into beaker
Ethyl ammonium hydroxide and 1.8g zinc acetate are sufficiently mixed stirring 1 hour or so, and it is mixed to obtain ZnAPSO-34 molecular sieve Primogel
Close object；Initial gel mixture is fitted into stainless steel cauldron, then reaction kettle is put into homogeneous reactor, is warming up to 50
DEG C, constant temperature 12 hours；After one section of pre- crystallization, 80 DEG C are continuously heating to, constant temperature 12h；After two sections of pre- crystallization, continue
210 DEG C are warming up to, constant temperature 10h.After crystallization, reaction kettle and chilling are taken out；Solid product is centrifuged, and uses deionization
Water washing obtains ZnAPSO-34 molecular screen primary powder to neutrality, and after being dried overnight；Original powder roasts 10 hours through 450 DEG C to obtain the final product
To ZnAPSO-34 molecular sieve (being denoted as C-4).The XRD spectra of C-4 is as shown in Figure 1.
Embodiment 5
32.4g water, 10.9g Aluminum sol, 10g silica solution, 21.1g phosphoric acid, 1g nitric acid is successively added under room temperature into beaker
Nickel and 1.4g zinc nitrate are sufficiently mixed after mixing evenly, 30g diethylamine and 27.6g etamon chloride are added, continues stirring 1
Hour or so, obtain NiZnAPSO-34 molecular sieve initial gel mixture；Initial gel mixture is packed into stainless steel reaction
In kettle, then reaction kettle is put into homogeneous reactor, is warming up to 180 DEG C, constant temperature 30h.After crystallization, reaction kettle is taken out simultaneously
Chilling；Solid product is centrifuged, and is washed with deionized to neutrality, and after being dried overnight, and obtains NiZnAPSO-34 points
Son sieve original powder；Original powder roasts 7 hours through 500 DEG C and obtains NiZnAPSO-34 molecular sieve (being denoted as C-5).The XRD spectra of C-5
As shown in Figure 1.
Embodiment 6
100g water, 6g nickel nitrate and 5.3g cobaltous sulfate is first added under room temperature into beaker, keeps nickel nitrate and cobaltous sulfate complete
Dissolution.Then 750g water, 33.7g triethylamine, 122.8g tetraethyl ammonium hydroxide, 122.5g are separately added into another beaker
The water-soluble of configured metal salt is added after being sufficiently mixed stirring 2 hours in boehmite, 192g phosphoric acid and 50g silica solution
Liquid stirs evenly, and obtains NiCoAPSO-34 molecular sieve initial gel mixture；Initial gel mixture is packed into 2L synthesis reactor
It is interior, it is warming up to 80 DEG C, constant temperature 8 hours；After one section of pre- crystallization, 130 DEG C are continuously heating to, constant temperature 5h；Two sections of pre- crystallization knots
Shu Hou is continuously heating to 200 DEG C, constant temperature 30h.After crystallization, cooling synthesis reactor；Solid product is centrifuged, spend from
Sub- water washing obtains NiCoAPSO-34 molecular screen primary powder to neutrality, and after being dried overnight；Original powder roasts 6 hours through 550 DEG C
Obtain NiCoAPSO-34 molecular sieve (being denoted as C-6).The XRD spectra of C-6 is as shown in Figure 1.
Comparative example 1
86.8g water, 12.14g boehmite, 19.22g phosphoric acid and 6.67g silicon are first sequentially added under room temperature into beaker
Colloidal sol is sufficiently mixed stirring 1 hour, is eventually adding 32.04g triethylamine, continues stirring 1 hour, obtains SAPO-34 molecular sieve
Initial gel mixture；Initial gel mixture is fitted into stainless steel cauldron, then reaction kettle is put into homogeneous reactor
It is interior, it is warming up to 70 DEG C, constant temperature 5 hours；After one section of pre- crystallization, 120 DEG C are continuously heating to, constant temperature 5h；Two sections of pre- crystallization knots
Shu Hou is continuously heating to 200 DEG C, constant temperature 48h.After crystallization, reaction kettle and chilling are taken out；Solid product is centrifuged,
It is washed with deionized to neutrality, and after being dried overnight, obtains SAPO-34 molecular screen primary powder；Original powder roasts 4 hours through 600 DEG C
Obtain SAPO-34 molecular sieve (being denoted as A-1).The XRD spectra of A-1 is as shown in Figure 1.
Comparative example 2
80g water, 24.8g triethylamine, 15.3g morpholine, 8.5g aluminium isopropoxide, 16.4g is successively added under room temperature into beaker
Phosphoric acid and 14.8g ethyl orthosilicate obtain SAPO-34 molecular sieve initial gel mixture after being sufficiently mixed stirring 1 hour；It will
Initial gel mixture is fitted into stainless steel cauldron, then reaction kettle is put into homogeneous reactor, is warming up to 100 DEG C, constant temperature
4 hours；After one section of pre- crystallization, 150 DEG C are continuously heating to, constant temperature 8h；After two sections of pre- crystallization, it is continuously heating to 170
DEG C, constant temperature 80h.After crystallization, reaction kettle and chilling are taken out；Solid product is centrifuged, and is washed with deionized into
Property, and after being dried overnight, obtain SAPO-34 molecular screen primary powder；Original powder roasts 6 hours through 550 DEG C and obtains SAPO-34 molecule
It sieves (being denoted as A-2).The XRD spectra of A-2 is as shown in Figure 1.
