CN112156784A - Layered composite material and preparation method and application thereof - Google Patents
Layered composite material and preparation method and application thereof Download PDFInfo
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- CN112156784A CN112156784A CN202010994623.0A CN202010994623A CN112156784A CN 112156784 A CN112156784 A CN 112156784A CN 202010994623 A CN202010994623 A CN 202010994623A CN 112156784 A CN112156784 A CN 112156784A
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- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000000227 grinding Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 5
- 239000013504 Triton X-100 Substances 0.000 claims description 5
- 229920004890 Triton X-100 Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 5
- -1 ethylene, propylene Chemical group 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910008051 Si-OH Inorganic materials 0.000 claims description 3
- 229910006358 Si—OH Inorganic materials 0.000 claims description 3
- 125000001165 hydrophobic group Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 36
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 20
- 150000001336 alkenes Chemical class 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000004711 α-olefin Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 239000012456 homogeneous solution Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 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 description 1
- 238000009792 diffusion process Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
-
- 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
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a layered composite material, a preparation method and application thereof, in particular to a Fe-based material for preparing alpha olefin with high selectivity. The catalyst of the invention inhibits the secondary hydrogenation reaction of primary olefin and the WGS reaction of water gas shift reaction, thereby improving the selectivity of olefin and effectively reducing CO2The product distribution with high added value is generated and regulated, the yield of the alpha olefin is particularly improved, and the industrial application value is obvious.
Description
Technical Field
The invention relates to a layered composite material, a preparation method and application thereof, in particular to a Fe-based material for preparing alpha olefin with high selectivity.
Background
Under the situation of shortage of petroleum energy in the world, the method has important strategic significance in vigorously developing the preparation of low-carbon olefin by taking the synthesis gas as the raw material. CO and CO2The low-carbon olefin is prepared by hydrogenation, and the method has the advantages of short flow, low energy consumption and low coal consumption. Synthesis gasThe traditional approach of using methanol as an intermediate is abandoned by directly converting to prepare the olefin, and one of the key technologies is the research and development of the catalyst.
Due to the limitation of the distribution of F-T synthetic products Anderson-Schulz-Flory (A-S-F), the Fe-based catalyst has the problems of wide product distribution range and low total olefin yield. In addition, the non-supported Fe catalyst can obtain excellent activity and low-carbon olefin selectivity under the action of an auxiliary agent. However, in the case where no carrier is dispersed, the particles are easily sintered, and the mechanical stability of the catalyst is poor.
In order to improve the selectivity of the low-carbon olefin, the scholars adjust CO and H by adding electron assistants such as Mn, K, Mo and Zn2The chemical adsorption state on the surface of the catalyst promotes the improvement of the CO conversion rate and the olefin selectivity. The electronic assistant is mostly introduced by impregnation or mechanical mixing, but the in-situ preparation or utilization of the material property is still in research and exploration stage.
The hydrophobic modification of the Fe base can inhibit WGS reaction and reduce CO in two reaction processes of reverse water gas and Fischer-Tropsch synthesis2Selectivity of (a); the Fe radical is subjected to hydrophilic modification, so that the reabsorption of olefin can be inhibited, the secondary reaction of olefin is reduced, and the selectivity of olefin is improved. How to take care of the catalyst design is the key point of selecting proper conditions.
