CN111715201A - Boron-doped silicon dioxide fiber material and preparation method and application thereof - Google Patents
Boron-doped silicon dioxide fiber material and preparation method and application thereof Download PDFInfo
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- CN111715201A CN111715201A CN202010568026.1A CN202010568026A CN111715201A CN 111715201 A CN111715201 A CN 111715201A CN 202010568026 A CN202010568026 A CN 202010568026A CN 111715201 A CN111715201 A CN 111715201A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 223
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 110
- 239000002657 fibrous material Substances 0.000 title claims abstract description 93
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910015395 B-O-Si Inorganic materials 0.000 claims abstract description 5
- 229910015403 B—O—Si Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 84
- 238000009987 spinning Methods 0.000 claims description 65
- 229910052796 boron Inorganic materials 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000003054 catalyst Substances 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 33
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 25
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010041 electrostatic spinning Methods 0.000 claims description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 239000001294 propane Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000001282 iso-butane Substances 0.000 claims description 5
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 5
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000001523 electrospinning Methods 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 24
- 238000012360 testing method Methods 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 9
- -1 carbon olefin Chemical class 0.000 description 8
- 238000009616 inductively coupled plasma Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920001155 polypropylene Polymers 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
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
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Abstract
The invention provides a boron-doped silicon dioxide fiber material and a preparation method and application thereof. According to the boron-doped silicon dioxide fiber material provided by the invention, boron atoms are connected into a silicon dioxide framework through B-O-Si chemical bonds. The boron-doped silicon dioxide fiber material provided by the invention anchors active sites in a chemical bond form, and ensures the stability in the catalytic reaction process.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a boron-doped silicon dioxide fiber material and a preparation method and application thereof.
Background
The low-carbon olefin is widely applied to the fields of building, medicine, aerospace, agriculture and the like as an important petrochemical raw material in industry. In industrial production, low-carbon olefin is mainly from steam cracking of naphtha, the reaction temperature is generally over 800 ℃, the energy consumption is high, the distribution of reaction products is wide, and a complex separation process is required. In addition, it is difficult to obtain C by steam cracking4Olefin and propylene have low selectivity and are difficult to meet industrial requirements. The technology for preparing olefin by dehydrogenating low-carbon alkane has the advantages of high selectivity of target products, few byproducts, low reaction temperature and the like, so that the preparation of olefin by dehydrogenating low-carbon alkane is an effective path for solving the problem of insufficient supply of low-carbon olefin.
The existing alkane dehydrogenation process comprises direct dehydrogenation and oxidative dehydrogenation, compared with the direct dehydrogenation process, the oxidative dehydrogenation process has the advantages that the alkane oxidative dehydrogenation is not limited by thermodynamic equilibrium, can be carried out at a lower temperature (less than 600 ℃), no carbon deposit is generated, and the reaction efficiency is favorably improved. The catalysts commonly used in oxidative dehydrogenation processes are mostly transition metal oxides, such as V oxide catalyst (CN104475117A) and Mo, V, Nb composite oxide catalyst (CN 105849069A). Although transition metal oxides are effective in activating C-H bonds in alkanes, these catalysts themselves also have the ability to activate C-H bonds in olefin products, which leads to poor selectivity of the target product at high conversion rates of the catalyst during the reaction, and increased deep oxidation (Catal. today,2007,127,113). For example, the selectivity to propylene for vanadium system catalysts is typically less than 60% at 10% propane conversion (j.am. chem. soc.,2014,136,12691).
Recently, hexagonal boron nitride (h-BN) has been used as a non-metal catalyst in oxidative dehydrogenation of lower alkanes (ChemCatchem,2017,9, 1718; Science,2016,354,1570). BN catalyst can effectively inhibit COxShows high catalytic activity and olefin selectivity which is obviously higher than that of the traditional catalyst. Some of the boron-containing compounds were subsequently used in alkane oxidative dehydrogenation reactions and had similar catalytic activity to h-BN and BO at the catalyst surfacexThe species being a catalytically active site (Che)Commun.,2018,54, 10936). Boron oxide (B)2O3) The BO-rich chemical is cheap and easily available, has stable chemical properties and is rich in BOxThe material of the species is suitable for the oxidative dehydrogenation reaction of the low-carbon alkane. But due to B2O3The melting point is low, and the loss phenomenon exists at high temperature, so that the application of the catalyst in alkane oxidative dehydrogenation is limited.
Prior art CN110124647A discloses a supported non-metallic catalyst comprising a boron oxide supported on silicon oxide and silicon oxide, wherein the boron oxide is 0.1-30 mass%. The catalyst does not form a stable B-O-Si chemical bond, and boron atoms are easy to lose in the catalytic reaction process.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a boron-doped silicon dioxide fiber material.
The invention also provides a preparation method and application of the boron-doped silicon dioxide fiber material.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a boron doped silica fibre material in which the boron atoms are bonded to the silica backbone by B-O-Si chemical bonds.
