CN108187736B - Gibbsite @ SAPO molecular sieve compound with core-shell structure, preparation method and application thereof in catalyzing methanol to olefin - Google Patents
Gibbsite @ SAPO molecular sieve compound with core-shell structure, preparation method and application thereof in catalyzing methanol to olefin Download PDFInfo
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- CN108187736B CN108187736B CN201810055930.5A CN201810055930A CN108187736B CN 108187736 B CN108187736 B CN 108187736B CN 201810055930 A CN201810055930 A CN 201810055930A CN 108187736 B CN108187736 B CN 108187736B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910001679 gibbsite Inorganic materials 0.000 title claims abstract description 72
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 71
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 molecular sieve compound Chemical class 0.000 title abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims description 35
- 230000008025 crystallization Effects 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 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 description 11
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 10
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 7
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002202 Polyethylene glycol 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 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
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 238000001228 spectrum Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a gibbsite @ SAPO molecular sieve compound with a core-shell structure, a preparation method and application thereof in catalyzing methanol to olefin. The composite has a core-shell structure with gibbsite as a core and SAPO-34 as a shell, and an XRD diffraction spectrum of the composite shows the coexistence characteristic of the gibbsite and SAPO-34, wherein the ratio of the intensity of a peak with 2 theta at 18.3 degrees +/-0.10 degrees, which is attributed to the characteristic peak of the gibbsite, to the intensity of a peak with 2 theta at 18.05 degrees +/-0.10 degrees, which is attributed to the characteristic peak of the SAPO-34 is 0.2-10. The catalyst containing the gibbsite @ SAPO molecular sieve composite with the core-shell structure is used for the reaction of preparing olefin from methanol, and has high olefin selectivity and reaction life.
Description
Technical Field
The invention relates to a molecular sieve composite for catalyzing methanol to prepare olefin, in particular to a gibbsite @ SAPO molecular sieve composite with a core-shell structure.
Background
The Methanol To Olefin (MTO) technology is a key technology in a novel coal chemical industry which is mainly developed in China in the new century, can replace the traditional petroleum route so as to realize the diversification of olefin raw materials, and currently realizes large-scale industrial application.
An important class of catalysts used in the MTO technology is Silicoaluminophosphate (SAPO) family of molecular sieves. The molecular sieve is invented by UCC company in the beginning of the eighties of the twentieth century, the framework of the molecular sieve is composed of phosphorus-oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxygen tetrahedron, the framework has negative charges, and the molecular sieve can be used as a solid acid catalyst for reactions such as hydrocarbon cracking, isomerization, alcohol dehydration and the like. Among them, small pore SAPO molecular sieves having an eight-membered oxygen ring pore size (about 4 angstroms in diameter), such as SAPO-34, SAPO-18, etc., are widely used in MTO catalysts. In recent years, researchers have continually strived to improve the performance of MTO catalysts.
In the prior art, the selectivity of the MTO reaction is usually improved by modulating the types of the silicon source and the template to synthesize a molecular sieve material with a dual structure characteristic or a dual pore channel characteristic, but in the prior art, the raw materials are expensive to select, the preparation process is complex, and the like, so that the prior art still has room for improvement.
Disclosure of Invention
The invention aims to provide a gibbsite @ SAPO molecular sieve compound with a core-shell structure, which has low cost, high activity and good catalytic effect.
The invention also aims to provide a preparation method of the gibbsite @ SAPO molecular sieve composite with the core-shell structure.
The invention also aims to provide an application of the gibbsite @ SAPO molecular sieve composite with the core-shell structure in catalyzing methanol to olefin.
