CN114570412A - Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application - Google Patents
Fischer-Tropsch aromatic hydrocarbon catalyst, preparation method and application Download PDFInfo
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- CN114570412A CN114570412A CN202210153161.9A CN202210153161A CN114570412A CN 114570412 A CN114570412 A CN 114570412A CN 202210153161 A CN202210153161 A CN 202210153161A CN 114570412 A CN114570412 A CN 114570412A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000002808 molecular sieve Substances 0.000 claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 76
- 239000011258 core-shell material Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
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- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 8
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
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- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 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 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical group [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 3
- 150000003839 salts Chemical class 0.000 claims 2
- 239000002904 solvent Substances 0.000 claims 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 150000002696 manganese Chemical class 0.000 claims 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims 1
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims 1
- 239000012286 potassium permanganate Substances 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 44
- 230000000694 effects Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
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- 239000012153 distilled water Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
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- 238000005119 centrifugation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
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- 239000008188 pellet Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- 238000012805 post-processing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000001016 Ostwald ripening Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
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- 230000000087 stabilizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/334—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing molecular sieve catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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Abstract
本发明公开了一种费托芳烃催化剂和制备方法及用途，其特征是，催化剂为Fe2O3@SiO2/分子筛，Fe2O3活性金属氧化物的形貌为碟形、笼形、多面体、立方形或纺锤形；SiO2壳层为无定形结构；分子筛为多孔分级结构。本发明本发明所制备的催化剂的反应温度低，制备过程简单、产量高，通过控制反应条件可以得到不同形貌和壳层厚度的多孔单核双壳催化剂，在本发明技术方案范围内，不同形貌Fe2O3核的形貌为碟形、笼形、多面体、立方形或纺锤形。本发明制备的催化剂芳烃选择性可达70wt％；此外，本发明所制备的催化剂的形貌可控、尺寸可调，这为费托反应提供了不同的限域空间，进而可实现费托反应的高活性和高选择性。
The invention discloses a Fischer-Tropsch aromatics catalyst and a preparation method and application thereof, which are characterized in that the catalyst is Fe 2 O 3 @SiO 2 /molecular sieve, and the morphology of Fe 2 O 3 active metal oxide is dish-shaped, cage-shaped, Polyhedron, cubic or spindle shape; SiO 2 shell is amorphous structure; molecular sieve is porous hierarchical structure. The catalyst prepared by the present invention has low reaction temperature, simple preparation process and high yield, and can obtain porous single-core double-shell catalysts with different morphologies and shell thicknesses by controlling the reaction conditions. Within the scope of the technical scheme of the present invention, different Morphology The morphology of Fe 2 O 3 nuclei is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped. The aromatics selectivity of the catalyst prepared by the present invention can reach 70 wt%; in addition, the catalyst prepared by the present invention has controllable morphology and adjustable size, which provides different confinement spaces for the Fischer-Tropsch reaction, thereby realizing the Fischer-Tropsch reaction. high activity and selectivity.
Description
技术领域technical field
本发明涉及一种费托芳烃催化剂和制备方法及用途，尤其涉及一种形貌和壳层厚度可控的Fe2O3@SiO2/分子筛费托催化剂及制备方法，属于催化剂纳米限域技术领域。The invention relates to a Fischer-Tropsch arene catalyst, a preparation method and use thereof, in particular to a Fe 2 O 3 @SiO 2 /molecular sieve Fischer-Tropsch catalyst with controllable morphology and shell thickness and a preparation method, which belong to the catalyst nano-confinement technology field.
背景技术Background technique
核壳结构催化剂能有效消除纳米颗粒在费托反应过程中颗粒内外表面压力不一致导致的结构坍塌和奥斯特瓦尔德熟化机制引起的纳米颗粒长大，也就能够解决积碳和烧结问题。核壳结构凭借其较高的催化活性和稳定性受到研究者的青睐。费托是将合成气(H2+CO)催化转化成液体燃料的反应，在催化剂表面进行的聚合反应。费托反应中合成气在活性颗粒内外表面的填充，会破坏催化剂结构的完整性、降低纳米限域效应，进而降低催化活性和产物选择性。核壳催化剂的制备能抑制费托反应中活性颗粒内外压力不一致导致的结构坍塌，进而有效提高孔的纳米限域效应、避免活性位被烧结，而且不影响合成气与活性位的接触。在保持催化活性和稳定性的同时，能够实现对目标产物100％的选择性。为了有效的提高芳香烃产率，可调控壳层的气孔率、孔尺寸、壳层厚度来调控反应物和产物向活性位的扩散速度；调控活性颗粒的形貌，最大化活性金属与壳层材料的协同效应。The core-shell structure catalyst can effectively eliminate the structure collapse caused by the inconsistency of the inner and outer surface pressures of the nanoparticles during the Fischer-Tropsch reaction process and the nanoparticle growth caused by the Ostwald ripening mechanism, which can also solve the problems of carbon deposition and sintering. The core-shell structure is favored by researchers due to its high catalytic activity and stability. Fischer-Tropsch is a reaction that catalyzes the conversion of syngas (H 2 +CO) into liquid fuel, a polymerization reaction that takes place on the surface of a catalyst. The filling of syngas on the inner and outer surfaces of the active particles in the Fischer-Tropsch reaction will destroy the structural integrity of the catalyst, reduce the nanoconfinement effect, and then reduce the catalytic activity and product selectivity. The preparation of core-shell catalysts can inhibit the structural collapse caused by the inconsistency of internal and external pressures of active particles in the Fischer-Tropsch reaction, thereby effectively improving the nano-confinement effect of pores, avoiding the sintering of active sites, and does not affect the contact between syngas and active sites. While maintaining catalytic activity and stability, 100% selectivity to target products can be achieved. In order to effectively improve the yield of aromatic hydrocarbons, the porosity, pore size, and thickness of the shell layer can be adjusted to control the diffusion rate of reactants and products to the active sites; the morphology of active particles can be adjusted to maximize the active metal and shell layer. Synergy of materials.