Preferably, the boron-doped silica fiber material comprises the components in percentage by mass, and the active component proportion is measured by atomic mass, wherein boron atoms account for 0.03-6 wt% of the mass of the boron-doped silica fiber material; the silicon atoms account for 36.8-46.7 wt% of the mass of the boron-doped silicon dioxide fiber material; the balance being oxygen atoms.
Specifically, boron atoms comprise 0.03 wt%, 1 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt% of the mass of the boron-doped silica fiber material and ranges between any two of the foregoing values.
Specifically, silicon atoms comprise 36.8 wt%, 40 wt%, 40.5 wt%, 41 wt%, 41.5 wt%, 42 wt%, 42.5 wt%, 43 wt%, 43.5 wt%, 44 wt%, 44.5 wt%, 45 wt%, 45.5 wt%, 46 wt%, 46.7 wt% of the mass of the boron-doped silica fiber material and ranges between any two of the foregoing values.
Preferably, the boron doped silica fiber material microstructure is fibrous, preferably the fiber diameter is 50nm-2 μm, in particular the fiber diameter is 50nm, 100nm, 150nm, 200nm, 500nm, 700nm, 1000nm, 1200nm, 1500nm, 1700nm, 2000nm and ranges between any two of the above.
In a second aspect, the present invention provides a method for preparing the boron-doped silica fiber material, the method comprising the steps of:
(1) preparing a spinning solution of boron-doped silicon dioxide;
(2) preparing the precursor of the boron-doped silicon dioxide fiber material by electrostatic spinning, and roasting the precursor of the boron-doped silicon dioxide fiber material to obtain the boron-doped silicon dioxide fiber material.
Preferably, the step (1) comprises:
1) dissolving a boron source in a mixed solvent of ethanol and water, preparing a solution with a corresponding boron content, and adjusting the solution to be acidic;
2) adding a silicon source into the acidic solution obtained in the step 1) to prepare a solution with a corresponding silicon content;
3) adding spinning aid aqueous solution with equal mass into the solution obtained in the step 2) to obtain spinning solution.
Preferably, the step (1) further comprises adding a surfactant before adding the silicon source.
Preferably, in step (1) 2), the silicon source is added and then the mixture is stirred for 0.5 to 1 hour.
Preferably, in the step (1) 3), after adding the spinning assistant aqueous solution, stirring for 4-12 hours to obtain a spinning solution.
Preferably, in step 1) of step (1), the boron concentration in the solution is 0.01 to 1 wt% based on the mass of boron atoms.
Specifically, the boron concentration is 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, and a range between any two of the foregoing, in terms of boron atomic mass.
Preferably, the mass ratio of the ethanol to the water is 1: 10-1: 1.
Preferably, the pH of the solution is 2-4.
Preferably, the boron source is any one or combination of two or more of water-soluble or hydrolysable boron-containing substances, and more preferably, the boron source is selected from one or two or more of boric acid, trimethyl borate, triethyl borate and tributyl borate.
Preferably, the surfactant concentration in the solution is 0-10 wt%, specifically 0 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, and a range between any two of the foregoing values.
Preferably, the surfactant is any one or a combination of two or more soluble in water.
More preferably, the surfactant is selected from one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), F127, P123, P103, P104.
Preferably, in the step (1) 2), the solution has a silicon concentration of 1 to 10 wt% based on the mass of silicon atom.
Specifically, the concentration of silicon in the solution is 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, and a range between any two of the foregoing values, based on the mass of silicon atoms.
Preferably, the silicon source is any one of organic or inorganic silicon sources that is soluble or hydrolysable in water.
More preferably, the silicon source is selected from one or more of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrabutyl orthosilicate (TBOS), and silica sol.
Preferably, in the step (1) 3), the concentration of the spinning aid in the solution is 5 to 15 wt%, specifically, the concentration of the spinning aid in the aqueous solution is 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, and a range between any two of the above values.
Preferably, the spinning aid is a high molecular material which can increase the viscosity of the solution after being dissolved in water.
More preferably, the spinning aid is selected from one or a combination of more than two of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and Polyacrylonitrile (PAN).
Preferably, in the step (2), the electrostatic spinning speed is 1-10 ml/h, and preferably, the voltage is 7-14 kV; or, preferably, the receiving mode is flat plate or roller receiving, and the receiving distance is 15-30 cm;
preferably, in the step (2), the roasting temperature is 450-1000 ℃, and preferably, the roasting time is 0.5-5 h; or, preferably, the boron-doped silica fiber material precursor is roasted in a muffle furnace, and the heating rate of the muffle furnace is 0.5-5 ℃/min.
In a third aspect, the invention provides a boron-doped silica fiber material prepared by the preparation method.
In a fourth aspect, the invention provides an application of the boron-doped silica fiber material or the boron-doped silica fiber material prepared by the preparation method as a catalyst in preparation of low-carbon olefin through oxidative dehydrogenation of low-carbon alkane.
Preferably, the lower alkane is an alkane containing 2 to 8 carbon atoms, in particular, the lower alkane is an alkane containing 2, 3, 4, 5, 6, 7 or 8 carbon atoms.