The magadiite is a hydrated sodalite, belongs to a layered silicate, and is used as a novel layered silicate material, compared with other layered silicates such as montmorillonite, the active Si-OH of the magadiite is positioned on the surface between layers, so that the magadiite is beneficial to functional modification of the magadiite, and the charge density between the layers is obviously improved, thereby improving the ion exchange capacity of the magadiite. The magadiite has a regular laminate structure and adjustable interlamellar spacing, and molecules with different functions can be introduced between layers to serve as a base material for assembling the multifunctional composite material. The magadiite is a pure silicon system, has good biocompatibility, a single lamella is thick (1.12 nm), the structural stability is good, a high-purity product can be obtained by controlling a synthesis process, and the magadiite is low in price and has market competitive advantages. In the application aspect, the magadiite has higher ion exchange capacity and larger specific surface area, so that the magadiite can be used as an adsorption material to adsorb heavy metal ions, organic dyes and the like. Due to the layered structure and the larger specific surface area, the magadiite can be used as a silicon source to synthesize the zeolite molecular sieve, and has higher hydrothermal stability and certain acid resistance. The magadiite can effectively load the catalytic material due to chemical stability and strong loading capacity, so that the catalytic material obtains good dispersion effect and the catalytic performance of the magadiite is enhanced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a composite material formed by double-unit nano-chain imitated flower-shaped links, which is controlled by a layered structure of the material, flower-shaped appearance, an active phase of a metal oxide, in-situ modification of sodium element and hydrophilic groups of the material, and aims to inhibit a primary olefin secondary hydrogenation reaction and a water gas shift reaction WGS (WGS), thereby improving the selectivity of olefin and effectively reducing CO2The product distribution with high added value is generated and regulated, the yield of the alpha olefin is particularly improved, and the industrial application value is obvious.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
application of the composite material of the invention to CO2The hydrogenation reaction for preparing ethylene, propylene and butylene is carried out under the reaction condition of H2/CO=1~4 ，280~350℃、1~3 MPa，1000~4000 h–1。
The composite material is formed by connecting double-unit nanochain in a flower-like shape, wherein the double units consist of iron oxide and magadiite; the iron oxide at least comprises ferroferric oxide; iron oxide refers to FeO and Fe2O3、Fe3O4(ii) a Wherein, part of ferroferric oxide particles are uniformly distributed on the surface of the layered magadiite and are mixed into the magadiite material under the control of the proportion to bridge and stabilize the layered structure; treating by a surfactant, and exposing the magadiite Si-OH around ferroferric oxide particles to enhance alkaline sites; through two groups of precursor preparation and nitric acid etching, magadiite and iron oxide coact, and the sodium element in the composite material and the reaction atmosphere pull Fe to change phase.
The preparation method of the composite material comprises the following steps:
(1) white carbon black, NaOH and Na are prepared according to the proportion2CO3Stirring the mixed solution of the surfactant and the mixed solution, crystallizing the mixed solution for 10 to 30 hours at the temperature of 150 to 250 ℃ in a hydrothermal kettle, and drying the solid for later use to mark as a precursor I; (2) preparing FeCl according to the mixture ratio3·6H2Preparing anhydrous sodium acetate and a 1-shrinkage-2-glycol mixed solution B according to a ratio, adding the solution B into the solution A under a stirring condition, uniformly stirring, crystallizing for 8-12 hours in a hydrothermal kettle at 150-250 ℃, drying the solid in a vacuum drying oven for later use, and marking as a precursor II; (3) mixing the first precursor and the second precursor according to a ratio, and adding a small amount of alcohol, including at least one of ethanol, isopropanol and 2-butanol; give alcohol natural evaporation time, then HNO3And washing, drying and grinding to obtain the target composite material.
In the step (1), the selected surfactant contains hydrophilic groups and hydrophobic groups, so that the surface energy of particles is reduced, the particles are prevented from agglomerating, and the addition amount of the surfactant is 1-3 times of the mass of the white carbon black. In the step (1), the white carbon black is gas-phase SiO2Precipitated SiO2Any one of them; white carbon black, NaOH and anhydrous Na2CO3And the surfactant is (0.5-5.0) by mass: (0.05-0.5): (0.05-3): (1-20). FeCl in step (2)3·6H2O, triton X-100 and anhydrous sodium acetate in a mass ratio of 10: 6: 15, the volume ratio of the ethylene glycol to the 1-condensed-2-ethylene glycol is 4: 3. in the step (3), the mass ratio of the first precursor to the second precursor is 1: 0.5 to 1, HNO used3The concentration of (b) is 0.1 to 0.2 mol/L.
The composite material has a layered structure and a flower-like appearance.