制备核壳结构的方法一般为浸渍法。即以模板为核层或壳层，将所需材料通过真空抽滤手段包覆在模板核上或吸附在模板壳上，通过煅烧去处杂质，形成核壳结构的催化剂。文献“C Wu，L Dong，J Onwudili，PT Williams，J Huang[J].Acs SustainableChemistry&Engineering，2013，1，1083-1091.”、文献“X Zhang，CY Guo，ZC Zhang,JS Gao，CM Xu[J].Journal of Catalysis，2012，292，213-226.”都公开了核壳催化剂的制备方法，这些方法都是浸渍法；所合成的纳米颗粒与载体间存在强相互作用，在一定程度上影响合成气与活性位的接触，不利于催化活性和目标产物选择性的提高。另外，浸渍法适用于核壳结构的制备，不适合单核双壳催化剂的合成。文献“J Bao，J He，Y Zhang，Y Yoneyama，NTsubaki[J].Angewandte Chemie International Edition，2008，120，359-362.”、文献“SSartipi，JE van Dijk，J Gascon，F Kapteijn[J].Applied Catalysis A：General，2013，456，11-22.”公开了双核壳催化剂的合成方法，该方法中核壳结构通过浸渍法合成，最外层壳层通过水热法合成，然后加热、煅烧除去软模板获得核壳结构催化剂。The method for preparing the core-shell structure is generally the impregnation method. That is, the template is used as the core layer or shell layer, the desired material is coated on the template core or adsorbed on the template shell by vacuum filtration, and impurities are removed by calcination to form a catalyst with a core-shell structure. Literature "C Wu, L Dong, J Onwudili, PT Williams, J Huang [J].Acs Sustainable Chemistry&Engineering, 2013, 1, 1083-1091.", literature "X Zhang, CY Guo, ZC Zhang, JS Gao, CM Xu[ J]. Journal of Catalysis, 2012, 292, 213-226. "All disclosed the preparation methods of core-shell catalysts, these methods are all impregnation methods; there is a strong interaction between the synthesized nanoparticles and the carrier, to a certain extent It affects the contact between the syngas and the active site, which is not conducive to the improvement of the catalytic activity and the selectivity of the target product. In addition, the impregnation method is suitable for the preparation of core-shell structures, but not for the synthesis of single-core and double-shell catalysts. Literature "J Bao, J He, Y Zhang, Y Yoneyama, NTsubaki [J]. Angewandte Chemie International Edition, 2008, 120, 359-362.", Literature "SSartipi, JE van Dijk, J Gascon, F Kapteijn [J] .Applied Catalysis A: General, 2013, 456, 11-22." discloses a method for synthesizing a dual-core-shell catalyst, in which the core-shell structure is synthesized by an impregnation method, the outermost shell layer is synthesized by a hydrothermal method, and then heated and calcined. The core-shell structure catalyst was obtained by removing the soft template.
现今核壳费托催化剂的合成需要采用浸渍法通过真空抽滤获得核壳催化剂，煅烧后去除杂质；随后通过水热法在溶液中通过模板物质合成及煅烧后才能得到最终的核壳结构。其过程相对繁琐，所制备活性颗粒的形貌和尺寸不可控，不能根据需要方便、快捷的制备出所需的核壳催化剂。At present, the synthesis of core-shell Fischer-Tropsch catalysts requires the impregnation method to obtain core-shell catalysts through vacuum filtration, and calcination to remove impurities; then the final core-shell structure can be obtained after the synthesis and calcination of template substances in solution by hydrothermal method. The process is relatively cumbersome, the morphology and size of the prepared active particles are uncontrollable, and the desired core-shell catalyst cannot be conveniently and quickly prepared as required.
发明内容SUMMARY OF THE INVENTION
本发明针对现有技术中存在的不足，提供了一种费托芳烃催化剂，该结构具有形貌可控、壳层厚度可调、尺寸可调，便于应用。Aiming at the deficiencies in the prior art, the present invention provides a Fischer-Tropsch aromatic catalyst, which has the advantages of controllable morphology, adjustable shell thickness and adjustable size, and is convenient for application.
本发明还提供了不同形貌的活性金属氧化物Fe2O3核、壳层厚度可控的Fe2O3@SiO2核壳结构及分级多孔分子筛的制备方法，该方法简单易行、方便快捷，所制形貌和尺寸可控的核壳催化剂的形貌和尺寸更容易控制。The invention also provides active metal oxide Fe 2 O 3 cores with different morphologies, Fe 2 O 3 @SiO 2 core-shell structures with controllable shell layer thicknesses, and a preparation method for a graded porous molecular sieve. The method is simple, feasible and convenient. Fast, and the morphology and size of the prepared core-shell catalysts with controllable morphology and size are easier to control.
本发明还提供了一种费托芳烃催化剂的用途，用于芳香烃的制备。The invention also provides the use of a Fischer-Tropsch aromatic catalyst for the preparation of aromatic hydrocarbons.
本发明提供了一种简单、方便的制备形貌和尺寸可控的费托芳烃催化剂的方法以及所得的Fe2O3@SiO2/分子筛费托催化剂，具体技术方案如下：The invention provides a simple and convenient method for preparing a Fischer-Tropsch aromatic catalyst with controllable morphology and size and the obtained Fe 2 O 3 @SiO 2 /molecular sieve Fischer-Tropsch catalyst. The specific technical solutions are as follows:
一种费托芳烃催化剂，其性能参数为：是Fe2O3核的形貌为碟形、笼形、多面体、立方形、纺锤形。A Fischer-Tropsch aromatic hydrocarbon catalyst whose performance parameters are as follows: Fe 2 O 3 nuclei are in the shape of a dish, a cage, a polyhedron, a cube and a spindle.
碟形Fe2O3的直径为100～300纳米、厚度为6～15纳米；笼形Fe2O3的直径为1000～3000纳米；多面体Fe2O3的长度为30～100纳米；立方形Fe2O3的长度为20～80纳米，纺锤形Fe2O3的长度为500～3000纳米；SiO2壳层厚度为5～40纳米、孔径为3～4纳米；多孔分子筛的Si/Al比为15～30。The diameter of dish-shaped Fe 2 O 3 is 100-300 nm and the thickness is 6-15 nm; the diameter of cage-shaped Fe 2 O 3 is 1000-3000 nm; the length of polyhedral Fe 2 O 3 is 30-100 nm; The length of Fe 2 O 3 is 20-80 nanometers, the length of spindle-shaped Fe 2 O 3 is 500-3000 nanometers; the thickness of SiO 2 shell is 5-40 nanometers, and the pore size is 3-4 nanometers; Si/Al of porous molecular sieves The ratio is 15-30.