In a fifth aspect, the present invention provides a method for preparing a low carbon olefin by oxidative dehydrogenation of a low carbon alkane, the method comprising the following steps:
the boron-doped silicon dioxide fiber material provided by the invention or the boron-doped silicon dioxide fiber material prepared by the preparation method is contacted with mixed gas containing alkane, oxidant and diluent gas, and dehydrogenation reaction is carried out at 380-610 ℃ to prepare low-carbon olefin.
Preferably, the volume ratio of the alkane is 5-30%, the volume ratio of the oxidant gas is 5-30%, and the balance is the diluent gas.
Preferably, the boron-doped silica fiber material is contacted with mixed gas containing alkane, oxidant and diluent gas in a fixed bed reactor to perform dehydrogenation reaction; preferably, the reaction Weight Hourly Space Velocity (WHSV) of the fixed bed reactor is 2.4-84.6L g-1·h-1。
Preferably, the alkane is one of ethane, propane, isobutane and n-butane.
Preferably, the oxidant is one or both of oxygen and air.
Preferably, the diluent gas is an inert gas, preferably one of nitrogen, helium and argon.
The invention has the beneficial effects that:
according to the boron-doped silicon dioxide fiber material provided by the invention, boron atoms are connected into a silicon dioxide framework through chemical bonds, and active sites are anchored through the chemical bonds, so that the stability in the catalytic reaction process is ensured.
Compared with a supported catalyst, the boron-doped silicon dioxide fiber material provided by the invention does not need to be molded, and can react at a higher airspeed, for example, the WHSV of the material can be 2.4-84.6 h-1Reacting under the condition; meanwhile, the boron-doped silicon dioxide fiber material has better stability, and basically has no inactivation after reacting for 20 hours under the conditions of high temperature and high space velocity. This is primarily due to the uniform fiber structure that makes the boron doped silica fiber material conducive to reactant diffusion so that the boron doped silica fiber material can react at higher space velocities.
Compared with the traditional supported catalyst, the boron-doped silicon dioxide fiber material provided by the invention is an integral fiber material obtained by spinning, can be directly filled in a reactor, does not need the step of conventional powder catalyst bonding molding, has small pressure drop due to an integral structure, can operate under the condition of higher airspeed, has excellent catalytic stability and selectivity, and has good industrial application prospect.
Drawings
Fig. 1 is an SEM image of the boron-doped silica fiber material prepared in example 1.
FIG. 2 is an infrared spectrum of a boron-doped silica fiber material prepared in example 3.
FIG. 3 is a graph of the change in conversion and selectivity over 20h in example 11.
FIG. 4 is a graph of the change in conversion and selectivity over 20h in example 12.
FIG. 5 is an infrared spectrum of the supported catalyst prepared in comparative example 3.
FIG. 6 is a graph showing the change in conversion and selectivity within 10 hours in comparative example 5.
Detailed Description
The invention provides a boron-doped silica fiber material. In the preparation process of the boron-doped silicon dioxide fiber material, firstly, a boron-doped silicon dioxide precursor sol is prepared, then, the sol is prepared into a boron-doped silicon dioxide fiber material precursor through electrostatic spinning, and finally, the boron-doped silicon dioxide fiber material is prepared through oxidizing roasting. Boron atoms in the boron-doped silica fiber material are linked into the silica framework through strong chemical bonds to anchor the active component.
The following further describes specific embodiments of the present invention with reference to the drawings and technical solutions, but the present invention is not limited to these embodiments.
Boron-doped silicon dioxide fiber material using n% B-SiO2Wherein n represents the mass percentage of boron atoms.
The contents of boron atoms and silicon atoms in the examples of the present invention and the comparative examples were measured as follows:
putting a sample to be detected into a polytetrafluoroethylene high-pressure reaction kettle, adding concentrated hydrochloric acid and hydrofluoric acid (mixed according to a ratio of 1:1), dissolving at 150 ℃, and evaporating the solution. And adding deionized water into the polytetrafluoroethylene high-pressure reaction kettle for multiple times to dissolve a sample, finally performing constant volume by using a polypropylene volumetric flask, and testing the contents of boron atoms and silicon atoms by using an inductively coupled plasma emission spectrometer (ICP-OES).
The product of the catalytic reaction is analyzed by a gas chromatograph (5A molecular sieve, 2m × 4 mm; GDX-102 column, 0.5 × 3 mm; TCD detector) on linexAnd calculating the conversion, selectivity and yield of the reaction. Wherein:
alkane conversion (%) < 100 × (alkane mole before reaction-alkane mole after reaction)/alkane mole before reaction;
olefin selectivity (%). 100 x total moles of olefin produced/(moles of pre-reacted alkanes-moles of post-reacted alkanes);
yield (%). cndot.alkane conversion (%). cndot.olefin selectivity (%).
The manufacturers of the reagents and instruments used in the present examples are described below, wherein the chemical substances are not indicated as being of the chemically pure grade of conventional reagents. Information and instruments of the reagents used in the examples are shown in tables 1 and 2, respectively.