The alternative method of the invention is to disperse the layered magadiite precursor obtained in the step (1) in deionized water, perform ultrasonic treatment and mechanically stir the mixture to form a homogeneous solution 1. Mixing FeCl according to a certain proportion2·4H2O and FeCl3·6H2Adding O into a three-neck flask containing deionized water in the presence of inert gas, and mechanicallyStirring to obtain a mixed solution 2. Solution 1 was added to solution 2 and then the alkali solution was added dropwise until a black precipitate appeared. And (3) keeping the reaction solution in an inert gas atmosphere all the time, separating the obtained precipitate by using a permanent magnet, washing, centrifuging and drying to obtain a sample. Wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 0.5 to 5. Inert gases introduced are generally Ar and N2。
Alternative methods of step (2) may also be: and (2) dipping the layered magadiite precursor obtained in the step (1) into a certain amount of ferric nitrate aqueous solution, ultrasonically stirring and drying. Then heating to 280-380 ℃ in the air atmosphere, calcining for 2-4 h at constant temperature, adding a grinding aid after calcining, and grinding to obtain a reddish brown powder sample; the grain diameter of the reddish brown powder is 30-80 nm. The mass ratio of the grinding aid to the reddish brown powder is 20-40: 100.
further, in the above technical scheme, the precursor one and the precursor two are mixed according to a ratio, mechanically stirred, dried, added with a grinding aid and ground to obtain a sample. And (4) soaking the sample obtained in the step (3) in a certain amount of manganese nitrate aqueous solution, ultrasonically stirring, filtering and drying. And then heating to 280-380 ℃ in the air atmosphere, calcining for 2-4 h at constant temperature, adding a grinding aid after calcining, and grinding to obtain the sample.
The optimization of the composite material of the invention can also be: and (4) co-impregnating the sample obtained in the step (3) with a certain amount of magnesium nitrate and manganese nitrate according to a ratio. Weighing a certain amount of Mg (NO)3)2And Mn (NO)3)2·4H2And preparing O powder into a mixed solution, dropwise adding the mixed solution into the sample, fully and uniformly mixing, and drying at 75 ℃ for 10-14 h. And adding a grinding aid after drying, and grinding to obtain a sample.
The grinding aid used for grinding is an alcohol organic solvent with a branched structure, for example, the alcohol organic solvent can be isopropanol or 2-butanol, and isopropanol is more preferable. The invention adopts the alcohol organic solvent with a branched chain structure, has more reaction active points, can obviously inhibit powder agglomeration in the grinding process and is beneficial to obtaining products with smaller grain diameter. The grinding aid plays an important role in compounding the first precursor and the second precursor. The mass ratio of the grinding aid to the precursor II is 20-40: 100.
further, according to the above technical scheme, in the mixed solution in the step (1), the solutes are white carbon black, NaOH and Na2CO3The solvent is deionized water; wherein: the solute white carbon black is gas-phase SiO2Precipitated SiO2Any one of them. Preferably, in the above technical solution, the solute in step (1) is gas-phase SiO2. Preferably, in the above technical solution, in the mixed solution in the step (1), the dosage ratio of the solute to the solvent is (0.5-8.0) g: (10-200) mL. Preferably, in the above technical scheme, the concentration of the alkali solution in the step (1) is 1-10 mol/L, and more preferably 5-8 mol/L.
Further, in the above technical solution, the surfactant in the step (1) is preferably polyethylene glycol 600. The surfactant molecules adopted by the invention contain hydrophilic groups and hydrophobic groups, and are commonly used for reducing the surface energy of ultrafine particles and preventing the agglomeration of new particles. Therefore, the use of surfactants is often advantageous for obtaining ultrafine powders.
Further, in the above technical solution, the SiO in the mixed solution in the step (1)2NaOH and anhydrous Na in alkali solution2CO3And the surfactant is (0.5-5.0) by mass: (0.05-0.5): (0.05-3): (1-20). The filling degree of the mixed liquid in the hydrothermal reaction kettle is preferably controlled to be 50-80% of the volume of the reaction kettle.
Further, according to the technical scheme, when stirring in the step (1), the temperature is preferably 20-30 ℃, and the rotating speed is preferably 900-1100 rpm. Further, in the technical scheme, the drying process in the step (1) is specifically to place the solid product obtained by centrifugation and washing in an oven, control the drying temperature of the oven to be 40-150 ℃, and control the drying time to be 8-24 h.