本发明一种费托芳烃催化剂的制备方法，包括以下步骤：A preparation method of a Fischer-Tropsch aromatic catalyst of the present invention comprises the following steps:
(1)不同形貌的Fe2O3的制备：将铁盐溶于去离子水中配成溶液；将水解促进剂和保护剂溶于上述溶液中，在搅拌下充分混合得混合溶液，随后移入水热反应釜中180～200℃保温反应8～10h；(1) Preparation of Fe 2 O 3 with different morphologies: Dissolve the iron salt in deionized water to make a solution; dissolve the hydrolysis accelerator and the protective agent in the above solution, mix well under stirring to obtain a mixed solution, and then move it into 180～200℃ heat preservation reaction in the hydrothermal reactor for 8～10h;
(2)后处理：将步骤(1)所得产物离心分离、洗涤，得碟形、笼形、多面体、立方形、纺锤形Fe2O3；(2) post-processing: centrifuging and washing the product obtained in step (1) to obtain disc-shaped, cage-shaped, polyhedral, cubic, and spindle-shaped Fe 2 O 3 ;
(3)核壳Fe2O3@SiO2的制备：将步骤(1)合成的不同形貌的Fe2O3和正硅酸四乙酯分散于无水乙醇中，搅拌反应一定时间后引入氨水和去离子水，继续搅拌反应；(3) Preparation of core-shell Fe 2 O 3 @SiO 2 : Disperse Fe 2 O 3 and tetraethyl orthosilicate with different morphologies synthesized in step (1) in absolute ethanol, stir and react for a certain period of time and then introduce ammonia water And deionized water, continue to stir the reaction;
(4)后处理：将步骤(3)所得产物离心分离、洗涤，得核壳Fe2O3@SiO2；(4) post-processing: centrifuging and washing the product obtained in step (3) to obtain core-shell Fe 2 O 3 @SiO 2 ;
(5)分子筛的制备：将异丙醇铝、正硅酸四乙酯、四丙基氢氧化铵溶于去离子水中、回流反应；搅拌加入质量为三氨基三甲氧基硅烷；(5) Preparation of molecular sieve: aluminum isopropoxide, tetraethyl orthosilicate and tetrapropyl ammonium hydroxide are dissolved in deionized water, and refluxed for reaction; stirring and adding quality are triaminotrimethoxysilane;
(6)后处理：将步骤(5)所得产物离心分离、洗涤，煅烧得分子筛。(6) Post-treatment: the product obtained in step (5) is centrifuged, washed, and calcined to obtain molecular sieves.
(7)将Fe2O3@SiO2与分子筛物理混合压片造粒得Fe2O3@SiO2/分子筛核壳费托催化剂。(7) Fe 2 O 3 @SiO 2 was physically mixed with molecular sieve and pressed into pellets to obtain Fe 2 O 3 @SiO 2 /molecular sieve core-shell Fischer-Tropsch catalyst.
本发明所述步骤(1)所述铁盐为二水合草酸亚铁、六水氯化铁、硝酸铁、柠檬酸铁铵或硫酸亚铁氨；所述无水乙酸盐为无水乙酸钾、无水乙酸钠、无水乙酸铵；所述保护剂为聚乙烯吡咯烷酮、N-甲基吡咯烷酮、乙烯基吡咯烷酮、2-吡咯烷酮或十六烷基三甲基溴化铵。The iron salt described in step (1) of the present invention is ferrous oxalate dihydrate, ferric chloride hexahydrate, ferric nitrate, ferric ammonium citrate or ferrous ammonium sulfate; the anhydrous acetate is anhydrous potassium acetate , anhydrous sodium acetate, anhydrous ammonium acetate; the protective agent is polyvinylpyrrolidone, N-methylpyrrolidone, vinylpyrrolidone, 2-pyrrolidone or cetyltrimethylammonium bromide.
本发明步骤(1)中，步骤(1)中铁盐:水解促进剂:保护剂的浓度比为0.06～0.69:0.02～0.66:0.02～0.7，可以通过控制反应物浓度大小来调整Fe2O3的性能参数。In step (1) of the present invention, in step (1), the concentration ratio of iron salt: hydrolysis accelerator: protective agent is 0.06-0.69: 0.02-0.66: 0.02-0.7, and Fe 2 O 3 can be adjusted by controlling the concentration of reactants performance parameters.
本发明步骤(1)中，反应温度为150-200℃，反应时间为6-15h。In the step (1) of the present invention, the reaction temperature is 150-200° C., and the reaction time is 6-15 h.
本发明步骤(3)中，Fe2O3:无水乙醇体积比为1:40～90。In step (3) of the present invention, the volume ratio of Fe 2 O 3 : absolute ethanol is 1:40-90.
本发明步骤(3)中，无水乙醇:正硅酸四乙酯:氨水:水的体积比为300:0.5～1.5:2～8:10～30,可以通过调节这三者之间的比例关系来调控水解速度进而调控SiO2壳层的厚度和孔尺寸。In step (3) of the present invention, the volume ratio of absolute ethanol: tetraethyl orthosilicate: ammonia water: water is 300: 0.5-1.5: 2-8: 10-30, which can be adjusted by adjusting the ratio between the three. The relationship can be used to control the hydrolysis rate and thus the thickness and pore size of the SiO2 shell.
本发明步骤(3)中，搅拌反应时间依次为2～5h和3～6h，可以通过调节反应时间来调整SiO2壳层的厚度。In the step (3) of the present invention, the stirring reaction time is successively 2-5h and 3-6h, and the thickness of the SiO 2 shell can be adjusted by adjusting the reaction time.
本发明步骤(5)中，异丙醇铝、正硅酸四乙酯、四丙基氢氧化铵、三氨基三甲氧基硅烷的质量比为1:10～40:10～30:0.5～2。In step (5) of the present invention, the mass ratio of aluminum isopropoxide, tetraethyl orthosilicate, tetrapropylammonium hydroxide, and triaminotrimethoxysilane is 1:10～40:10～30:0.5～2 .
本发明步骤(5)中，回流时间为15～30h，水热反应温度为150～200℃，水热反应时间100～150h。In step (5) of the present invention, the reflux time is 15-30h, the hydrothermal reaction temperature is 150-200°C, and the hydrothermal reaction time is 100-150h.
