CN113083371A - Phosphotungstic acid loaded iron-based MOF material and preparation and application thereof - Google Patents
Phosphotungstic acid loaded iron-based MOF material and preparation and application thereof Download PDFInfo
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- CN113083371A CN113083371A CN202110444752.7A CN202110444752A CN113083371A CN 113083371 A CN113083371 A CN 113083371A CN 202110444752 A CN202110444752 A CN 202110444752A CN 113083371 A CN113083371 A CN 113083371A
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- phosphotungstic acid
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- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 34
- 230000023556 desulfurization Effects 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000013144 Fe-MIL-100 Substances 0.000 claims abstract description 19
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003345 natural gas Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 239000003245 coal Substances 0.000 claims abstract 2
- 239000003208 petroleum Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000013291 MIL-100 Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 abstract description 19
- 239000011593 sulfur Substances 0.000 abstract description 19
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000007789 sealing Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011964 heteropoly acid Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 4
- 230000000149 penetrating effect Effects 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WHBHBVVOGNECLV-OBQKJFGGSA-N 11-deoxycortisol Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 WHBHBVVOGNECLV-OBQKJFGGSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical class [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000000407 epitaxy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229940079826 hydrogen sulfite Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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Abstract
The invention discloses a phosphotungstic acid loaded iron-based MOF material, which is prepared by adding phosphotungstic acid into an MOF material precursor solution taking iron salt and 1,3, 5-benzenetricarboxylic acid as raw materials and adopting a hydrothermal synthesis method, wherein the MOF material is prepared by sealing phosphotungstic acid with the MOF materialThe material is filled in an MIL-100(Fe) hole cage, and the load mass percentage of phosphotungstic acid is 20-40%. The phosphotungstic acid loaded iron-based MOF material prepared by the method can be used as a fine desulfurization catalyst to realize H at normal temperature2The selective catalytic oxidation of S solves the problem of the prior medium-high temperature catalytic oxidation H2S is easy to generate sulfur by-products and has high energy consumption, and is suitable for the chemical industry of natural gas, petroleum and coal containing H2And (4) fine removal treatment of S gas.
Description
Technical Field
The invention belongs to the technical field of fine desulfurization, and relates to a normal-temperature fine desulfurizing agent, in particular to a normal-temperature fine desulfurizing agent based on an iron-based metal organic framework material, and a preparation method and application of the normal-temperature fine desulfurizing agent.
Background
Fossil raw materials mainly comprising coal, petroleum and natural gas are important basic energy sources in China, however, the fossil energy sources all contain H2The sulfur-containing compounds mainly containing S not only corrode pipelines and equipment, but also poison catalysts in downstream processes, and have great influence on chemical production; the sulfide enters the air and can seriously affect the health of human bodies, such as high-concentration H2S can suffocate people, and high-concentration dimethyl sulfide can paralyze nerves and the like; at the same time, these sulfur compounds are converted to SO during high temperature combustion2，SO2Acid rain can be formed when tail gas enters the atmospheric environment, so that buildings and open-air devices are corroded, and water resources and agriculture and forestry resources are seriously damaged. In view of the great influence of sulfur-containing compounds on the production process, it is very important how to achieve better desulfurization.
The Claus process is the most widely used desulfurization technique in the process. But subject to thermodynamic limitations, the process is only suitable for high concentrations of H2S treatment, and 3-5% of H still remains in tail gas2The S content.
The selective catalytic oxidation is a desulfurization method with good development prospect, environmental protection, economy and excellent performance. TheThe method is to use H2S and the component with oxidability are directly reacted and oxidized to generate elemental sulfur, thereby realizing the recycling of sulfur resources.
The selective catalytic oxidation process is mainly accompanied by the following reactions:
H2S+1/2O2→1/n Sn+H2O 1）；
1/n Sn+ O2→SO2 2）；
H2S+3/2O2→SO2+H2O 3）。
wherein 1) is the main reaction, 2) and 3) are SO obtained after deep oxidation2And (4) a byproduct.
SO2The formation of by-products greatly reduces the selectivity of selective catalytic oxidation, so it is extremely important to select a suitable catalyst in the process. Carbon materials and metal oxide materials are currently receiving much attention in the field of selective catalytic oxidation.
Xinchen Wang et al (N-Rich Carbon Catalysts with economical Feasibility for the Selective Oxidation of Hydrogen Sulfide to Sulfide [ J]. Environmental Science &Technology 2020, 54(19): 12621-2And S. The abundant pyridine nitrogen active sites in the material promote H2The adsorption and the desorption of S realize the conversion rate of 99 percent and the ultrahigh selectivity of more than 95 percent under the condition of 180 ℃.