TABLE 1 information on the reagents used in the examples
| Raw materials | Purity of | Manufacturer of the product |
| Tetraethyl orthosilicate | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetra methyl ortho silicate | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Boric acid | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Boric acid trimethyl ester | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Boric acid tributyl ester | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Ethanol | Analytical purity | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Polyvinyl alcohol | Analytical purity | Aladdin |
| Polyvinylpyrrolidone | Analytical purity | Aladdin |
| Polyacrylonitrile | Analytical purity | Aladdin |
| F127 | Analytical purity | Sigma |
| P123 | Analytical purity | Sigma |
| Ethane (III) | >99.9％ | DALIAN SPECIAL GAS INDUSTRY Co. |
| Propane | >99.9％ | DALIAN SPECIAL GAS INDUSTRY Co. |
| Isobutane | >99.9％ | DALIAN SPECIAL GAS INDUSTRY Co. |
| N-butane | >99.9％ | DALIAN SPECIAL GAS INDUSTRY Co. |
| Nitrogen gas | >99.999％ | DALIAN SPECIAL GAS INDUSTRY Co. |
| Oxygen gas | >99.999％ | DALIAN SPECIAL GAS INDUSTRY Co. |
TABLE 2 instruments used in the examples
Example 1
A boron-doped silica fiber material is prepared by the following steps:
(1) preparation of a spinning solution of boron-doped silica
1) 27mg of tributyl borate was dissolved in 30g of an ethanol-water solution (mass ratio 1:1), and the pH of the solution was adjusted to 2.
2) 15g TEOS and the above solution were mixed and stirred for 0.5 h.
3) Mixing 45g of PVA aqueous solution with the solution, wherein the PVA content in the PVA aqueous solution is 15 wt%; stirring for 4h to obtain a spinning solution.
(2) And (2) sucking 20ml of spinning solution into an injector, putting the injector into a spinning device for spinning, wherein the spinning speed is 10ml/h, the voltage is 7kV, the receiving mode is flat plate receiving, the receiving distance is 20cm, after the spinning is finished, putting the received sample into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, and roasting for 2h to obtain the final boron-doped silicon dioxide fiber material.
The boron-doped silica fiber material obtained was measured for the content of boron atoms and silicon atoms using the aforementioned method using an inductively coupled plasma emission spectrometer (ICP-OES), and found to be 0.03 wt% for boron atoms, 46.70 wt% for silicon atoms and 53.27 wt% for oxygen atoms. The SEM image of the obtained boron-doped silica fiber material is shown in fig. 1, and it can be seen from fig. 1 that the obtained boron-doped silica fiber material is fibrous and has a fiber diameter of about 200 nm.
Example 2
A boron-doped silica fiber material prepared by the process of:
(1) preparation of a spinning solution of boron-doped silica
1) 27mg of tributyl borate was dissolved in 30g of an ethanol-water solution (mass ratio 1:1), and the pH of the solution was adjusted to 2.
2) 450mg of P123 were dissolved in the above solution.
3) 15g TEOS and the above solution were mixed and stirred for 0.5 h.
4) Mixing 45g of PVA aqueous solution with the solution, wherein the PVA content in the PVA aqueous solution is 15 wt%; stirring for 4h to obtain a spinning solution.
(2) And (2) sucking 20ml of spinning solution into an injector, putting the injector into a spinning device for spinning, wherein the spinning speed is 10ml/h, the voltage is 7kV, the receiving mode is flat plate receiving, the receiving distance is 20cm, after the spinning is finished, putting the received sample into a muffle furnace, heating to 800 ℃ at the speed of 5 ℃/min, and roasting for 2h to obtain the final boron-doped silicon dioxide fiber material.
The boron-doped silica fiber material obtained was measured for the content of boron atoms and silicon atoms using the aforementioned method using an inductively coupled plasma emission spectrometer (ICP-OES), and found to be 0.03 wt% for boron atoms, 46.70 wt% for silicon atoms and 53.27 wt% for oxygen atoms.
Example 3
A boron-doped silica fiber material is prepared by the following steps:
(1) preparing a spinning solution of boron-doped silicon dioxide;
1) 119mg of trimethyl borate was dissolved in 6.4g of an ethanol-water solution (mass ratio of 1:2.2), and the pH of the solution was adjusted to 3.
2) 650mg of P123 were dissolved in the above solution.
3) 1.64g of TMOS and the above solution were mixed and stirred for 1 h.
4) Mixing 8.94g of PVP aqueous solution with the solution, wherein the content of PVP in the PVP aqueous solution is 7 wt%; stirring for 8h to obtain a spinning solution.
(2) Sucking the obtained spinning solution into an injector, and putting the injector into a spinning device for spinning; the spinning speed is 2ml/h, the voltage is 9kV, the receiving mode is flat plate receiving, the receiving distance is 15cm, after spinning is finished, the received sample is placed into a muffle furnace, the temperature is raised to 700 ℃ at the speed of 3 ℃/min, and roasting is carried out for 4h, so that the final boron-doped silicon dioxide fiber material is obtained.