发明步骤(6)中，煅烧温度为400～650℃，煅烧时间为4-8h。In the inventive step (6), the calcination temperature is 400-650° C., and the calcination time is 4-8h.
本发明步骤(7)中，Fe2O3@SiO2与分子筛的质量比为1.0：0.3～1.0。In step (7) of the present invention, the mass ratio of Fe 2 O 3 @SiO 2 to molecular sieve is 1.0:0.3-1.0.
费托芳烃催化剂，所述催化剂用于费托反应，反应条件为300～350℃、2MPa、流速为2000～3000mlh-1gcat -1、合成气(H2/CO)为1:1,费托产物为芳香烃。A Fischer-Tropsch aromatic catalyst, the catalyst is used for Fischer-Tropsch reaction, the reaction conditions are 300-350° C., 2MPa, flow rate is 2000-3000mlh -1 g cat -1 , synthesis gas (H 2 /CO) is 1:1, and the The products are aromatic hydrocarbons.
本发明的有益效果：本发明采用水热法合成一种费托芳烃催化剂，首先将铁盐、水解促进剂和保护剂溶解于去离子水中，然后将溶液置于水热反应釜中反应一定时间得不同形貌的Fe2O3；其次，将一定量的Fe2O3核与正硅酸四乙酯分散于一定量的无水乙醇中在室温下搅拌反应一定时间，然后分别加入一定量的氨水和去离子水，继续在室温下搅拌反应一定时间，得多孔核壳Fe2O3@SiO2；再次，将异丙醇铝、正硅酸四乙酯、四丙基氢氧化铵溶于去离子水中、回流反应；搅拌加入质量为三氨基三甲氧基硅烷，水热反应得分子筛；最后，将Fe2O3@SiO2与分子筛物理混合压片造粒得Fe2O3@SiO2/分子筛核壳费托催化剂。本发明利用简单的水热反应把合成出了形貌和尺寸可控的Fe2O3@SiO2/分子筛费托催化剂，由于SiO2壳层的存在，可避免活性金属氧化物(Fe2O3)在费托反应过程中由于活性颗粒内外表面压力不一致导致的结构坍塌。此方法也为其它种类SiO2稳定的催化剂的制备提供了技术支撑。Fe2O3核的形貌和尺寸大小由起始反应物的浓度、水解促进剂和保护剂的类型、反应温度和反应时间决定，核壳Fe2O3@SiO2中SiO2壳层厚度与无水乙醇、正硅酸四乙酯、氨水、水的体积比和反应时间有关，分子筛的Si/Al比由起始反应物的浓度决定。因此，可以通过调节这些反应条件的关系得到所需尺寸和壳层厚度的Fe2O3@SiO2/分子筛费托催化剂。与现有的浸渍法、共沉淀法相比，本发明方法简单，制备的可重复性好，形貌、尺寸和壳层厚度更容易控制，粒度和孔尺寸分布窄。Beneficial effects of the present invention: the present invention adopts a hydrothermal method to synthesize a Fischer-Tropsch aromatic catalyst. First, the iron salt, the hydrolysis accelerator and the protective agent are dissolved in deionized water, and then the solution is placed in a hydrothermal reactor to react for a certain period of time. Fe 2 O 3 with different morphologies was obtained; secondly, a certain amount of Fe 2 O 3 cores and tetraethyl orthosilicate were dispersed in a certain amount of absolute ethanol, stirred and reacted at room temperature for a certain period of time, and then a certain amount of Ammonia water and deionized water were obtained, and the reaction was stirred at room temperature for a certain period of time to obtain porous core-shell Fe 2 O 3 @SiO 2 ; again, aluminum isopropoxide, tetraethyl orthosilicate and tetrapropylammonium hydroxide were dissolved in In deionized water, reflux reaction; stir and add triaminotrimethoxysilane, hydrothermal reaction to obtain molecular sieve; finally, Fe 2 O 3 @SiO 2 and molecular sieve are physically mixed and pressed into pellets to obtain Fe 2 O 3 @SiO 2 / Molecular sieve core-shell Fischer-Tropsch catalyst. The invention utilizes a simple hydrothermal reaction to synthesize a Fe 2 O 3 @SiO 2 /molecular sieve Fischer-Tropsch catalyst with controllable morphology and size. Due to the existence of the SiO 2 shell layer, active metal oxides (Fe 2 O 2 ) can be avoided. 3 ) Structural collapse due to inconsistent internal and external surface pressures of active particles during the Fischer-Tropsch reaction. This method also provides technical support for the preparation of other kinds of SiO2 -stabilized catalysts. The morphology and size of Fe 2 O 3 cores are determined by the concentration of starting reactants, the types of hydrolysis promoters and protective agents, reaction temperature and reaction time, and the thickness of SiO 2 shell in core-shell Fe 2 O 3 @SiO 2 It is related to the volume ratio of absolute ethanol, tetraethyl orthosilicate, ammonia water, water and reaction time, and the Si/Al ratio of molecular sieve is determined by the concentration of starting reactants. Therefore, Fe 2 O 3 @SiO 2 /zeolite Fischer-Tropsch catalysts with desired size and shell thickness can be obtained by adjusting the relationship of these reaction conditions. Compared with the existing impregnation method and co-precipitation method, the method of the invention is simple, the preparation repeatability is good, the morphology, size and shell thickness are easier to control, and the particle size and pore size distribution are narrow.