Á lvanoReyes-Carmona et al (Iron-stabilizing SBA-15 as catalyst for partial oxidation of hydrogen sulfite [ J)]Catalysis today, 2013, 210: 117-xMaterials and their use in H2The selective catalytic oxidation of S, the form of iron present being mainly determined by the Si/Fe ratio (isolated Fe)3+Elemental, additional framework iron oligomers or aggregated iron oxide clusters). At H2S/air/He =1.2/5.0/93.8, H2The S conversion decreases with increasing iron content, at 200SBA-Fe at DEG C590% of H can be obtained2S conversion and sulfur selectivity of nearly 99%. The catalyst deactivation is mainly due to the presence of sulfate.
The metal organic framework Materials (MOFs) are novel materials composed of organic ligands and inorganic metal center clusters, have the characteristics of large specific surface area, high porosity, easy adjustment, easy modification and the like, and are easy for uniform loading of other materials. Meanwhile, the MOFs material has abundant and dispersed metal center active sites, especially some MOFs materials with variable valence, and is an ideal material for selective catalytic oxidation.
Jianellong et al (Iron-Based Metal-Organic Frameworks as Platform for H)2S Selective Conversion: Structure-Dependent Desulfurization Activity[J]Inorganic Chemistry 2020, 59(7): 4483-4492) reported three classes of Fe-MOFs that were investigated for their selective catalytic oxidation of H2The structure activity relation and the catalytic mechanism of S show that MIL-100(Fe) has the highest catalytic activity. This is strongly related to the number of Lewis acid sites on the surface of different Fe-MOF species, Fe3+Can adsorb H2S is directly oxidized to generate simple substance S and Fe3+Is reduced to Fe2+，Fe2+Reacting with oxygen free radicals to make Fe3+Regeneration thereby allowing for cyclic catalytic oxidation.
However, as far as the present research is concerned, the research on selective catalytic oxidation is mainly focused on medium and high temperatures. Very easy to make H at this temperature2Deep oxidation of S to SO2And byproducts such as COS and the like, greatly reduce the selectivity of S, and simultaneously avoid secondary environmental pollution and influence on industrial production. Therefore, the reaction temperature is reduced, and the desulfurization is realized under the normal temperature condition to avoid SO2Etc. to achieve 100% sulfur selectivity, is desirable and necessary.
However, the performance of the MOFs material as a catalyst under normal temperature is not ideal, probably because oxygen is relatively stable and not easily activated in the reaction process, and H is simultaneously used as a catalyst2S is not easy to dissociate or react with metal active sites at normal temperatureFor this reason, the selective oxidation activity of the MOFs is low.
The heteropoly acid (HPA) is oxygen-containing polyacid which is bridged by heteroatoms and polyatomic atoms through oxygen atom coordination according to a certain structure, and is a bifunctional green catalyst with both acid-base property and oxidation-reduction property. The method has less related research on removing hydrogen sulfide by using heteropoly acid and is mainly used for a solution absorption method, and the process is extremely easy to corrode equipment, has high energy consumption and can cause secondary pollution.
Research on desulfurization performance of phosphotungstic acid (HPW), and theoretical analysis and experimental research on removal of hydrogen sulfide by heteropoly acid [ C]The very early chemical engineering science and technology report of the ninth national chemical engineering society 1998) showed that the reaction rate was not high initially for the single heteropolyacid system, and therefore the tail gas H2The S concentration increases rapidly with time, the reaction thereafter accelerates, and the tail gas H rises for a long period of time2The S concentration is reduced until reaching a minimum value, and then begins to rise, so the desulfurization precision of the process is very low, and tail gas is inevitably accompanied by H2And (4) releasing S.
In fact, the oxygen-containing polyacid abundant in the heteropoly acid is likely to provide a good oxygen source for selective catalytic oxidation, and the combined acidity and basicity and redox have a promoting effect on oxygen activation. In view of the above, the development of the double-component phosphotungstic acid loaded MOFs catalyst can effectively improve H2The selective catalytic oxidation performance of S can not only improve the conversion rate, but also greatly improve the selectivity of sulfur, and is a significant research.
Disclosure of Invention
The invention aims to provide a phosphotungstic acid loaded iron-based MOF material which is used as a fine desulfurization catalyst to realize H at normal temperature2The selective catalytic oxidation of S solves the problem of the prior medium-high temperature catalytic oxidation H2S is easy to generate sulfur by-products and has high energy consumption.