The technical scheme adopted by the invention is as follows: the gibbsite @ SAPO molecular sieve composite with the core-shell structure is prepared by taking gibbsite as a core and SAPO-34 as a shell; the X-ray diffraction pattern of the gibbsite @ SAPO molecular sieve composite has at least one diffraction peak in each of the ranges shown in table 1 below:
TABLE 1
| 2θ | Relative strength |
| 9.45-9.65 | s-vs |
| 16.0-16.2 | w-m |
| 17.95-18.15 | w-s |
| 18.20-18.40 | w-s |
| 20.55-20.9 | m-vs |
| 24.95-25.4 | w-s |
| 30.5-30.7 | w-s |
In Table 1, w, m, s and vs respectively represent the relative ratio of the diffraction peak intensity to the strongest diffraction peak, wherein w is 0-20%, m is 20-60%, s is 60-80%, and vs is 80-100%.
Furthermore, in the invention, the gibbsite @ SAPO molecular sieve composite with the core-shell structure has an XRD diffraction spectrum which shows the coexistence characteristic of gibbsite and SAPO-34, and in an X-ray diffraction pattern, the ratio of the intensity of a characteristic peak belonging to gibbsite when the 2 theta is positioned at 18.3 degrees +/-0.10 degrees to the intensity of a characteristic peak belonging to SAPO-34 when the 2 theta is positioned at 18.05 degrees +/-0.10 degrees is 0.2-10.
Furthermore, in the gibbsite @ SAPO molecular sieve composite with the core-shell structure, in an X-ray diffraction diagram, the ratio of the intensity of a characteristic peak attributed to gibbsite when the 2 theta is positioned at 18.3 +/-0.10 degrees to the intensity of a characteristic peak attributed to SAPO-34 when the 2 theta is positioned at 18.05 +/-0.10 degrees is 0.3-5.
The preparation method of the gibbsite @ SAPO molecular sieve compound with the core-shell structure comprises the following steps: mixing an aluminum source, a silicon source, a phosphorus source, an organic template agent, a crystallization regulator and water at 5-60 ℃ to form glue, heating to 80-250 ℃, and carrying out hydrothermal crystallization reaction for 1-100 hours under autogenous pressure; the aluminum source is one or the mixture of more than two of gibbsite or gibbsite and pseudo-boehmite, aluminum hydroxide and activated alumina.
Further, in the above preparation method, the silicon source is one or a mixture of two or more of silica sol, silica gel, water glass, ethyl silicate and methyl silicate; the phosphorus source is one or a mixture of more than two of phosphoric acid, metaphosphoric acid, aluminum phosphate, aluminum dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the organic template agent is one or the mixture of more than two of morpholine, diethylamine, triethylamine, tetraethyl ammonium hydroxide and di-n-propylamine; the crystallization regulator is one or the mixture of more than two of glycerol, tert-butyl alcohol, polyethylene glycol and isopropanol.
Further, the preparation method comprises the steps of preparing an aluminum source, a phosphorus source, a silicon source, an organic template agent, a crystallization regulator and water according to Al2O3:P2O5:SiO2The organic template agent, the crystallization regulator and water are mixed according to the molar ratio of 1 (0.5-2), (0.01-0.8), (0.1-5), (0.01-1) and (10-150).
Furthermore, in the synthesis process of the gibbsite @ SAPO molecular sieve composite with the core-shell structure, 0.1-10% of molecular sieve composite product per se calculated on a dry basis of gel can be added into the mixed gel to serve as seed crystal. The hydrothermal crystallization reaction process is well known to those skilled in the art, and can be performed by single-stage crystallization or multi-stage crystallization, and for example, two-stage crystallization can be performed by a first-stage low-temperature crystallization temperature of 80-150 ℃ and a crystallization time of 3-72 hours, and a second-stage high-temperature crystallization temperature of 150-250 ℃ and a crystallization time of 1-96 hours. And after crystallization is finished, filtering the slurry to obtain a molecular sieve compound filter cake. The filter cake can be dried, roasted to remove organic matters and then supplied to catalyst preparation for use.
Application of gibbsite @ SAPO molecular sieve composite with a core-shell structure in catalyzing methanol to olefin. The gibbsite @ SAPO molecular sieve composite with the core-shell structure is used as an active component to be mixed with an inorganic oxide binder and clay to prepare the catalyst which is used for catalyzing methanol to prepare olefin.