The boron-doped silica fiber material obtained was subjected to the aforementioned method to measure the contents of boron atoms and silicon atoms by means of inductively coupled plasma emission spectroscopy (ICP-OES), and the boron-doped dioxygen was measuredThe silicon dioxide fiber material contains 1.8 wt% of boron atoms, 44.0 wt% of silicon atoms and 54.2 wt% of oxygen atoms. The obtained boron-doped silica fiber material has an infrared spectrum of 1425cm as shown in FIG. 2-1And 1370cm-1The vibration peak is B-O species signal, 1100cm-1And 815cm-1The vibration peak is Si-O species signal, and 920cm is observed-1Shows the formation of B-O-Si bonds. The boron element in the boron-doped silicon dioxide fiber material provided by the invention is uniformly dispersed in the material structure, and the boron species and the carrier silicon dioxide have stronger effects.
Example 4
A boron-doped silica fiber material is prepared by the following steps:
(1) preparing a spinning solution of boron-doped silicon dioxide;
1) 426mg of boric acid was dissolved in 6.4g of an ethanol-water solution (mass ratio of 1:2.2), and the pH of the solution was adjusted to 2.
2) 200mg of F127 were dissolved in the above solution.
3) 3.47g TEOS was mixed with the above solution and stirred for 2 h.
4) Mixing 10.37g of PAN aqueous solution with the solution, wherein the PAN content in the PAN solution is 5 wt%; stirring for 12h to obtain a spinning solution.
(2) Sucking the obtained spinning solution into an injector, and putting the injector into a spinning device for spinning; the spinning speed is 2ml/h, the voltage is 7kV, the receiving mode is flat plate receiving, the receiving distance is 30cm, after spinning is finished, the received sample is placed into a muffle furnace, the temperature is raised to 900 ℃ at the speed of 3 ℃/min, and roasting is carried out for 1h, so that the final boron-doped silicon dioxide fiber material is obtained.
The boron-doped silica fiber material obtained was tested for boron atom and silicon atom contents using the aforementioned method using an inductively coupled plasma emission spectrometer (ICP-OES), and found to be 6 wt% for boron atoms, 37.7 wt% for silicon atoms and 56.3 wt% for oxygen atoms.
Example 5
0.1g of the boron-doped silica fiber material prepared in example 1 was taken inAnd evaluating the performance of the oxidative dehydrogenation of the ethane. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C2H6:O2:N21:1:4, WHSV 25.6h-1The catalytic reaction is carried out at 580 ℃ and 600 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Example 6
0.1g of the boron-doped silica fiber material prepared in example 2 was taken for evaluation of the ethane oxidative dehydrogenation performance. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C2H6:O2:N21:1:4, WHSV 25.6h-1The catalytic reaction is carried out at 580 ℃ and 600 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Example 7
0.1g of the boron-doped silica fiber material prepared in example 4 was taken for evaluation of the ethane oxidative dehydrogenation performance. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C2H6:O2:N21:1:4, WHSV 25.6h-1The catalytic reaction is carried out at 550 ℃ and 570 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Example 8
0.1g of the boron-doped silica fiber material prepared in example 3 was taken for evaluation of the oxidative dehydrogenation performance of propane. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C3H8:O2:N21:1.5:3.5, WHSV of 84.6h-1The catalytic reaction is carried out at 515 ℃ and 535 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Example 9
0.1g of the boron-doped silica fiber material prepared in example 4 was taken for evaluation of the oxidative dehydrogenation performance of isobutane. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the feed gas ratio is i-C4H10:O2:N21:1:4, WHSV 12.4h-1At 470 ℃ and 490 ℃ respectivelyCarrying out catalytic reaction for 1h under normal pressure, and the test results are shown in Table 3.
Example 10
0.1g of the boron-doped silica fiber material prepared in example 4 was taken for evaluation of the n-butane oxidative dehydrogenation performance. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the feed gas ratio is n-C4H10:O2:N21:0.5:4.5, WHSV of 2.4h-1The catalytic reaction is respectively carried out at 380 ℃ and 400 ℃ and the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Example 11
0.1g of the boron-doped silica fiber material prepared in example 3 was taken for evaluation of the oxidative dehydrogenation performance of propane. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C3H8:O2:N21:1.5:3.5, temperature 530 ℃, WHSV 84.6h-1As shown in fig. 3, conversion and selectivity remained stable over the 20 hour test.
Example 12
0.1g of the boron doped silica fiber material prepared in example 3 was taken for evaluation of the ethane alkoxylation dehydrogenation performance. Placing the boron-doped silicon dioxide fiber material in a fixed bed reactor, wherein the proportion of the feeding gas is C2H6:O2:N21:1:4, temperature 595 ℃, WHSV 25.6h-1As shown in fig. 4, conversion and selectivity remained stable over the 20 hour test. Table 4 shows that the boron atoms in the boron doped silica fiber material are stable during the reaction.
Comparative example 1
(1) Preparing a spinning solution of boron-doped silicon dioxide;
1) 298mg of trimethyl borate were dissolved in 6.4g of an ethanol-water solution (mass ratio of 1:1), and the pH of the solution was adjusted to 3.
2) 300mg of P123 was dissolved in the above solution.