The invention provides a simple and efficient preparation method of the phosphotungstic acid loaded iron-based MOF material, which is another invention purpose of the invention.
The phosphotungstic acid loaded iron-based MOF material is an MOF material prepared by adding phosphotungstic acid into an MOF material precursor solution which takes iron salt and 1,3, 5-benzenetricarboxylic acid as raw materials and adopting a hydrothermal synthesis method, wherein the MOF material encapsulates the phosphotungstic acid in a pore cage of MIL-100(Fe), and the loading mass percentage of the phosphotungstic acid is 20-40%.
The invention selects representative MIL-100(Fe) as the iron-based MOF material loaded with phosphotungstic acid, is based on that the MOF material has a quite large pore structure and pore volume, contains abundant unsaturated metal sites and can be used as an active component of a catalyst, and meanwhile, the synthesis method of the material is simple and the yield is high.
Further, the invention also provides a preparation method of the phosphotungstic acid loaded iron-based MOF material, which comprises the steps of adding 1,3, 5-benzenetricarboxylic acid into a soluble iron salt aqueous solution to obtain a mixed solution, adding phosphotungstic acid into the mixed solution according to the loading mass percentage of the phosphotungstic acid being 20-40%, heating for hydrothermal synthesis reaction, and preparing the phosphotungstic acid loaded iron-based MOF material HPW-MIL-100 (Fe).
Specifically, the hydrothermal synthesis reaction is carried out at 120-160 ℃, and the hydrothermal synthesis reaction time is 12-36 h.
More specifically, the hydrothermal synthesis reaction of the present invention is preferably carried out at 150 ℃ for 24 hours.
The phosphotungstic acid loaded iron-based MOF material prepared by the invention can be used as a fine desulfurization catalyst for H at normal temperature2Selective catalytic oxidation of S.
According to the invention, a certain amount of phosphotungstic acid is added into a precursor solution for preparing the iron-based MOF material, and the phosphotungstic acid loaded iron-based MOF material is prepared by one step through a one-pot method, so that the prepared MOF material has an ultra-high pore structure, rich Fe Lewis acidic sites and highly dispersed phosphotungstic acid active components, and has excellent selective catalytic oxidation H under the normal temperature condition2The performance of S.
The phosphotungstic acid loaded iron-based MOF material is used as a fine desulfurization catalyst, phosphotungstic acid provides an active center, MOF is used as a metal organic framework material, rich Fe Lewis acid sites are provided, a large specific surface area and a large pore volume are provided for the phosphotungstic acid, and the high dispersion of the phosphotungstic acid is realized. The Fe-MOF structure of the phosphotungstic acid loaded catalyst is more stable, and a small amount of loaded catalyst increases the specific surface area and pore volume of the catalyst, thereby providing space for storing more elemental S.
Loading phosphotungstic acid on Fe-MOF, and catalytically oxidizing H by the combined action of the phosphotungstic acid and the Fe-MOF2And S has the function of mutual complementation, and forms excellent catalytic oxidation performance. The appropriate amount of phosphotungstic acid active components can coordinate with unsaturated metal centers and complement each other to jointly improve selective catalytic oxidation H2Activity of S.
Furthermore, soluble iron salt is selected to replace Fe powder and nitric acid as synthesis raw materials of the MOF material, and hydrofluoric acid is not added in the synthesis process for adjustment, so that pollution is reduced, and after the adjustment effect of the hydrofluoric acid is cancelled, the obtained MOF structure generates more mesopores and defects in the spontaneous growth process, and the loading and catalysis are facilitated.
The invention uses phosphotungstic acid loaded iron-based MOF material as a fine desulfurization catalyst for H at normal temperature2S is selectively catalyzed and oxidized, and the generated simple substance S can be well stored in a pore cage structure of the MOF, so that the recovery and the utilization are convenient, and the secondary pollution is reduced.
The phosphotungstic acid loaded iron-based MOF material prepared by the invention is mainly used for H in industrial processes of coal gas, natural gas and the like2The S gas is finely removed, the penetrating sulfur capacity can reach more than 50mg S/g, and the catalyst has better normal-temperature selective catalytic oxidation desulfurization performance.
Drawings
FIG. 1 is an XRD spectrum of phosphotungstic acid loaded iron-based MOF materials with different mass percentages.