Further, the catalyst provided by the invention comprises the following components in percentage by weight: 5-90% of gibbsite @ SAPO molecular sieve composite with a core-shell structure, 5-50% of inorganic oxide binder and 5-70% of clay.
Further, the inorganic oxide binder is selected from one or a mixture of more than two of alumina sol, silica sol, alumina, silica, aluminum phosphate or amorphous silica-alumina.
Further, the clay is one or a mixture of more than two of kaolin, bentonite, montmorillonite or diatomite.
Further, the preparation method of the catalyst is as follows but not limited thereto: the synthesized gibbsite @ SAPO molecular sieve composite with the core-shell structure is directly or after being roasted to remove organic matters, mixed with inorganic oxide binder and clay by adding water and beaten uniformly, then spray-dried to prepare microspheres with the particle size of 10-200 microns, and then roasted at 400-800 ℃ for 0.1-8 h to obtain the high-wear-resistance microsphere catalyst.
Furthermore, the application of the gibbsite @ SAPO molecular sieve composite with the core-shell structure in catalyzing methanol to prepare olefin is as follows: adopting a fluidized bed reactor, and filling the gibbsite @ SAPO molecular sieve compound with a core-shell structure into the fluidized bed reactor, wherein the reaction temperature is 300-700 ℃, the reaction pressure is 0.01-1 MPa, and the methanol feeding airspeed is 0.01-10 h-1。
The gibbsite @ SAPO molecular sieve composite with the core-shell structure has the following chemical composition of an inorganic framework after roasting: (Si)xAlyPz)O2Wherein: x, y and z represent mole fractions of Si, Al and P, and the ranges of x is 0.01 to 0.28, y is 0.35 to 0.55, z is 0.28 to 0.50, and x + y + z is 1.
The catalyst provided by the invention can be used in the reaction process of preparing olefin from methanol. For example, a fluidized bed reactor is adopted for the reaction of preparing olefin from methanol, the reaction temperature is 300-700 ℃, the reaction pressure is 0.01-1 MPa, and the space velocity of methanol feeding is 0.01-10 h-1。
The invention has the beneficial effects that:
according to multiple experiments, the invention discovers that a molecular sieve compound with double structural characteristics and double pore distribution can be obtained by controlling the type of an aluminum source for synthesizing the SAPO-34 molecular sieve and combining with a crystallization regulator to regulate the activity of the aluminum source in crystallization reaction, and the molecular sieve compound can be seen from an XRD (X-ray diffraction) diagram and an SEM (scanning Electron microscope) picture, wherein the XRD diagram has characteristic diffraction peaks of gibbsite and SAPO-34, and the SEM picture shows that the molecular sieve compound is perfect in crystallization, has no amorphous substances and has large pores with larger pore diameters on the surface of crystals, thereby indicating that the synthesized product is a crystalline compound and is not a mechanical mixture. Moreover, the molecular sieve compound has proper silicon oxide content and distribution, namely the content and the distribution of acid centers in the molecular sieve can be regulated and controlled. The molecular sieve compound has the advantages of proper acidity and distribution of micropores and macropores which are beneficial to macromolecular diffusion, has high methanol conversion activity when being used in the reaction process of preparing olefin from methanol, and can reduce the probability of secondary reactions such as hydrogen transfer and the like of primary reaction products such as light olefin and the like, thereby improving the yield of the light olefin.
The abrasion-resistant microspherical catalyst containing the gibbsite @ SAPO molecular sieve composite with the core-shell structure, which is prepared by selecting a proper binder and a preparation process, is applied to an MTO device, so that the consumption of the catalyst can be reduced, and the production cost can be reduced.
Drawings
Figure 1 is an XRD pattern of gibbsite @ SAPO molecular sieve composite with core-shell structure synthesized in example 1.
Figure 2 is an XRD pattern of the gibbsite @ SAPO molecular sieve composite with a core-shell structure synthesized in example 2.