本发明所制备的催化剂的反应温度低，制备过程简单、产量高，通过控制反应条件可以得到不同形貌和壳层厚度的多孔单核双壳催化剂，在本发明技术方案范围内，不同形貌Fe2O3核的形貌为碟形、笼形、多面体、立方形或纺锤形。碟形Fe2O3的直径为100～300纳米、厚度为6～15纳米；笼形Fe2O3的直径为1000～3000纳米；多面体Fe2O3的长度为30～100纳米；立方形Fe2O3的长度为20～80纳米，纺锤形Fe2O3的长度为500～3000纳米；SiO2壳层厚度为5～40纳米、孔径为3～4纳米；多孔分子筛的Si/Al比为15～30。由于SiO2壳层的稳定作用可有效避免活性Fe2O3核在费托反应过程中的结构坍塌所致的失活和积碳现象，进而可大幅度提高费托芳烃催化剂的催化活性和产物选择性，与现有无壳层保护的铁基催化剂相比(Wen CX,et al.,Fuel 2019,244,492-498；Wen CX,et al.,Energy&Fuel 2020,34(9),11282-11289)，本发明制备的催化剂芳烃选择性可达70wt％；此外，本发明所制备的催化剂的形貌可控、尺寸可调，这为费托反应提供了不同的限域空间，进而可实现费托反应的高活性和高选择性。此外，本发明所制备的催化剂在光催化和生物质催化转化等方面具有极大的应用价值。The catalyst prepared by the invention has low reaction temperature, simple preparation process and high yield, and can obtain porous single-core double-shell catalysts with different morphologies and shell thicknesses by controlling the reaction conditions. The morphology of Fe 2 O 3 nuclei is dish-shaped, cage-shaped, polyhedral, cubic or spindle-shaped. The diameter of dish-shaped Fe 2 O 3 is 100-300 nm and the thickness is 6-15 nm; the diameter of cage-shaped Fe 2 O 3 is 1000-3000 nm; the length of polyhedral Fe 2 O 3 is 30-100 nm; The length of Fe 2 O 3 is 20-80 nanometers, the length of spindle-shaped Fe 2 O 3 is 500-3000 nanometers; the thickness of SiO 2 shell is 5-40 nanometers, and the pore size is 3-4 nanometers; Si/Al of porous molecular sieves The ratio is 15-30. Due to the stabilizing effect of the SiO2 shell, the deactivation and carbon deposition caused by the structural collapse of the active Fe2O3 core during the Fischer - Tropsch reaction can be effectively avoided, which in turn can greatly improve the catalytic activity and products of the Fischer-Tropsch arene catalyst. Selectivity, compared with existing iron-based catalysts without shell protection (Wen CX, et al., Fuel 2019, 244, 492-498; Wen CX, et al., Energy & Fuel 2020, 34(9), 11282-11289) , the aromatics selectivity of the catalyst prepared by the present invention can reach 70 wt%; in addition, the catalyst prepared by the present invention has controllable morphology and adjustable size, which provides different confinement spaces for the Fischer-Tropsch reaction, thereby realizing the Fischer-Tropsch reaction. high activity and selectivity of the reaction. In addition, the catalyst prepared by the present invention has great application value in photocatalysis and biomass catalytic conversion.
附图说明Description of drawings
图1为本发明实例1合成的碟形Fe2O3的扫描电子显微镜(SEM)图片。FIG. 1 is a scanning electron microscope (SEM) picture of the disk-shaped Fe 2 O 3 synthesized in Example 1 of the present invention.
图2为本发明实例1合成的Si/Al比为26的分子筛的扫描电子显微镜(SEM)图片Fig. 2 is the scanning electron microscope (SEM) picture of the molecular sieve with Si/Al ratio of 26 synthesized in Example 1 of the present invention
图3为本发明实例2合成的笼形Fe2O3的扫描电子显微镜(SEM)图片。3 is a scanning electron microscope (SEM) picture of the clathrate Fe 2 O 3 synthesized in Example 2 of the present invention.
图4为本发明实例2合成的笼形Fe2O3@SiO2的透射电子显微镜(TEM)图片。FIG. 4 is a transmission electron microscope (TEM) picture of the clathrate Fe 2 O 3 @SiO 2 synthesized in Example 2 of the present invention.
图5为本发明实例3合成的Si/Al比为26的分子筛的扫描电子显微镜(SEM)图片。5 is a scanning electron microscope (SEM) picture of a molecular sieve with a Si/Al ratio of 26 synthesized in Example 3 of the present invention.
图6为本发明实例5合成的多面体Fe2O3的扫描电子显微镜(SEM)图片。6 is a scanning electron microscope (SEM) picture of polyhedral Fe 2 O 3 synthesized in Example 5 of the present invention.
图7为本发明实例6合成的立方形Fe2O3的扫描电子显微镜(SEM)图片。7 is a scanning electron microscope (SEM) picture of the cubic Fe 2 O 3 synthesized in Example 6 of the present invention.
图8为本发明实例7合成的纺锤形Fe2O3的扫描电子显微镜(SEM)图片。8 is a scanning electron microscope (SEM) picture of the spindle-shaped Fe 2 O 3 synthesized in Example 7 of the present invention.
图9为本发明实例7合成的壳层厚度为22nm的纺锤形Fe2O3@SiO2的透射电子显微镜(TEM)图片。9 is a transmission electron microscope (TEM) picture of the spindle-shaped Fe 2 O 3 @SiO 2 with a shell thickness of 22 nm synthesized in Example 7 of the present invention.
图10为本发明实例8合成的壳层厚度为66nm的纺锤形Fe2O3@SiO2的透射电子显微镜(TEM)图片。10 is a transmission electron microscope (TEM) picture of the spindle-shaped Fe 2 O 3 @SiO 2 with a shell thickness of 66 nm synthesized in Example 8 of the present invention.
图11为本发明实例9合成的壳层厚度为48nm的纺锤形Fe2O3@SiO2的透射电子显微镜(TEM)图片。11 is a transmission electron microscope (TEM) picture of the spindle-shaped Fe 2 O 3 @SiO 2 with a shell thickness of 48 nm synthesized in Example 9 of the present invention.
具体实施方式Detailed ways
下面通过具体实施例对本发明进行进一步阐述。下述实施例着重解释本发明技术方案部分，应该明白的是，下述说明仅是示例性的，并不对本发明进行限制。The present invention will be further described below through specific embodiments. The following examples focus on explaining the technical solutions of the present invention. It should be understood that the following descriptions are only exemplary and do not limit the present invention.