FIG. 2 shows N of iron-based MOF materials loaded with phosphotungstic acid in different mass percentages2Adsorption-desorption isotherm diagram.
FIG. 3 is a graph of pore size distribution for different mass percent phosphotungstic acid loaded iron-based MOF materials.
FIG. 4 is a graph of the penetration curves of different mass percent phosphotungstic acid loaded iron-based MOF materials.
Detailed Description
The following describes in detail a specific embodiment of the present invention with reference to the drawings, examples and comparative examples. The following examples and comparative examples are only for more clearly illustrating the technical aspects of the present invention so that those skilled in the art can well understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment related to the examples and comparative examples of the present invention are all conventional names in the art, and are clearly and clearly understood in the related fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names, and implement the process according to the conventional conditions or the conditions suggested by the manufacturers.
The various starting materials and reagents used in the examples and comparative examples of the present invention are not particularly limited in terms of their sources, and are all conventional products commercially available.
The selective catalytic oxidation performance of the fine desulfurization catalysts of the examples and comparative examples was tested using a dynamic fixed bed experimental apparatus. The specific operation process is as follows: and (3) taking a proper amount of fine desulfurization catalyst, and filling the fine desulfurization catalyst into a U-shaped tube reactor with the inner diameter of 6mm, wherein the filling height is 2 cm. Before the experiment is started, the fine desulfurization catalyst is purged at the high temperature of 150 ℃ for 12 hours by using nitrogen to remove residual micromolecules in the structure of the fine desulfurization catalyst. Then H is introduced2S and N2Introducing the mixed gas into the U-shaped tube reactor, and adjusting the gas inlet H2S concentration 800mg/m3The gas flow rate is 100ml/min, the reaction temperature is 30 ℃, and the reaction pressure is normal pressure.
Record the outlet gas H at different times2The concentration of S. When detecting the gas outlet H2S concentration is 1% of the inlet concentration, namely the outlet H2The S concentration is 8mg/m3And (3) considering the penetration of the fine desulfurization catalyst, and calculating the penetration sulfur capacity Q of the fine desulfurization catalyst according to the following formula.
Wherein:Nwhich is representative of the gas flow rate,C inandC outh representing inlet and outlet ports, respectively2The concentration of the S gas is controlled by the concentration of the S gas,mrepresenting the quality of the fine desulfurization catalyst.
Example 1.
3.03g of iron nitrate nonahydrate was weighed, added to 37.5ml of deionized water, stirred at room temperature to dissolve, and then 1.05g of 1,3, 5-benzenetricarboxylic acid was added thereto, and stirred at room temperature to obtain a mixed solution.
Weighing 0.816g of phosphotungstic acid, adding the phosphotungstic acid into the mixed solution, stirring the solution uniformly at room temperature, transferring the solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle in a forced air drying oven at 150 ℃ for 24 hours.
Cooling to room temperature after the reaction is finished, taking out a reaction product, performing suction filtration, washing with deionized water for three times until the supernatant is colorless and clear, soaking the precipitate in absolute ethyl alcohol for 4 hours, taking out the precipitate and drying at 80 ℃ to obtain the fine desulfurization catalyst HPW20MIL-100(Fe) samples.
The specific surface area and total pore volume of prepared fine desulfurization catalyst were 1039 m/g, and were obtained by thin film epitaxy at a height of 0.75cm, respectively, wherein the micropore volume was 0.298cm and the mesopore volume was 0.44cm, respectively. After testing, when H2When the outlet concentration of S is 1% of the inlet concentration, the breakthrough sulfur capacity is 70.73mg S/g, and the sulfur capacity is increased by 11.5 times as compared with comparative example 1.
Example 2.
3.03g of iron nitrate nonahydrate was weighed, added to 37.5ml of deionized water, stirred at room temperature to dissolve, and then 1.05g of 1,3, 5-benzenetricarboxylic acid was added thereto, and stirred at room temperature to obtain a mixed solution.
Weighing 1.224g of phosphotungstic acid, adding the phosphotungstic acid into the mixed solution, stirring the mixture evenly at room temperature, transferring the mixture into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle in a forced air drying oven at 150 ℃ for 24 hours.
Cooling to room temperature after reaction, taking out reaction product, vacuum filtering, washing with deionized water for three times until the supernatant is colorless and clear, soaking the precipitate in anhydrous ethanol for 4h, taking out the precipitate, and cooling to 80 deg.CDrying to obtain the fine desulfurization catalyst HPW30MIL-100(Fe) samples.