Preferably, in the technical scheme, the drying temperature in the step (1) is 50-70 ℃, and the drying time is 10-14 h. Further, the method can be used for preparing a novel materialIn the technical scheme, FeCl is adopted in the step (2)3·6H2O, triton X-100 and anhydrous sodium acetate in a mass ratio of 10: 6: 15, the volume ratio of the ethylene glycol to the 1-condensed-2-ethylene glycol is 4: 3.
in step (2), FeCl3·6H2O may be made of FeCl2·4H2O, ferric nitrate, or both, wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 0.5 to 5. Inert gases introduced are generally Ar and N2. The concentration of the alkali solution is 0.1-0.5 mol/L.
The calcination temperature of the material is preferably 280-320 ℃, and the calcination time is preferably 2-4 h. The calcination of the invention is aimed at converting the precursor of Fe into Fe2O3。
Compared with granular or porous materials, the layered structure of the magadiite has shorter transmission distance, is easy to quickly adsorb and diffuse raw materials and products on the surface of the catalyst, can reduce diffusion limitation to a certain extent, inhibits secondary hydrogenation reaction of olefin, and further regulates and controls product distribution. The rich active hydroxyl groups on the surface of the magadiite and the hydrated Na + between layers can reduce the Gibbs free energy of methane activation, thereby reducing the yield of methane. The layered magadiite-loaded iron-based catalyst can promote the activity of the catalyst in H2The dissociation and adsorption of the catalyst can form hydrogen species which can participate in hydrogenation reaction, thereby improving the CO conversion rate and the selectivity of the low-carbon olefin.
Compared with the prior art, the invention has the following beneficial effects:
(1) the layered magadiite-loaded iron-based catalyst prepared by the invention can provide activated hydroxyl groups and alkali metal auxiliaries, has a layered structure with a large specific surface area, can improve the CO hydrogenation conversion rate and reduce the yield of methane, and has high selectivity and good stability for low-carbon olefin.
(2) The catalyst has simple preparation process and lower raw material cost, and is suitable for industrial large-scale production.
(3) In the process of preparing the layered magadiite-loaded iron-based catalyst, the surfactant polyethylene glycol 600 is added, so that the particle size of the prepared catalyst is reduced.
(4) According to the invention, the grinding aid is added after roasting, so that the agglomeration of the ferric oxide superfine powder is inhibited, the dispersibility of the prepared catalyst is improved, and the selectivity of methane is reduced in the CO hydrogenation process.
(5) In the grinding process, the dispersant is added, so that CO is effectively inhibited2The selectivity and the alkene ratio of the low-carbon olefin are improved.
(6) In the CO hydrogenation reaction process, the surfactant, the grinding aid and the dispersing agent have the synergistic effect, so that the product distribution of the catalyst is improved, the carbon deposition of the catalyst is effectively inhibited, and the stability of the catalyst is improved.
Drawings
FIG. 1 is a scanning electron micrograph of a composite material.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In the following examples, all the starting components, unless otherwise specified, are commercially available products well known to those skilled in the art.
Example 1
The preparation method of the layered magadiite-supported iron-based catalyst of the embodiment comprises the following steps:
(1) and preparing a first precursor.
3.6g of gas-phase SiO were weighed2，0.7 gNaOH，0.94 gNa2CO3Transferring to a beaker, adding 120 mL of deionized water, magnetically stirring for 5min, transferring the solution to a polytetrafluoroethylene-lined high-pressure reaction kettle, and crystallizing for 27 h at 220 ℃. And after the reaction kettle is cooled to room temperature, taking out, washing, centrifuging, washing with deionized water until the pH value is 7-8, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a precursor I.
(2) And preparing a second precursor.
Weighing 10 g FeCl3·6H2O and 1 g Triton X-100 were transferred to a beaker, and 145 mL of ethylene glycol was added to the beaker and dissolved thoroughly to give a homogeneous solution. Weighing 15 g of anhydrous sodium acetate, dissolving the anhydrous sodium acetate into 125 ml of 1-shrinkage-2-glycol, fully stirring, pouring the mixture into the homogeneous solution prepared in the previous step, continuously stirring for 30 min, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, drying the mixture in an oven at 180 ℃ for 10 h, taking out the mixture after the reaction kettle is cooled to room temperature, centrifuging the mixture, washing the mixture for 4 to 5 times by using deionized water and ethanol, and drying the mixture at 60 ℃ overnight in vacuum to obtain a precursor II.