实施例1Example 1
1.1将0.5g六水氯化铁溶于30mL乙醇中，搅拌并加入1g聚乙烯吡咯烷酮，随后加入0.3ml氨水，然后置于180℃水热反应釜中反应8h；1.1 Dissolve 0.5g of ferric chloride hexahydrate in 30mL of ethanol, stir and add 1g of polyvinylpyrrolidone, then add 0.3ml of ammonia water, and then place it in a 180°C hydrothermal reactor for 8h;
1.2反应完毕，将上述反应溶液分别用蒸馏水离心洗涤3～4遍(离心速度6000rpm)，得碟形Fe2O3；图1是本实施例合成的Fe2O3的SEM图片，从图中可以看出，所得Fe2O3为碟形，平均直径为250nm、平均厚度为13nm；1.2 After the reaction is completed, the above-mentioned reaction solution is centrifugally washed with distilled water for 3 to 4 times respectively (centrifugation speed 6000rpm) to obtain disc-shaped Fe 2 O 3 ; Fig. 1 is the SEM picture of Fe 2 O 3 synthesized in the present embodiment, from the figure It can be seen that the obtained Fe 2 O 3 is dish-shaped, with an average diameter of 250 nm and an average thickness of 13 nm;
1.3将0.5g Fe2O3分散于300mL无水乙醇中，同时将1.0ml正硅酸四乙酯加入无水乙醇溶液中，常温搅拌3h，把5ml氨水和20ml水加入上述溶液中，继续搅拌4h；1.3 Disperse 0.5g Fe 2 O 3 in 300mL of absolute ethanol, at the same time add 1.0ml of tetraethyl orthosilicate into the absolute ethanol solution, stir at room temperature for 3h, add 5ml of ammonia water and 20ml of water to the above solution, and continue to stir 4h;
1.4反应完毕，将上述反应溶液用蒸馏水和无水乙醇离心洗涤3～4遍(离心速度12000rpm)，得Fe2O3@SiO2，SiO2壳层的平均厚度为6nm。1.4 After the reaction is completed, the above reaction solution is centrifugally washed with distilled water and absolute ethanol for 3 to 4 times (centrifugation speed 12000rpm) to obtain Fe 2 O 3 @SiO 2 , and the average thickness of the SiO 2 shell is 6nm.
1.5将0.5g异丙醇铝、15g正硅酸四乙酯、10g四丙基氢氧化铵溶于30ml去离子水中，将该混合溶液置于90℃装置中回流20h；搅拌加入质量为0.6g三氨基三甲氧基硅烷；搅拌6h后将该混合溶液置于温度为170℃的水热反应釜中反应120h；1.5 Dissolve 0.5g of aluminum isopropoxide, 15g of tetraethyl orthosilicate, and 10g of tetrapropylammonium hydroxide in 30ml of deionized water, and place the mixed solution in a 90°C device to reflux for 20h; stir and add a mass of 0.6g Triaminotrimethoxysilane; after stirring for 6h, the mixed solution was placed in a hydrothermal reactor with a temperature of 170°C for 120h;
1.6反应完毕，将上述反应溶液用蒸馏水和无水乙醇离心洗涤3～4遍(离心速度12000rpm)，干燥后置于550℃煅烧5h得Si/Al为26的分子筛。图2是本实施例合成的分子筛的SEM图片，从图中可以看出，所得分子筛为分级多孔结构，平均尺寸为500nm。1.6 After the reaction is completed, the above reaction solution is centrifugally washed 3-4 times with distilled water and absolute ethanol (centrifugation speed 12000rpm), dried and then calcined at 550°C for 5h to obtain a molecular sieve with Si/Al of 26. Fig. 2 is a SEM picture of the molecular sieve synthesized in the present embodiment. It can be seen from the figure that the obtained molecular sieve has a hierarchical porous structure with an average size of 500 nm.
1.7将0.4gFe2O3@SiO2与0.4g分子筛物理混合后，压片造粒，得催化剂，然后置于固定床反应器中，并在330℃、2MPa、流速为3000mlh-1gcat -1、1:1的合成气(H2/CO)氛围中进行反应，得芳香烃。1.7 After physically mixing 0.4g Fe 2 O 3 @SiO 2 with 0.4g molecular sieve, press pellets to obtain the catalyst, which is then placed in a fixed-bed reactor and heated at 330°C, 2MPa, and a flow rate of 3000mlh -1 g cat - 1 , 1:1 synthesis gas (H 2 /CO) atmosphere for the reaction to obtain aromatic hydrocarbons.
实施例2Example 2
2.1将1g六水氯化铁溶于30mL去离子水中，搅拌并加入1g聚乙烯吡咯烷酮，随后加入0.3ml氨水，然后置于200℃水热反应釜中反应10h。2.1 Dissolve 1g of ferric chloride hexahydrate in 30mL of deionized water, stir and add 1g of polyvinylpyrrolidone, then add 0.3ml of ammonia water, and then place it in a 200°C hydrothermal reactor for 10h reaction.
2.2样品的洗涤过程同上实施例1.2。图3是本实施例合成的Fe2O3的SEM图片，从图中可以看出，所得Fe2O3为笼形，平均尺寸为1000nm。2.2 The washing process of the sample is the same as in Example 1.2 above. FIG. 3 is an SEM picture of Fe 2 O 3 synthesized in this example. It can be seen from the figure that the obtained Fe 2 O 3 is cage-shaped with an average size of 1000 nm.
2.3样品的制备及洗涤过程同上实施例1.3、1.4，图4是本实施例合成Fe2O3@SiO2的TEM图片，从图中可以看出，所得Fe2O3@SiO2为核壳结构，SiO2壳层厚度为160nm。2.3 The preparation and washing process of the samples are the same as those in Examples 1.3 and 1.4 above. Figure 4 is a TEM picture of Fe 2 O 3 @SiO 2 synthesized in this example. It can be seen from the figure that the obtained Fe 2 O 3 @SiO 2 is a core-shell structure with a SiO shell thickness of 160 nm.
2.4分子筛的制备及洗涤过程同上实施例1.5、1.6，制备得催化剂用于费托反应，费托反应条件同上实施例1.7。2.4 The preparation and washing process of molecular sieves are the same as those in Examples 1.5 and 1.6 above, and the prepared catalyst is used for the Fischer-Tropsch reaction, and the conditions of the Fischer-Tropsch reaction are the same as those in Example 1.7 above.
实施例3Example 3
3.1样品的制备及洗涤过程同上实施例2.1、2.2、2.3。3.1 The preparation and washing process of the samples are the same as those in Examples 2.1, 2.2 and 2.3 above.