The specific surface area and total pore volume of the prepared fine desulfurization catalyst were 922 m/g, and were obtained by thin film epitaxy, wherein the micropore volume was 0.29cm and the mesopore volume was 0.29 cm. After testing, when H2When the outlet concentration of S is 1% of the inlet concentration, the breakthrough sulfur capacity is 92.09mg S/g. The sulfur capacity was improved by 14.7 times as compared with comparative example 1.
Example 3.
3.03g of iron nitrate nonahydrate was weighed, added to 37.5ml of deionized water, stirred at room temperature to dissolve, and then 1.05g of 1,3, 5-benzenetricarboxylic acid was added thereto, and stirred at room temperature to obtain a mixed solution.
1.632g of phosphotungstic acid is weighed and added into the mixed solution, the mixed solution is stirred uniformly at room temperature, the mixture is transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and the reaction kettle is heated and reacted for 24 hours in a forced air drying oven at 150 ℃.
Cooling to room temperature after the reaction is finished, taking out a reaction product, performing suction filtration, washing with deionized water for three times until the supernatant is colorless and clear, soaking the precipitate in absolute ethyl alcohol for 4 hours, taking out the precipitate and drying at 80 ℃ to obtain the fine desulfurization catalyst HPW40MIL-100(Fe) samples.
The specific surface area and total pore volume of the prepared fine desulfurization catalyst were respectively and respectively obtained by performing thin film chemical vapor deposition and vacuum evaporation on the obtained thin film chemical vapor deposition, wherein the micropore volume was 0.26cm and 0.31cm respectively. After testing, when H2When the outlet concentration of S is 1% of the inlet concentration, the penetrating sulfur capacity is 54.2mg S/g, and the sulfur capacity is improved by 8.6 times compared with that of comparative example 1.
Comparative example 1.
3.03g of iron nitrate nonahydrate was weighed, added to 37.5ml of deionized water, stirred at room temperature to dissolve, and then 1.05g of 1,3, 5-benzenetricarboxylic acid was added thereto, and stirred at room temperature to obtain a mixed solution.
And transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, and heating the reaction kettle in an air-blast drying oven at 150 ℃ for 24 hours.
And cooling to room temperature after the reaction is finished, taking out a reaction product, performing suction filtration, washing with deionized water for three times until the supernatant is colorless and clear, soaking the precipitate in absolute ethyl alcohol for 4 hours, taking out the precipitate, and drying at 80 ℃ to obtain an MIL-100(Fe) sample.
The specific surface area of the prepared MIL-100(Fe) sample was 981 m/g, total pore volume was 0.79cm thin ethers/g, wherein micropore volume was 0.24cm thin ethers/g, and mesopore volume was 0.52cm thin ethers/g. After testing, when H2When the outlet concentration of S is 1 percent of the inlet concentration, the penetrating sulfur capacity is only 6.28mg S/g, and the desulfurization effect is poor.
Comparative example 2.
Directly weighing phosphotungstic acid solid particles with a certain mass, filling the phosphotungstic acid solid particles into a U-shaped tube reactor with the inner diameter of 6mm, and testing the dynamic desulfurization performance of the fixed bed, wherein the filling height is 2 cm. The results show that the solid phosphotungstic acid has almost no desulfurization performance, and the sample reaches the penetrating sulfur capacity almost instantly after being placed.
In order to clearly compare the performance difference between the examples and the comparative examples, the results of the specific performance tests are summarized in table 1. It can be seen that the sulfur capacity of the iron-based MOF material loaded with phosphotungstic acid with different mass percentage contents is remarkably improved, the material shows a trend of increasing firstly and then reducing, and the effect is optimal when the phosphotungstic acid loading capacity is 30%. It can also be seen from table 1 that a small amount of phosphotungstic acid is preferentially loaded in the mesopores, and the change of the micropore volume is not obvious; when the loading amount of the phosphotungstic acid exceeds 30%, the micropores of the MOF material are obviously reduced, which shows that the excessive phosphotungstic acid loading can occupy the pore channels of the micropores to block the structure, and the reason is that the performance of the excessive phosphotungstic acid loading is reduced.