3) 1.64g of TMOS and the above solution were mixed and stirred for 1 h.
4) Mixing 8.94g of PVP aqueous solution with the solution, wherein the content of PVP in the PVP aqueous solution is 18 wt%; stirring for 12h to obtain a spinning solution.
(2) Sucking the obtained spinning solution into an injector, and putting the injector into a spinning device for spinning; under the conditions that the spinning speed is 1ml/h, the voltage is 6kV, the receiving mode is flat plate receiving, and the receiving distance is 40cm, the spinning sample cannot be received by the receiving plate.
Due to the fact that the content of PVP in the spinning assistant PVP water solution is increased, a receiving plate of the electrostatic spinning device cannot receive spinning samples.
Comparative example 2
(1) Preparing a spinning solution of boron-doped silicon dioxide;
1) 800mg of boric acid was dissolved in 6g of an ethanol-water solution (mass ratio of 1:2), and the pH of the solution was adjusted to 2.
2) 200mg of F127 were dissolved in the above solution.
3) 3.47g TEOS was mixed with the above solution and stirred for 5 h.
4) Mixing 10.37g of PVA aqueous solution with the solution, wherein the PVA content in the PVA solution is 3 wt%; stirring for 12h to obtain a spinning solution.
(2) Sucking the obtained spinning solution into an injector, and putting the injector into a spinning device for spinning; the spinning speed is 1ml/h, the voltage is 20kV, the receiving mode is flat plate receiving, and the receiving plate can not receive the spinning sample under the condition that the receiving distance is 10 cm.
The receiving plate of the electrostatic spinning device can not receive the spinning sample due to the fact that the content of the boron element in the spinning solution is too high.
Comparative example 3
Preparing load type B/SiO according to the patent [ CN110124647A ]2Catalyst, 535.5mg boric acid is taken in a 10mL glass bottle, 5mL ethylene glycol is added, and boron precursor solution is obtained after stirring and dissolving at 50 ℃. And (3) soaking 0.5mL of the solution on 0.5g of SBA-15, standing at room temperature for 2h, placing in a 50 ℃ oven overnight, heating the obtained sample at 5 ℃/min to 700 ℃, and roasting for 3h to obtain the supported B/SBA-15 catalyst.
The resulting catalyst was tested for boron and silicon atom content using inductively coupled plasma emission spectrometry (ICP-OES) using the method described above, and the B-The SBA-15 catalyst contained 1.8 wt% of boron atoms. The obtained infrared spectrum of the catalyst is shown in FIG. 5, and is at 920cm-1No distinct vibrational peak of Si-O-B bond was observed in the vicinity.
As can be seen from FIG. 5, no significant signal of Si-O-B bond can be observed by infrared, because the material prepared by the method has boron atoms only loaded on the surface of the carrier SBA-15, and the boron atoms and the carrier have only the contact surface on the surface of the carrier, and the interaction is weak, so no significant signal of Si-O-B bond can be observed by infrared.
Comparative example 4
Preparing load type B/SiO according to the patent [ CN110124647A ]2Catalyst, 3.57g boric acid is taken to be put in a 20mL glass bottle, 1mL ethylene glycol is added, and boron precursor solution is obtained after stirring and dissolving at 50 ℃. And (3) soaking 1mL of the solution on 1g of SBA-15, standing at room temperature for 2h, placing in a 50 ℃ oven overnight, heating the obtained sample at 5 ℃/min to 700 ℃, and roasting for 3h to obtain the supported B/SBA-15 catalyst.
The obtained catalyst was measured for the contents of boron atoms and silicon atoms using the aforementioned method using an inductively coupled plasma emission spectrometer (ICP-OES), and it was found that the B/SBA-15 catalyst contained 6 wt% of boron atoms.
Comparative example 5
0.1g of the catalyst prepared in comparative example 3 was taken to evaluate the performance of oxidative dehydrogenation of ethane. The catalyst is placed in a fixed bed reactor, and the proportion of the feed gas is C2H6:O2:N21:1:4, temperature 595 ℃, WHSV 25.6h-1As shown in fig. 6, the conversion of the catalyst gradually decreased over a reaction time of 10 h. Table 4 shows partial loss of boron atoms from the catalyst during the reaction.
Comparative example 6
0.1g of the catalyst prepared in comparative example 3 was taken and placed in a fixed bed reactor with a feed gas ratio C3H8:O2:N21:1.5:3.5, WHSV of 84.6h-1The catalytic reaction is carried out at 515 ℃ and 535 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Comparative example 7
0.1g of the catalyst prepared in comparative example 4 was taken for evaluation of the oxidative dehydrogenation performance of isobutane. The catalyst is placed in a fixed bed reactor, and the proportion of the feeding gas is i-C4H10:O2:N21:1:4, WHSV 12.4h-1The catalytic reaction is carried out at 470 ℃ and 490 ℃ respectively, the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
Comparative example 8
0.1g of the catalyst prepared in comparative example 4 was taken for evaluation of n-butane oxidative dehydrogenation performance. The catalyst is placed in a fixed bed reactor, and the feed gas proportion is n-C4H10:O2:N21:0.5:4.5, WHSV of 2.4h-1The catalytic reaction is respectively carried out at 380 ℃ and 400 ℃ and the reaction is carried out for 1h under normal pressure, and the test results are shown in Table 3.