Figure 3 is an XRD pattern of the gibbsite @ SAPO molecular sieve composite with a core-shell structure synthesized in example 3.
Figure 4 is an XRD pattern of the SAPO-34 molecular sieve synthesized in comparative example 1.
FIG. 5 is a Scanning Electron Microscope (SEM) photograph of the gibbsite @ SAPO molecular sieve composite with a core-shell structure synthesized in example 2.
Detailed Description
The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.
Example 1 gibbsite @ SAPO molecular sieve composite having a core-shell structure
284.8 g of phosphoric acid (85)Phosphoric acid (wt%), chemical reagent) and 421 g deionized water, and 93 g gibbsite (65 wt% Al) is slowly added2O3Manufactured by Shandong aluminum industry) and 84 g of pseudo-boehmite (72 wt% Al)2O3Manufactured in Shandong aluminum industry), stirred vigorously for 1h, added with 356.5 g of organic template agent and 68.4 g of tetraethylammonium hydroxide aqueous solution (25.3 wt.% TEAOH, manufactured by Jiangsu Kent New Material), added with 47 g of polyethylene glycol 400 (chemically pure agent), added with 23.5 g of alkaline silica sol (30 wt.% SiO)2Production of new Qingdao Gray material), stirring vigorously for 1h, mixing uniformly, the obtained slurry has the following composition of molar ratio, Al2O3：P2O5：SiO2: triethylamine: tetraethylammonium hydroxide: polyethylene glycol 400: water 1: 1.05: 0.1: 3: 0.1: 0.1: 40. transferring the raw material slurry into a sealed stainless steel thermal crystallization kettle, and rotating and crystallizing for 72 hours at 175 ℃ and autogenous pressure. And after crystallization is finished, filtering, washing and separating out a crystallization product, and drying in a drying oven at 100 ℃ to obtain the gibbsite @ SAPO molecular sieve composite with the core-shell structure, which is marked as A.
The X-ray diffraction pattern of the resulting sample is shown in fig. 1. The ratio of the intensity of the characteristic peak attributed to gibbsite at 2 θ at 18.29 ° to the intensity of the characteristic peak attributed to SAPO-34 at 2 θ at 18.1 ° was 3.55.
Example 2 gibbsite @ SAPO molecular sieve composite having a core-shell structure
Pulping 298.4 g of phosphoric acid and 297 g of deionized water, slowly adding 130 g of gibbsite and 50.4 g of pseudo-boehmite, violently stirring for 1h, adding 237.6 g of triethylamine and 205.7 g of tetraethylammonium hydroxide aqueous solution serving as organic template agents, adding 23.5 g of polyethylene glycol 400, adding 47.1 g of alkaline silica sol, violently stirring for 1h, and uniformly mixing, wherein the obtained slurry comprises the following components in molar ratio, and Al2O3：P2O5：SiO2: triethylamine: tetraethylammonium hydroxide: polyethylene glycol 400: water 1: 1.1: 0.2: 2: 0.3: 0.05: 40. transferring the raw material slurry into a sealed stainless steel thermal crystallization kettle, performing rotary crystallization at 120 ℃ for 24h, then increasing the temperature to 175 ℃ and rotating under autogenous pressureAnd crystallizing for 60 hours. And after crystallization is finished, filtering, washing and separating out a crystallization product, and drying in an oven at 100 ℃ to obtain the gibbsite @ SAPO molecular sieve compound with the core-shell structure, which is marked as B.
The X-ray diffraction pattern of the resulting sample is shown in fig. 2. The ratio of the intensity of the characteristic peak attributed to gibbsite at 2 θ at 18.28 ° to the intensity of the characteristic peak attributed to SAPO-34 at 2 θ at 18.13 ° was 1.96. The morphology of the scanning electron microscope is shown in FIG. 5, and as can be seen from FIG. 5, the obtained molecular sieve composite is cubic crystals, which are typical of SAPO-34 crystals, and no other types of materials are found. And a plurality of macroporous pore channels are arranged in the middle of the SAPO-34 crystal face, and the composite crystal has a double-pore channel structure. Since the compound contains two crystal types in XRD diffraction pattern, the combination of SEM morphology and crystallization process is believed that the compound crystal is formed by embedding gibbsite crystal nucleus in inner core through SAPO-34 molecular sieve shell.