(3) Weighing 0.75 g of the first precursor, dissolving in 50mL of deionized water, mechanically stirring for 1 h, then adding the weighed 1.5 g of the second precursor, stirring for 2 h, and drying at 80 ℃ in vacuum overnight to obtain a catalyst sample. This sample was labeled as sample 1.
Example 2
The preparation method of the layered magadiite-supported iron-based catalyst of the embodiment comprises the following steps:
(1) 3.6g of gas-phase SiO were weighed2，0.7 gNaOH，0.94 gNa2CO3Transferring to a beaker, adding 120 mL of deionized water, magnetically stirring for 5min, transferring the solution to a polytetrafluoroethylene-lined high-pressure reaction kettle, and crystallizing for 27 h at 220 ℃. And after the reaction kettle is cooled to room temperature, taking out, washing, centrifuging, washing with deionized water until the pH value is 7-8, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a precursor I.
(2) 2.52 g of the precursor I is dispersed in 50mL of deionized water, ultrasonic treatment is carried out for 20 min, and mechanical stirring is carried out for 12 h, so as to obtain a solution 1. 0.02 mol FeCl2·4H2O and 0.01 mol FeCl3·6H2O is in N2Adding the mixture into a three-neck flask containing 50mL of deionized water under the atmosphere, mechanically stirring for 30 min to obtain a solution 2, then adding the solution 1 into the solution 2, and dropwise adding 0.35 mol/L NaOH solution until a black precipitate is generated. The reaction solution was maintained at 80 ℃ and N2And (3) separating precipitates by using a permanent magnet under the atmosphere for 2 h, washing the precipitates by using absolute ethyl alcohol for three times, and drying the precipitates in vacuum at 80 ℃ overnight to obtain a catalyst sample. This sample was labeled as sample 2.
Example 3
(1) 3.6g of gas-phase SiO were weighed2，0.7 gNaOH，0.94 gNa2CO3Transferring to a beaker, adding 120 mL of deionized water, magnetically stirring for 5min, transferring the solution to a polytetrafluoroethylene-lined high-pressure reaction kettle, and crystallizing for 27 h at 220 ℃. And after the reaction kettle is cooled to room temperature, taking out, washing, centrifuging, washing with deionized water until the pH value is 7-8, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a precursor I.
(2) Weighing 10 g FeCl3·6H2O and 1 g Triton X-100 were transferred to a beaker, and 145 mL of ethylene glycol was added to the beaker and dissolved thoroughly to give a homogeneous solution. Weighing 15 g of anhydrous sodium acetate, dissolving into 125 ml of 1-shrinkage-2-glycol, fully stirring, pouring into the mixtureAnd (3) continuously stirring the homogeneous solution prepared in the last step for 30 min, transferring the homogeneous solution to a polytetrafluoroethylene-lined high-pressure reaction kettle, drying the homogeneous solution in a 180 ℃ oven for 10 h, taking out the homogeneous solution after the reaction kettle is cooled to room temperature, centrifuging the homogeneous solution, washing the homogeneous solution for 4-5 times by using deionized water and ethanol, and drying the homogeneous solution at 60 ℃ overnight in vacuum to obtain a precursor II.
(3) 2.2 g of the first precursor, 0.25 g of the second precursor and 0.8 g of 0.8 gMn (NO) were weighed out3)2·4H2Mixing O with 30 mL of high-purity ethanol, stirring the mixture in a water bath at constant temperature of 40 ℃ until the solvent is completely evaporated, and adding 0.5M HNO into the obtained solid3And washing, carrying out suction filtration, and then drying at 80 ℃ for 24 h to obtain a catalyst sample. The sample after grinding was labeled as sample 3.