FIG. 1 is an XRD spectrum of MIL-100(Fe) loaded with phosphotungstic acid with different mass percentages. As can be seen, the XRD diffraction peak positions of MIL-100(Fe) are mainly concentrated at the positions of 3.4, 4.0, 5.3, 10.3, 11.0 and the like, which are all characteristic positions of MIL-100(Fe), and the fact that the MIL-100(Fe) can be prepared well by replacing iron powder with ferric nitrate and eliminating nitric acid and hydrofluoric acid is proved. The diffraction peak position is almost unchanged by adding 20% of phosphotungstic acid, which shows that the crystal structure of the material is not changed by a small amount of phosphotungstic acid load, while when the phosphotungstic acid load reaches 40%, part of the diffraction peaks are obviously changed, wherein the peak positions of 4.0 and 10.3 are almost disappeared, which shows that the crystal structure of the material is probably influenced by excessive phosphotungstic acid load, which is probably caused by excessive phosphotungstic acid agglomeration or structural damage.
FIG. 2 is a nitrogen adsorption isotherm of different mass percent phosphotungstic acid loaded MIL-100 (Fe). In the figure, MIL-100(Fe) and phosphotungstic acid loaded MIL-100(Fe) both have typical type I and type IV adsorption isotherms, which show that both micropores and mesopores exist in the material, and the micropores are mainly used. It can be seen that a small amount of phosphotungstic acid loading has little effect on the specific surface area of the material, but 40% of phosphotungstic acid loading decreases the specific surface area.
FIG. 3 is a distribution diagram of pore diameters of MIL-100(Fe) loaded with phosphotungstic acid with different mass percentages, and it can be seen that micropores and mesopores in the MIL-100(Fe) structure are widely distributed. It is worth noting that the influence of 20% and 30% phosphotungstic acid load on micropores changes little, the mesoporous changes greatly, which indicates that a small amount of phosphotungstic acid is mainly loaded in the mesopores, while the micropore is reduced when the 40% phosphotungstic acid load is compared with the 20% and 30% load, which indicates that the micropores are occupied by excessive phosphotungstic acid. A small amount of phosphotungstic acid is uniformly distributed in and on the mesoporous pore canal of the MOF, so that the active sites and the specific surface area are enlarged, and the catalytic performance of the MOF is improved; and the excessive phosphotungstic acid load can lead the phosphotungstic acid and the metal active sites to agglomerate, reduce the utilization rate of the active sites, and simultaneously reduce the storage volume of the generated simple substance S, thereby reducing the catalytic performance.
FIG. 4 is a penetration curve diagram of different mass percent contents of phosphotungstic acid loaded MIL-100(Fe), and it can be seen that the addition of phosphotungstic acid can effectively improve the desulfurization catalytic performance. With the increase of the addition amount of the phosphotungstic acid, the performance shows a trend of increasing first and then decreasing, which shows that the loading amount of the phosphotungstic acid has a large influence on the catalytic performance, and the performance is best when the loading amount is 30%. This is because the loading of 30% will not cause the blocking of MOF pore channels and the aggregation of active sites, and can coordinate the coordination of phosphotungstic acid and metal active center, so the performance is the best.
The above comparative examples and embodiments are only for more clearly illustrating the technical solutions of the present invention, so as to enable those skilled in the art to better understand and utilize the present invention, and do not limit the protection scope of the present invention. Various changes, modifications and alterations to these embodiments will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
Claims (5)
1. A phosphotungstic acid loaded iron-based MOF material is prepared by adding phosphotungstic acid into an MOF material precursor solution which takes iron salt and 1,3, 5-benzenetricarboxylic acid as raw materials, and encapsulating the phosphotungstic acid in an MIL-100(Fe) pore cage by adopting a hydrothermal synthesis method, wherein the phosphotungstic acid is loaded with the MOF material with the mass percentage of 20-40%.
2. The preparation method of the phosphotungstic acid loaded iron-based MOF material as claimed in claim 1, adding 1,3, 5-benzenetricarboxylic acid into a soluble iron salt aqueous solution to obtain a mixed solution, adding phosphotungstic acid into the mixed solution according to the loading mass percentage of the phosphotungstic acid being 20-40%, heating for hydrothermal synthesis reaction, and preparing to obtain the phosphotungstic acid loaded iron-based MOF material HPW-MIL-100 (Fe).
3. The preparation method according to claim 2, wherein the hydrothermal synthesis reaction temperature is 120-160 ℃ and the hydrothermal synthesis reaction time is 12-36 h.
4. The phosphotungstic acid supported iron-based MOF material of claim 1 as H at room temperature2The application of S selective catalytic oxidation fine desulfurization catalyst.
5. The phosphotungstic acid supported iron-based MOF material as claimed in claim 1, which contains H as a fine desulfurization catalyst in the chemical industries of natural gas, petroleum and coal2The application in S gas fine removal.
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