Example 3 gibbsite @ SAPO molecular sieve composite having a core-shell structure
298.4 g of phosphoric acid and 605 g of deionized water are pulped, 93 g of gibbsite and 84 g of pseudo-boehmite are slowly added, vigorous stirring is carried out for 1h, 166.4 g of triethylamine, 82 g of morpholine (chemical pure reagent) and 68.4 g of tetraethylammonium hydroxide aqueous solution which are compounded with organic template agent are added, 17.4 g of tert-butyl alcohol (chemical pure reagent) is added, and 70.6 g of acidic silica sol (25 weight percent of SiO 2) is added2Production of new Qingdao Gray material), stirring vigorously for 1h, mixing uniformly, the obtained slurry has the following composition of molar ratio, Al2O3：P2O5：SiO2: triethylamine: morpholine: tetraethylammonium hydroxide: polyethylene glycol 400: water 1: 1.1: 0.25: 1.4: 0.8: 0.1: 0.2: 42. transferring the raw material slurry into a stainless steel thermal crystallization kettle, rotating and crystallizing at 140 ℃ for 12h, and then heating to 175 ℃ and rotating and crystallizing under autogenous pressure for 24 h. And after crystallization is finished, filtering, washing and separating out a crystallization product, and drying in an oven at 100 ℃ to obtain the gibbsite @ SAPO molecular sieve compound with the core-shell structure, which is marked as C.
The X-ray diffraction pattern of the resulting sample is shown in fig. 3. The ratio of the intensity of the characteristic peak attributed to gibbsite at 2 θ at 18.29 ° to the intensity of the characteristic peak attributed to SAPO-34 at 2 θ at 18.12 ° was 0.69.
Comparative example 1
Comparative experiments were set up according to the feed proportioning of example 2, with the exception that no gibbsite and no crystallization modifier polyethylene glycol were added.
298.4 g of phosphoric acid and 499 g of deionized water are pulped, 168.7 g of pseudo-boehmite is slowly added, vigorous stirring is carried out for 1h, 237.6 g of organic template agent and 205.7 g of tetraethylammonium hydroxide aqueous solution are added, 47.1 g of alkaline silica sol is added, vigorous stirring is carried out for 1h, uniform mixing is carried out, the obtained slurry has the following molar ratio, Al is2O3：P2O5：SiO2: triethylamine: tetraethylammonium hydroxide: water 1: 1.1: 0.2: 2: 0.3: 40. transferring the raw material slurry into a sealed stainless steel thermal crystallization kettle, performing rotary crystallization at 120 ℃ for 24 hours, and then raising the temperature to 175 ℃ and performing rotary crystallization under autogenous pressure for 60 hours. And after crystallization is finished, filtering, washing and separating out a crystallized product, and drying in a drying oven at 100 ℃ to obtain a molecular sieve raw powder product, which is marked as DB.
The X-ray diffraction pattern of the obtained sample is shown in fig. 4. The result shows that the obtained sample is SAPO-34 molecular sieve, and the 2 theta is positioned at 18.28 degrees without diffraction peak.
As can be seen from examples 1-3 and comparative example 1, the present invention synthesizes a crystalline composite having crystal structures of gibbsite and SAPO-34, cubic regular morphology and high crystallinity, with SAPO-34 embedding gibbsite core, by using aluminum hydroxide having a gibbsite structure as an aluminum source and by finely controlling the crystallization precursor and crystallization conditions.
Example 4
The gibbsite @ SAPO molecular sieve composite A with the core-shell structure prepared in the embodiment 1 is roasted at 600 ℃ for 4 hours and then cooled to obtain roasted powder.