TABLE 3 reactivity of boron-doped silica fiber materials for the oxidative dehydrogenation of lower alkanes to olefins
Remarking: WHSV: refers to the mass of the reactant passing through the boron-doped silica fiber material per unit mass per unit time
Comparing the test results of inventive example 5 and inventive example 6, i.e., comparing the properties of the materials provided in inventive example 1 and inventive example 2, it can be seen from table 3 that the alkane conversion, olefin selectivity and yield of the material measured in example 5 are all higher than those measured in example 6 under the same conditions of catalytic oxidative dehydrogenation of ethane, indicating that the properties of the material prepared in inventive example 2 are better than those of the material prepared in example 1, indicating that the addition of surfactant helps to improve the properties of the boron-doped silica fiber material when preparing the boron-doped silica fiber material provided in the present invention.
As can be seen from table 3, the results of the tests of comparative examples 8, 9, 10 and comparative examples 6, 7, 8, i.e. the properties of the materials prepared in comparative examples 3, 4 and comparative examples 3, 4, show that the catalytic reaction is carried out under the same conditions, and the materials provided in examples 3 and 4 have higher alkane conversion, olefin selectivity and yield in the catalytic alkane dehydrogenation process than the materials prepared in comparative documents 3 and 4. The materials prepared in the comparative examples 3 and 4 are powdery, the materials prepared by the electrostatic spinning process are integral, the integral materials are favorable for mass and heat transfer, olefin can be prevented from being further oxidized, hot spots formed on a reaction bed layer can be avoided, and the selectivity of the olefin is further improved.
Example 13 stability determination of boron in boron-doped silica fiber Material
Taking the materials after the catalytic reaction in the embodiment 12 and the comparative example 5 of the invention, and measuring the content of the boron element in the materials after the catalytic reaction, wherein the measuring method comprises the steps of putting a 20mg material sample into a polytetrafluoroethylene high-pressure reaction kettle, adding 3ml of concentrated hydrochloric acid and 3ml of hydrofluoric acid, dissolving at 150 ℃, and evaporating the solution. And adding deionized water into the polytetrafluoroethylene high-pressure reaction kettle for multiple times to dissolve the sample, finally performing constant volume by using a 25ml polypropylene volumetric flask, and testing the content of the boron element by using an inductively coupled plasma emission spectrometer. The measurement results are shown in Table 4.
TABLE 4 boron content of materials before and after the reaction for preparing olefin by oxidative dehydrogenation of light alkane
As can be seen from table 4, the boron-doped silica fiber material participating in the catalytic reaction in example 12 had a boron element mass percentage of 1.8% both before and after the reaction. The boron-doped silica fiber material participating in the catalytic reaction in example 12 is more stable in terms of the uniform dispersion of the boron species in the material structure and the existence of the confinement effect of the physical system. This allows for greater stability of the material at high temperatures. The mass percentage of the boron element in the material participating in the catalytic reaction in the comparative example 5 is reduced from 1.8% to 1.1% before and after the reaction, which indicates that the boron element in the material participating in the catalytic reaction in the comparative example 5 is unstable, and the boron element is lost in the catalytic reaction process.
The foregoing is considered as illustrative and not restrictive in character, and that various modifications, equivalents, and improvements made within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (14)
1. A boron doped silica fibre material, wherein boron atoms in the boron doped silica fibre material are bonded to a silica backbone by B-O-Si chemical bonds.
2. The material according to claim 1, wherein the boron-doped silica fiber material comprises the components in mass percent, in terms of atomic mass active component ratio, and boron atoms account for 0.03-6 wt% of the mass of the boron-doped silica fiber material; the silicon atoms account for 36.8-46.7 wt% of the mass of the boron-doped silicon dioxide fiber material; the balance being oxygen atoms.
3. A material according to claim 1 or 2, characterized in that the boron doped silica fiber material microstructure is fibrous, preferably the fiber diameter is 50nm-2 μ η ι.
4. A method of producing a boron doped silica fibre material according to any one of claims 1 to 3, characterised in that the method of production comprises the steps of:
(1) preparing a spinning solution of boron-doped silicon dioxide;
(2) preparing the precursor of the boron-doped silicon dioxide fiber material by electrostatic spinning, and roasting the precursor of the boron-doped silicon dioxide fiber material to obtain the boron-doped silicon dioxide fiber material.
5. The method according to claim 4, wherein the step (1) comprises:
1) dissolving a boron source in a mixed solvent of ethanol and water, preparing a solution with a corresponding boron content, and adjusting the solution to be acidic;
2) adding a silicon source into the acidic solution obtained in the step 1) to prepare a solution with a corresponding silicon content;
3) adding a spinning assistant aqueous solution with equal mass into the solution obtained in the step 2) to obtain a spinning solution;
preferably, the step (1) further comprises adding a surfactant before adding the silicon source;
preferably, in the step (1) 2), a silicon source is added and then the mixture is stirred for 0.5 to 1 hour;
preferably, in the step (1) 3), after adding the spinning assistant aqueous solution, stirring for 4-12 hours to obtain a spinning solution.