Embodiment 7
8 samples made from embodiment 1-6 and comparative example 1,2 are subjected to tabletting, are crushed to 40~60 mesh.Weigh 1g
Sample is fitted into fixed bed reactors, carries out methanol to olefins reaction evaluation.Methanol is carried by nitrogen, nitrogen flow rate 35ml/
Min, 450 DEG C of reaction temperature, methanol (40wt%) weight space velocity 1.5h-1.Obtained product is divided online by gas-chromatography
Analysis.It the results are shown in Table 1.From table 1 it follows that compare unmodified SAPO-34 molecular sieve, the ethylene of metal-modified sample and
The overall selectivity of propylene is higher (highest (ethylene+propylene) selectivity when 100% methanol conversion), the especially selection of ethylene
Property is higher, and catalyst life has also obtained greatly extending.
1 sample methanol to olefins reaction result of table
Claims (7)
1. a kind of in-situ synthetic method of metal SAPO-34 molecular sieve, which is characterized in that the method is by silicon source, phosphorus source, silicon
Source, water, metal salt solution and organic amine template R mixing, and stir evenly, obtain the Primogel of MeAPSO-34 molecular sieve
Mixed liquor；Gel is fitted into crystallization in hydrothermal synthesis kettle, after crystallization, centrifuge separation, washing, dry, roasting obtain solid
Product, i.e. MeAPSO-34 molecular sieve catalyst.
2. according to the method described in claim 1, the mol ratio of each component is as follows in mixed liquor: SiO2: Al2O3: P2O5: R:
H2O=(0.08~1.2): (0.8~1.2): (0.8~1.2): (0.04~8): (30~90), metal salt are accounted in above-mentioned solution and are done
The 0.3%~15% of base weight amount.
3. the method according to claim 1, wherein the following steps are included:
(1) silicon source, phosphorus source, silicon source, water, template and the metal salt solution completely dissolved in water are mixed at room temperature, and
It stirs evenly；
(2) above-mentioned mixed liquor is fitted into hydrothermal synthesis kettle, a Duan Laohua, 0~12h of ageing time is carried out at 50~100 DEG C；
After (3) one sections of agings, it is continuously heating to 80~150 DEG C of progress, two sections of agings, 0~12h of ageing time, two sections of agings
Temperature is at least 20 DEG C high compared with one section of aging temperature；
After (4) two sections of agings, 160~220 DEG C are continuously heating to, carries out 10~80 h of hydrothermal crystallizing；
(5) it after crystallization, is centrifugated, washs, being dried to obtain solid product, and being roasted at 450~650 DEG C in air
Template contained in 3~10 hours removal original powders, obtains MeAPSO-34 molecular sieve.
4. the synthetic method of MeAPSO-34 molecular sieve according to claim 1 or 3, which is characterized in that the silicon source is selected from
In silica solution, ethyl orthosilicate, active silica, sodium metasilicate, the kaolin through overactivation or the gangue through overactivation
One or more of mixing；Source of aluminium is selected from boehmite, boehmite, Aluminum sol, aluminium oxide, aluminium hydroxide, solvable
The mixing of one or more of property aluminium salt or aluminium isopropoxide；Phosphorus source is selected from orthophosphoric acid；The template be selected from diethylamine,
One in triethylamine, morpholine, tetraethyl ammonium hydroxide, etamon chloride, tetraethylammonium bromide, diisopropylamine or di-n-propylamine
Kind or several mixing.
5. the synthetic method of MeAPSO-34 molecular sieve according to claim 1 or 3, which is characterized in that the metal salt choosing
From the nitrate of the transition metal such as the alkaline-earth metal such as magnesium, calcium, barium, strontium and nickel, cobalt, zinc, manganese, iron, sulfate, acetate, chloro
One of salt or a variety of mixing, the metal salt are soluble easily in water.
6. the synthetic method of MeAPSO-34 molecular sieve according to claim 1 or 3, the metal salt be preferably selected from strontium,
One of nickel, cobalt, zinc, manganese salt or a variety of mixing.
7. a kind of MeAPSO-34 molecular sieve described in claim 1 or 3 is used as in catalysis preparing low-carbon olefin from oxygen-containing compounds reaction
With high selectivity of light olefin, especially high ethylene selectivity.
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| CN113213506A (en) * | 2021-06-01 | 2021-08-06 | 江西师范大学 | Preparation method and application of metal modified SAPO-34 molecular sieve |
| CN114890435A (en) * | 2022-06-22 | 2022-08-12 | 中国石油大学(华东) | Hollow-structure SAPO-34 molecular sieve prepared by MTO waste catalyst and preparation method and application thereof |
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