3.2将0.8g异丙醇铝、15g正硅酸四乙酯、10g四丙基氢氧化铵溶于30ml去离子水中，将该混合溶液置于90℃装置中回流20h；搅拌加入质量为0.6g三氨基三甲氧基硅烷；搅拌6h后将该混合溶液置于温度为170℃的水热反应釜中反应120h；3.2 Dissolve 0.8g of aluminum isopropoxide, 15g of tetraethyl orthosilicate, and 10g of tetrapropylammonium hydroxide in 30ml of deionized water, and place the mixed solution in a 90°C device to reflux for 20h; stir and add a mass of 0.6g Triaminotrimethoxysilane; after stirring for 6h, the mixed solution was placed in a hydrothermal reactor with a temperature of 170°C for 120h;
3.3反应完毕，将上述反应溶液用蒸馏水和无水乙醇离心洗涤3～4遍(离心速度12000rpm)，干燥后置于550℃煅烧5h得Si/Al为18的分子筛。图5是本实施例合成的分子筛的SEM图片，从图中可以看出，所得分子筛为分级多孔结构，平均尺寸为350nm。3.3 After the reaction is completed, the above reaction solution is centrifugally washed with distilled water and absolute ethanol for 3 to 4 times (centrifugal speed 12000rpm), dried and then calcined at 550°C for 5h to obtain a molecular sieve with Si/Al of 18. Fig. 5 is a SEM picture of the molecular sieve synthesized in this example. It can be seen from the figure that the obtained molecular sieve has a hierarchical porous structure with an average size of 350 nm.
3.4将0.4gFe2O3@SiO2与0.4g分子筛物理混合后，压片造粒，得催化剂，然后置于固定床反应器中，并在320℃、2MPa、流速为3000mlh-1gcat -1、1:1的合成气(H2/CO)氛围中进行反应，得芳香烃。3.4 After physical mixing of 0.4g Fe 2 O 3 @SiO 2 and 0.4g molecular sieve, tableting and granulation to obtain a catalyst, which was then placed in a fixed-bed reactor, and heated at 320°C, 2MPa, and a flow rate of 3000mlh -1 g cat - 1 , 1:1 synthesis gas (H 2 /CO) atmosphere for the reaction to obtain aromatic hydrocarbons.
实施例4Example 4
4.1样品的制备及洗涤过程同上实施例3.1、3.2、3.3。4.1 The preparation and washing process of the samples are the same as those in Examples 3.1, 3.2 and 3.3 above.
4.2将0.5g Fe2O3@SiO2与0.3g分子筛物理混合后，压片造粒，然后置于固定床反应器中，并在320℃、2MPa、流速为3000mlh-1gcat -1、1:1的合成气(H2/CO)4.2 After physical mixing of 0.5g Fe 2 O 3 @SiO 2 and 0.3g molecular sieve, tableting and granulation, and then placing in a fixed bed reactor, and at 320 ° C, 2MPa, flow rate of 3000mlh -1 g cat -1 , 1:1 syngas (H 2 /CO)
氛围中进行反应，得芳香烃。The reaction is carried out in the atmosphere to obtain aromatic hydrocarbons.
实施例5Example 5
5.1将1g六水氯化铁和2g无水乙酸钠溶于30mL去离子水中，搅拌并加入1g十六烷基三甲基溴化铵，随后加入0.3ml氨水，然后置于200℃水热反应釜中反应10h。5.1 Dissolve 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate in 30mL of deionized water, stir and add 1g of cetyltrimethylammonium bromide, then add 0.3ml of ammonia water, and then place at 200°C for hydrothermal reaction React in the kettle for 10h.
5.2样品的洗涤过程同上实施例1.2。图6是本实施例合成的Fe2O3的SEM图片，从图中可以看出，所得Fe2O3为多面体，平均尺寸为55nm。5.2 The washing process of the sample is the same as in Example 1.2 above. FIG. 6 is an SEM picture of Fe 2 O 3 synthesized in this example. It can be seen from the figure that the obtained Fe 2 O 3 is a polyhedron with an average size of 55 nm.
5.3样品的制备及洗涤过程同上实施例1.3、1.4，所得SiO2壳层厚度为5nm。5.3 The preparation and washing process of the samples are the same as those in Examples 1.3 and 1.4 above, and the thickness of the obtained SiO 2 shell is 5 nm.
5.4分子筛的制备及洗涤过程同上实施例1.5、1.6，费托反应条件同上实施例1.7。5.4 The preparation and washing process of molecular sieves are the same as those in Examples 1.5 and 1.6 above, and the Fischer-Tropsch reaction conditions are the same as those in Example 1.7 above.
实施例6Example 6
6.1将1g六水氯化铁和2g无水乙酸钠溶于30mL去离子水中，搅拌并加入1g聚乙烯吡咯烷酮，随后加入0.3ml氨水，然后置于200℃水热反应釜中反应10h。6.2样品的洗涤过程同上实施例1.2。图7是本实施例合成的Fe2O3的SEM图片，6.1 Dissolve 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate in 30mL of deionized water, stir and add 1g of polyvinylpyrrolidone, then add 0.3ml of ammonia water, and then place it in a 200°C hydrothermal reactor for 10h reaction. 6.2 The washing process of the sample is the same as in Example 1.2 above. Fig. 7 is the SEM picture of Fe 2 O 3 synthesized in the present embodiment,
从图中可以看出，所得Fe2O3为立方形，平均尺寸为45nm。As can be seen from the figure, the obtained Fe2O3 is cubic with an average size of 45 nm.
6.3样品的制备及洗涤过程同上实施例1.3、1.4，所得SiO2壳层厚度为4.5nm。6.3 The preparation and washing process of the sample are the same as those in Examples 1.3 and 1.4 above, and the thickness of the obtained SiO 2 shell is 4.5 nm.
6.4分子筛的制备及洗涤过程同上实施例1.5、1.6，费托反应条件同上实施例4.2。6.4 The preparation and washing process of molecular sieves are the same as those in Examples 1.5 and 1.6 above, and the Fischer-Tropsch reaction conditions are the same as those in Example 4.2 above.
实施例7Example 7
7.1将1g六水氯化铁和2g无水乙酸钠溶于30mL去离子水中，搅拌并加入1g聚乙烯吡咯烷酮，随后加入1.0ml乙二胺，然后置于200℃水热反应釜中反应10h。7.1 Dissolve 1g of ferric chloride hexahydrate and 2g of anhydrous sodium acetate in 30mL of deionized water, stir and add 1g of polyvinylpyrrolidone, then add 1.0ml of ethylenediamine, and then place it in a 200°C hydrothermal reactor for 10h reaction.