137 g of kaolin (product of China Kaolin Corp., 81% by weight solids) and 214 g of aluminum sol (Al) were mixed with 380 g of deionized water2O3Content 21 wt%, leuxpoxin chemical product) were slurried evenly and 145 g of the calcined product of example 1 was addedThe gibbsite @ SAPO molecular sieve composite A with the core-shell structure is homogenized and stirred uniformly to obtain slurry, the slurry is formed by a small spray dryer, the obtained microspheres are roasted for 4 hours at 600 ℃ in a muffle furnace, and the catalyst sample C-A is obtained after cooling. The catalyst contains 48 wt% of gibbsite @ SAPO molecular sieve composite A with a core-shell structure, 15 wt% of alumina sol and 37 wt% of kaolin.
Example 5
The gibbsite @ SAPO molecular sieve composite B with the core-shell structure prepared in the embodiment 2 is roasted at 550 ℃ for 8 hours, and then cooled to obtain roasted powder.
145 grams of kaolin and 240 grams of acidic silica Sol (SiO) were mixed with 300 grams of deionized water2Content 25 wt%, Qingdao girard product), adding 123 g of the calcined gibbsite @ SAPO molecular sieve composite B with the core-shell structure prepared in example 2, homogenizing and stirring uniformly to obtain slurry, forming the slurry by a small spray dryer, calcining the obtained microspheres in a muffle furnace at 600 ℃ for 1h, and cooling to obtain a catalyst sample C-B. The catalyst contains 41 weight percent of gibbsite @ SAPO molecular sieve compound B with a core-shell structure, 20 weight percent of silica sol and 39 weight percent of kaolin.
Example 6
167 g of kaolin and 171 g of alumina sol are uniformly pulped by 380 g of deionized water, 154 g of the gibbsite @ SAPO molecular sieve composite C with the core-shell structure prepared in the example 3 and the dried solid content of 80 wt% is added, the mixture is uniformly stirred to obtain slurry, the slurry is formed by a small spray dryer, the obtained microspheres are roasted for 6h at 600 ℃ in a muffle furnace, and the catalyst sample C-C is obtained after cooling. The catalyst contains 43 weight percent of gibbsite @ SAPO molecular sieve composite C with a core-shell structure, 12 weight percent of alumina sol and 45 weight percent of kaolin.
Comparative example 2
And roasting the molecular sieve raw powder product DB prepared in the comparative example 1 at 550 ℃ for 8 hours, and cooling to obtain roasted powder.
And (2) pulping 145 g of kaolin and 240 g of acidic silica sol by using 300 g of deionized water, adding 123 g of roasted SAPO-34 molecular sieve DB prepared in the comparative example 1, homogenizing and stirring uniformly to obtain slurry, forming the slurry by using a small spray dryer, roasting the obtained microspheres in a muffle furnace at 600 ℃ for 1h, and cooling to obtain a catalyst sample C-DB. The catalyst contains 41 weight percent of SAPO-34 molecular sieve DB, 20 weight percent of silica sol and 39 weight percent of kaolin.
EXAMPLE 7 MTO catalytic Performance of catalyst and comparative catalyst
The MTO reaction performance of the catalyst is evaluated by adopting a fixed bed micro reactor device, and the experimental conditions are as follows: the loading of the catalyst is 2.0g, the set value of the reaction temperature is 450 ℃, the reaction pressure is normal pressure, and the weight space velocities of methanol and water are respectively 2h-1And 2h-1. In the reaction evaluation, a water and gas drainage method is adopted to collect the gas metering volume generated by the MTO reaction, and a gas chromatograph is adopted to analyze the gas composition; and measuring the methanol content by using a gas chromatograph after the water phase product after gas-liquid separation is measured, and calculating the methanol conversion rate and the product distribution. Where catalyst life is defined as the mass of methanol processed per gram of catalyst at a methanol conversion of less than 95%. The ethylene and propylene light olefin product yield is the percentage of the carbonaceous amount in ethylene and propylene, calculated from the gas composition, to the carbonaceous amount of the feed methanol. The evaluation results are shown in Table 2.