Example 4
The preparation method of the layered magadiite-supported iron-based catalyst of the embodiment comprises the following steps:
(1) 3.6g of gas-phase SiO were weighed2，0.7 gNaOH，0.94 gNa2CO3Transferring to a beaker, adding 120 mL of deionized water, magnetically stirring for 5min, transferring the solution to a polytetrafluoroethylene-lined high-pressure reaction kettle, and crystallizing for 27 h at 220 ℃. And after the reaction kettle is cooled to room temperature, taking out, washing, centrifuging, washing with deionized water until the pH value is 7-8, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a precursor I.
(2) 0.85 g Mg (NO)3)2，0.204 gFe(NO3)3·9H2And O, adding 10mL of deionized water for dissolving, adding 0.5 g of the weighed first precursor into the solution, performing ultrasonic stirring, drying at 80 ℃ overnight, and calcining at 360 ℃ for 4 hours after grinding to obtain a sample. The sample was labeled as D-Fe2O3/A MAG. In the reaction evaluation, the reaction was carried out for 3 hours under normal pressure to obtain sample 4.
Example 5
The preparation method of the layered magadiite-supported iron-based catalyst of the embodiment comprises the following steps:
(1) 3.6g of gas-phase SiO were weighed2，0.7 gNaOH，0.94 gNa2CO3Transferring to a beaker, addingAdding 120 mL of deionized water, magnetically stirring for 5min, transferring the solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and crystallizing for 27 h at 220 ℃. And after the reaction kettle is cooled to room temperature, taking out, washing, centrifuging, washing with deionized water until the pH value is 7-8, and drying in a vacuum drying oven at 80 ℃ overnight to obtain a precursor I.
(2) Weigh 0.204 gFe (NO)3)3·9H2And O, adding 10mL of deionized water for dissolving, adding 0.5 g of the weighed first precursor into the solution, performing ultrasonic stirring, drying at 80 ℃ overnight, calcining at 360 ℃ for 4 hours to obtain a sample, and reducing for 3 hours at normal pressure for later use.
(3) 0.355 g Mg (NO) was weighed3)2And 0.425 gMn (NO)3)2·4H2And (3) preparing 10mL of O powder into a solution, dropwise adding 1.08 g of the solid reduced in the step (2), fully and uniformly mixing, drying at 75 ℃ for 10 h, and reducing at normal pressure for 3 h to obtain a sample 5.
Testing and characterizing the performance of the catalyst:
the catalysts prepared in the above examples 1 to 5 of the present invention were all prepared into 20 to 40 mesh catalyst particles.
The method adopts a miniature fixed bed reactor to evaluate the catalyst, and the process conditions are that 0.5-5 mL of 20-40 mesh catalyst, the reaction temperature is 280-400 ℃, the reaction pressure is 0.5-8 MPa, and the feed gas H is2the/CO =1 or 2, and the space velocity is 500-5000 h-1。
For example, the performance of the catalyst prepared in example 1 was evaluated in a mini-fixed bed reactor, with the following specific operating steps: weighing 0.5 mL of sample 1, placing the sample in a constant temperature area in the middle of a reaction tube, and feeding a feed gas H2/CO =2, temperature 280 ℃, pressure 1.5 MPa, space velocity (GHSV) 1000 h-1And after the steady state is reached, sampling and analyzing, and sampling once at an interval of 3 h. The gas chromatography is used for carrying out quantitative and qualitative analysis on the raw material gas and the product. By using H in coal-based Fischer-Tropsch synthesis tail gas2、N2、CO、CO2And C1～C8The CO conversion rate and the selectivity of each component substance are calculated by a methane correlation method of hydrocarbon determination and gas chromatography.
Table 1 is a comparison table of the hydrogenation catalytic process parameters and performance test results of the catalysts prepared in examples 1-5 of the present invention. As can be seen from Table 1, the catalysts of examples 1-5 have an increased CO conversion and, in the product distribution, a CO2The selectivity is increased, and the hydrocarbon products are obviously changed.
In the catalysts prepared by the embodiments of the invention, the sample 5 has the best performance in catalyzing CO hydrogenation, the selectivity of the low-carbon olefin is 40.5 percent, and C4Olefin n-isobutylene content 97.1%, C5The normal olefin content in the + is 68.2%, and the alkylene ratio (O/P) is 6.05.