7.2样品的洗涤过程同上实施例1.2。图8是本实施例合成的Fe2O3的SEM图片，从图中可以看出，所得Fe2O3为纺锤形，平均长度为1500nm；7.2 The washing process of the sample is the same as in Example 1.2 above. Fig. 8 is the SEM picture of Fe 2 O 3 synthesized in this example, it can be seen from the figure that the obtained Fe 2 O 3 is spindle-shaped with an average length of 1500 nm;
7.3样品的制备及洗涤过程同上实施例1.3、1.4，图9是本实施例合成的Fe2O3@SiO2的TEM照片，从图中可以看出，所得Fe2O3@SiO2为核壳结构，SiO2壳层厚度为22nm。7.3 The preparation and washing process of the sample are the same as those in Examples 1.3 and 1.4 above. Figure 9 is a TEM photo of Fe 2 O 3 @SiO 2 synthesized in this example. It can be seen from the figure that the obtained Fe 2 O 3 @SiO 2 is the core Shell structure, SiO2 shell thickness is 22nm.
7.4分子筛的制备及洗涤过程同上实施例1.5、1.6，费托反应条件同上实施例4.2。7.4 The preparation and washing process of molecular sieves are the same as those in Examples 1.5 and 1.6 above, and the Fischer-Tropsch reaction conditions are the same as those in Example 4.2 above.
实施例8Example 8
8.1样品的制备及洗涤过程同上实施例1.1、1.2。8.1 The preparation and washing process of the samples are the same as those in Examples 1.1 and 1.2 above.
8.2将0.5g Fe2O3分散于300mL无水乙醇中，同时将1.5ml正硅酸四乙酯加入无水乙醇溶液中，常温搅拌3h，把5ml氨水和20ml水加入上述溶液中，继续搅拌4h；8.2 Disperse 0.5g Fe 2 O 3 in 300mL absolute ethanol, at the same time add 1.5ml tetraethyl orthosilicate into the absolute ethanol solution, stir at room temperature for 3h, add 5ml ammonia water and 20ml water to the above solution, continue stirring 4h;
8.3样品的洗涤过程同上实施例1.4，图10是本实施例合成的Fe2O3@SiO2的TEM8.3 The washing process of the sample is the same as in Example 1.4 above, and Figure 10 is the TEM of Fe 2 O 3 @SiO 2 synthesized in this example
照片，从图中可以看出，所得Fe2O3@SiO2为核壳结构，SiO2壳层厚度为66nm。Photo, it can be seen from the figure that the obtained Fe 2 O 3 @SiO 2 has a core-shell structure, and the thickness of the SiO 2 shell is 66 nm.
8.4分子筛的制备及洗涤过程同上实施例1.5、1.6，费托反应条件同上实施例4.2。8.4 The preparation and washing process of molecular sieves are the same as those in Example 1.5 and 1.6 above, and the Fischer-Tropsch reaction conditions are the same as those in Example 4.2 above.
实施例9Example 9
9.1样品的制备及洗涤过程同上实施例1.1、1.2。9.1 The preparation and washing process of the samples are the same as those in Examples 1.1 and 1.2 above.
9.2将0.5g Fe2O3分散于300mL无水乙醇中，同时将2.0ml正硅酸四乙酯加入无水乙醇溶液中，常温搅拌3h，把5ml氨水和20ml水加入上述溶液中，继续搅拌4h；9.2 Disperse 0.5g Fe 2 O 3 in 300mL absolute ethanol, at the same time add 2.0ml tetraethyl orthosilicate into the absolute ethanol solution, stir at room temperature for 3h, add 5ml ammonia water and 20ml water to the above solution, continue stirring 4h;
9.3样品的洗涤过程同上实施例1.4，图11是本实施例合成的Fe2O3@SiO2的TEM9.3 The washing process of the sample is the same as in Example 1.4 above, and Figure 11 is the TEM of Fe 2 O 3 @SiO 2 synthesized in this example
照片，从图中可以看出，所得Fe2O3@SiO2为核壳结构，SiO2壳层厚度为48nm。Photo, it can be seen from the figure that the obtained Fe 2 O 3 @SiO 2 has a core-shell structure, and the thickness of the SiO 2 shell is 48 nm.
9.4分子筛的制备及洗涤过程同上实施例1.5、1.6，费托反应条件同上实施例4.2。9.4 The preparation and washing process of molecular sieves are the same as those in Example 1.5 and 1.6 above, and the Fischer-Tropsch reaction conditions are the same as those in Example 4.2 above.
实施例10Example 10
10.1将2g六水氯化铁和1g无水乙酸铵溶于30mL去离子中，搅拌并加入1g十六烷基三甲基溴化铵，然后置于180℃水热反应釜中反应8h。10.1 Dissolve 2g of ferric chloride hexahydrate and 1g of anhydrous ammonium acetate in 30mL of deionized water, stir and add 1g of cetyltrimethylammonium bromide, and then place it in a 180°C hydrothermal reactor for 8h reaction.
10.2样品的洗涤过程同上实施例1.2。本实施例中Fe2O3为分级多孔微球，平均直径为300nm。10.2 The washing process of the sample is the same as in Example 1.2 above. In this embodiment, Fe 2 O 3 is a graded porous microsphere with an average diameter of 300 nm.
10.3样品的制备及洗涤过程同上实施例1.3、1.4，所得SiO2壳层厚度为5nm。10.3 The preparation and washing process of the sample are the same as those in Examples 1.3 and 1.4 above, and the thickness of the obtained SiO 2 shell is 5 nm.
10.4分子筛的制备及洗涤过程同上实施例1.5、1.6。10.4 The preparation and washing process of molecular sieve are the same as those in Examples 1.5 and 1.6 above.
10.5将0.5gFe2O3@SiO2与0.3g分子筛物理混合后，压片造粒，然后置于固定床反应器中，并在300℃、2MPa、流速为2000mlh-1gcat -1、1:1的合成气(H2/CO)氛围中进行反应，得芳香烃。10.5 After physical mixing of 0.5g Fe 2 O 3 @SiO 2 and 0.3g molecular sieve, tableting and granulation, and then placed in a fixed bed reactor, and at 300°C, 2MPa, and a flow rate of 2000mlh -1 g cat -1 , 1 : 1 synthesis gas (H 2 /CO) atmosphere for the reaction to obtain aromatic hydrocarbons.
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