6. The method according to claim 5, wherein in step (1), the solution has a boron concentration of 0.01 to 1 wt% in terms of boron atomic mass;
preferably, the mass ratio of the ethanol to the water is 1: 10-1: 1;
preferably, the pH of the solution is 2-4;
preferably, the boron source is any one or combination of two or more of water-soluble or hydrolysable boron-containing substances, and more preferably, the boron source is selected from one or two or more of boric acid, trimethyl borate, triethyl borate and tributyl borate.
7. The method according to any one of claims 4 to 6, wherein the concentration of the surfactant in the solution is 0 to 10 wt%;
preferably, the surfactant is any one or a combination of two or more surfactants soluble in water;
more preferably, the surfactant is selected from one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), F127, P123, P103, P104.
8. The production method according to any one of claims 4 to 7, wherein in the step (1) 2), the solution has a silicon concentration of 1 to 10 wt% based on the mass of silicon atom;
preferably, the silicon source is any one of an organic or inorganic silicon source which is soluble or hydrolysable;
more preferably, the silicon source is selected from one or more of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrabutyl orthosilicate (TBOS), and silica sol.
9. The method according to any one of claims 4 to 8, wherein in step (1) 3), the concentration of the spinning aid in the aqueous solution of the spinning aid is 5 to 15 wt%;
preferably, the spinning aid is a high molecular material which can increase the viscosity of the solution after being dissolved in water;
more preferably, the spinning aid is selected from one or a combination of more than two of polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP) and Polyacrylonitrile (PAN).
10. The method according to any one of claims 4 to 9, wherein in the step (2), the electrospinning speed is 1 to 10ml/h, and preferably, the voltage is 7 to 14 kV; or, preferably, the receiving mode is flat plate or roller receiving, and the receiving distance is 15-30 cm;
11. the preparation method according to any one of claims 4 to 10, wherein in the step (2), the roasting temperature is 450 to 1000 ℃, preferably, the roasting time is 0.5 to 5 hours; or, preferably, the boron-doped silica fiber material precursor is roasted in a muffle furnace, and the heating rate of the muffle furnace is 0.5-5 ℃/min.
12. A boron-doped silica fiber material produced by the production method according to any one of claims 4 to 11.
13. Use of the boron doped silica fiber material of any one of claims 1 to 3 or claim 12 as a catalyst in the oxidative dehydrogenation of lower alkanes to lower alkenes;
preferably, the lower alkane is an alkane containing 2 to 8 carbon atoms.
14. The method for preparing the low-carbon olefin by the oxidative dehydrogenation of the low-carbon alkane is characterized by comprising the following steps of:
contacting the boron-doped silica fiber material of any one of claims 1 to 3 or claim 12 with a mixed gas containing alkane, oxidant and diluent gas, and carrying out dehydrogenation reaction at 380-610 ℃ to prepare low-carbon olefin;
preferably, the volume ratio of the alkane is 5-30%, the volume ratio of the oxidant gas is 5-30%, and the balance is diluent gas;
preferably, the boron-doped silica fiber material is contacted with mixed gas containing alkane, oxidant and diluent gas in a fixed bed reactor to perform dehydrogenation reaction; preferably, the reaction Weight Hourly Space Velocity (WHSV) of the fixed bed reactor is 2.4-84.6L g-1·h-1；
Preferably, the alkane is one of ethane, propane, isobutane and n-butane;
preferably, the oxidant is one or two of oxygen or air;
preferably, the diluent gas is an inert gas, preferably one of nitrogen, helium and argon.
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| CN108484349A (en) * | 2018-02-28 | 2018-09-04 | 厦门大学 | A method of carrying out alkanes oxidative dehydrogenation alkene using liquid oxidatively B catalyst |
| CN110124647A (en) * | 2019-06-27 | 2019-08-16 | 大连理工大学 | Support type non-metallic catalyst, preparation method and applications |
| CN111097297A (en) * | 2019-12-30 | 2020-05-05 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and preparation method and application thereof |
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| CN108484349A (en) * | 2018-02-28 | 2018-09-04 | 厦门大学 | A method of carrying out alkanes oxidative dehydrogenation alkene using liquid oxidatively B catalyst |
| CN110124647A (en) * | 2019-06-27 | 2019-08-16 | 大连理工大学 | Support type non-metallic catalyst, preparation method and applications |
| CN111097297A (en) * | 2019-12-30 | 2020-05-05 | 江西师范大学 | Boron-doped microporous silicon dioxide membrane and preparation method and application thereof |
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| CN115430460A (en) * | 2022-09-22 | 2022-12-06 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
| CN115430460B (en) * | 2022-09-22 | 2024-01-02 | 浙江大学 | Boron-silicon molecular sieve catalyst for oxidative dehydrogenation of low-carbon alkane and preparation method thereof |
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