TABLE 1 comparison table of hydrogenation catalytic reaction process parameters and performance test results of the layered magadiite-supported iron-based catalysts prepared in examples 1 to 5
Claims (7)
1. Use of a layered composite material, characterized in that: the composite material is applied to the reaction of preparing ethylene, propylene and butylene by CO hydrogenation reaction under the reaction condition of H2/CO2 =1~4，H2/CO=1~4 ，280~350℃、1~3 MPa，1000~4000 h–1；
The composite material is in a layered structure and in a flower-like shape, and is formed by double-unit nanochain flower-like connection, wherein the double units consist of iron oxide and magadiite; the iron oxide at least comprises ferroferric oxide; wherein, part of ferroferric oxide particles are uniformly distributed on the surface of the layered magadiite and are mixed into the magadiite material under the control of the proportion to bridge and stabilize the layered structure; treating by a surfactant, and exposing the magadiite Si-OH around ferroferric oxide particles to enhance alkaline sites; through two groups of precursor preparation and nitric acid etching, magadiite and iron oxide coact, and the phase of sodium element in the composite material and reaction atmosphere traction Fe is changed;
the preparation method of the composite material comprises the following steps:
(1) white carbon black, NaOH and Na are prepared according to the proportion2CO3Stirring the mixed solution of the surfactant and the mixed solution, crystallizing the mixed solution for 10 to 30 hours at the temperature of 150 to 250 ℃ in a hydrothermal kettle, and drying the solid for later use to mark as a precursor I;
(2) preparing FeCl according to the mixture ratio3·6H2Preparing anhydrous sodium acetate and a 1-shrinkage-2-glycol mixed solution B according to a ratio, adding the solution B into the solution A under a stirring condition, uniformly stirring, crystallizing for 8-12 hours in a hydrothermal kettle at 150-250 ℃, drying the solid in a vacuum drying oven for later use, and marking as a precursor II;
(3) mixing the first precursor and the second precursor according to a ratio, and adding a small amount of alcohol, including at least one of ethanol, isopropanol and 2-butanol; give alcohol natural evaporation time, then HNO3And washing, drying and grinding to obtain the target composite material.
2. A layered composite material according to claim 1, characterized in that:
and (3) optimizing the composite material, and introducing one or more of Mg, Mn, Zn and Zr by a dipping method after the step (3).
3. A layered composite material according to claim 1, characterized in that:
in the step (1), the selected surfactant contains hydrophilic groups and hydrophobic groups, so that the surface energy of particles is reduced, the particles are prevented from agglomerating, and the addition amount of the surfactant is 1-3 times of the mass of the white carbon black; the surfactant may be polyethylene glycol.
4. A layered composite material according to claim 1, characterized in that:
in the step (1), the white carbon black is gas-phase SiO2Precipitated SiO2Any one of them; white carbon black, NaOH and anhydrous Na2CO3And the surfactant is (0.5-5.0) by mass: (0.05-0.5): (0.05-3): (1-20); the concentration of NaOH is 1-10 mol/L.
5. A layered composite material according to claim 1, characterized in that:
FeCl in step (2)3·6H2O, triton X-100 and anhydrous sodium acetate in a mass ratio of 10: 6: 15, the volume ratio of the ethylene glycol to the 1-condensed-2-ethylene glycol is 4: 3.
6. a layered composite material according to claim 1, characterized in that:
in the step (3), the mass ratio of the first precursor to the second precursor is 1: 0.5 to 1, HNO used3The concentration of (b) is 0.1 to 0.2 mol/L.
7. A layered composite material according to claim 1, characterised in that an alternative method of step (2) can be: mixing FeCl according to a certain proportion2·4H2O and FeCl3·6H2Adding O into a three-neck flask containing deionized water in the presence of inert gas, dropwise adding an alkali solution under mechanical stirring until black precipitates appear, separating the obtained precipitates by using a permanent magnet, washing, centrifuging and drying to obtain a precursor II; wherein FeCl2·4H2O and FeCl3·6H2The molar ratio of O is 0.5 to 5.
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