TABLE 2
| Catalyst and process for preparing same | Catalyst Life/(g methanol/g catalyst) | Yield of vinyl carbon group/weight% | Propylene carbon based yield/weight% |
| Example 4C-A | 6.9 | 41.5 | 41.2 |
| Examples 5C to B | 7.3 | 42.7 | 41.4 |
| Examples 6C to C | 6.8 | 42.2 | 40.9 |
| Comparative examples 2C-DB | 6.0 | 40.6 | 39.2 |
As can be seen from Table 2, the MTO reaction life and the yield of light olefin products obtained by using the catalyst of the present invention are significantly improved compared with those of the comparative catalysts, which is favorable for reducing the use cost of the catalyst in the industrial practice of MTO.
Claims (8)
1. The gibbsite @ SAPO molecular sieve composite with the core-shell structure is characterized in that gibbsite is taken as a core, SAPO-34 is taken as a shell, and the gibbsite @ SAPO molecular sieve composite with the core-shell structure is obtained; the gibbsite @ SAPO molecular sieve composite has an X-ray diffraction pattern having at least one diffraction peak in each of the following ranges:
wherein 2 Ɵ is located at 18.3 in the X-ray diffraction patterno±0.10oThe intensity of the characteristic peak ascribed to gibbsite and 2 Ɵ are at 18.05o±0.10oThe ratio of the intensities of characteristic peaks ascribed to SAPO-34 is 0.69 to 3.55;
wherein w, m, s and vs respectively represent the relative ratio of the diffraction peak intensity and the strongest diffraction peak, w is 0-20%, m is 20-60%, s is 60-80%, and vs is 80-100%.
2. The preparation method of the gibbsite @ SAPO molecular sieve composite having a core-shell structure of claim 1, comprising the steps of: mixing an aluminum source, a silicon source, a phosphorus source, an organic template agent, a crystallization regulator and water at 5-60 ℃ to form glue, heating to 80-250 ℃, and carrying out hydrothermal crystallization reaction for 1-100 hours; the aluminum source is one or the mixture of more than two of gibbsite or gibbsite and pseudo-boehmite, aluminum hydroxide and activated alumina.
3. The preparation method according to claim 2, wherein the silicon source is one or a mixture of two or more of silica sol, silica gel, water glass, ethyl silicate and methyl silicate; the phosphorus source is one or a mixture of more than two of phosphoric acid, metaphosphoric acid, aluminum phosphate, aluminum dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the organic template agent is one or the mixture of more than two of morpholine, diethylamine, triethylamine, tetraethyl ammonium hydroxide and di-n-propylamine; the crystallization regulator is one or the mixture of more than two of glycerol, tert-butyl alcohol, polyethylene glycol and isopropanol.
4. The application of the gibbsite @ SAPO molecular sieve composite with the core-shell structure of claim 1 in catalyzing methanol to olefin.
5. The application of claim 4, wherein the gibbsite @ SAPO molecular sieve composite with a core-shell structure as described in claim 1 is used as an active ingredient to be mixed with an inorganic oxide binder and clay to prepare a catalyst for catalyzing methanol to olefin.
6. The use of claim 5, wherein the catalyst comprises, in weight percent: 5-90% of gibbsite @ SAPO molecular sieve composite with a core-shell structure, 5-50% of inorganic oxide binder and 5-70% of clay.
7. The use according to claim 5, wherein the inorganic oxide binder is selected from one or a mixture of two or more of alumina sol, silica sol, alumina, silica, aluminum phosphate or amorphous silica-alumina; the clay is one or more of kaolin, montmorillonite or diatomite.
8. Use according to claim 5, characterized in that the method is as follows: adopting a fluidized bed reactor, wherein the reaction temperature is 300-700 ℃, the reaction pressure is 0.01-1 MPa, and the space velocity of methanol feeding is 0.01-10 h-1。
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